CN113045093A - Treatment method of graphite product production wastewater - Google Patents
Treatment method of graphite product production wastewater Download PDFInfo
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- CN113045093A CN113045093A CN202110297003.6A CN202110297003A CN113045093A CN 113045093 A CN113045093 A CN 113045093A CN 202110297003 A CN202110297003 A CN 202110297003A CN 113045093 A CN113045093 A CN 113045093A
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- 239000002351 wastewater Substances 0.000 title claims abstract description 70
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000010439 graphite Substances 0.000 title claims abstract description 53
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 53
- 238000011282 treatment Methods 0.000 title claims abstract description 51
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000001914 filtration Methods 0.000 claims abstract description 19
- 238000001704 evaporation Methods 0.000 claims abstract description 13
- 230000008020 evaporation Effects 0.000 claims abstract description 13
- 238000010612 desalination reaction Methods 0.000 claims abstract description 10
- 239000006004 Quartz sand Substances 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000009287 sand filtration Methods 0.000 claims abstract description 3
- 239000010802 sludge Substances 0.000 claims description 21
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 20
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 20
- 239000004571 lime Substances 0.000 claims description 20
- 239000008267 milk Substances 0.000 claims description 20
- 210000004080 milk Anatomy 0.000 claims description 20
- 235000013336 milk Nutrition 0.000 claims description 20
- 239000000047 product Substances 0.000 claims description 19
- 239000001110 calcium chloride Substances 0.000 claims description 13
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 238000005345 coagulation Methods 0.000 claims description 11
- 230000015271 coagulation Effects 0.000 claims description 11
- 238000006115 defluorination reaction Methods 0.000 claims description 11
- 238000005189 flocculation Methods 0.000 claims description 11
- 230000016615 flocculation Effects 0.000 claims description 11
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 238000011033 desalting Methods 0.000 claims description 6
- 238000011221 initial treatment Methods 0.000 claims description 6
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000013505 freshwater Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 239000008394 flocculating agent Substances 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 2
- 238000004065 wastewater treatment Methods 0.000 abstract description 5
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- 238000004062 sedimentation Methods 0.000 description 14
- 239000012528 membrane Substances 0.000 description 11
- 239000002253 acid Substances 0.000 description 9
- 229920002401 polyacrylamide Polymers 0.000 description 8
- 239000003814 drug Substances 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- -1 fluorine ions Chemical class 0.000 description 4
- 238000012423 maintenance Methods 0.000 description 4
- 239000003595 mist Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007770 graphite material Substances 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000013535 sea water Substances 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000000701 coagulant Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000003403 water pollutant Substances 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 238000002306 biochemical method Methods 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007728 cost analysis Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000009285 membrane fouling Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/121—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering
- C02F11/122—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering using filter presses
-
- 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
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Sorption (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
本发明属于废水处理技术领域，具体涉及一种石墨产品生产废水的处理方法，所述处理方法包括预处理、脱盐处理；所述预处理依次包括石灰乳反应、除氟反应、混凝反应、絮凝反应、石英砂过滤、活性炭过滤步骤；所述脱盐处理依次包括三级反渗透处理、MVR蒸发步骤；所述反渗透处理前包括保安过滤，采用本发明方法处理石墨生产废水，达到了出水水质稳定、各项污染物均达到排放标准，水质达GB 3838‑2002的Ⅳ类标准和GB 30484‑2013的直接排放标准。
The invention belongs to the technical field of wastewater treatment, and in particular relates to a method for treating waste water from graphite product production. The steps of reaction, quartz sand filtration, and activated carbon filtration; the desalination treatment sequentially includes three-stage reverse osmosis treatment and MVR evaporation steps; before the reverse osmosis treatment, security filtration is included, and the method of the invention is used to treat the graphite production waste water, so as to achieve stable effluent water quality , All pollutants have reached the discharge standard, and the water quality has reached the Class IV standard of GB 3838‑2002 and the direct discharge standard of GB 30484‑2013.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a treatment method of graphite product production wastewater.
Background
China has abundant graphite resources, in order to improve the use value of graphite, the current deep processing technology of graphite is not much developed, and graphite products mainly comprise medium-carbon and high-carbon natural crystalline flake graphite, graphite electroplates, high-purity spherical graphite, graphite battery negative electrode materials and the like.
With the development of graphite deep processing technology, the environmental pollution is increased, and in the graphite processing technology, strong acid such as hydrofluoric acid, hydrochloric acid, nitric acid or sulfuric acid is generally adoptedThe graphite is purified by acid washing and sprayed with acid mist, which causes impurity reaction to generate soluble compounds such as NaCl, KCl and CaCl2、MgCl2、FeCl3、NaNO3、KNO3、Ca(NO3)2、Mg(NO3)2、Fe(NO3)3、Na2SO4、K2SO4、CaSO4、MgSO4、Fe2(SO4)3The high-salinity wastewater is formed by NaF, KF and the like, the wastewater produced by graphite is high in salt content and strong in acidity, so that the wastewater cannot be treated by a biochemical method, and the problems of membrane fouling and thick water treatment exist in a reverse osmosis process, electrodialysis and an ion exchange method.
Patent CN109133406A discloses a graphite production wastewater treatment system, which comprises a sewage collection tank, which is connected with an adjusting tank, a first sedimentation tank, a second sedimentation tank, a buffer tank and a reuse water tank in sequence through a pipeline and a pump, wherein a sedimentation inclined pipe is installed in the first sedimentation tank, and an air flotation device is installed in the second sedimentation tank; the bottoms of the regulating tank, the first sedimentation tank and the second sedimentation tank are all connected to a sludge concentration tank, a sludge dewatering device is further installed at the sludge concentration tank, and lime milk and a PAC coagulant are added into the regulating tank through the arrangement of the regulating tank, so that the content of fluoride in the wastewater is favorably reduced; simultaneously, the pH value is increased; and adding PAC coagulant and PAM flocculant into the first sedimentation tank and the second sedimentation tank to further remove fluorine ions in the wastewater and reduce the SS value of the wastewater. The first sedimentation tank is internally provided with a sedimentation inclined pipe, so that the sedimentation speed is increased, and the processing capacity of the sedimentation tank is enhanced. Set up the air supporting device in the second sedimentation tank, the aquatic lets in the air, produces fine bubble, makes the tiny suspended solid of aquatic adhere on the air bubble, goes up to the surface of water along with the bubble, forms the dross, reaches the purpose of getting rid of aquatic suspended solid, improvement quality of water. However, the method has the following disadvantages: 1) the desalting effect is not ideal; 2) the scum is difficult to treat and is easy to cause secondary pollution. Therefore, the method for treating the waste water generated in the production of graphite products is still worth of deep research.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for treating waste water produced in graphite product production.
The method is realized by the following technical scheme:
a treatment method of graphite product production wastewater comprises pretreatment and desalination treatment; the pretreatment sequentially comprises the steps of lime milk reaction, defluorination reaction, coagulation reaction, flocculation reaction, quartz sand filtration and active carbon filtration; the desalting treatment sequentially comprises three stages of reverse osmosis treatment and MVR evaporation; the reverse osmosis treatment comprises security filtration.
The lime milk reacts, and the used medicaments are lime milk and calcium chloride.
The lime milk is 148-3Waste water from graphite production.
The dosage of the calcium chloride is 48-53kg/1028m3Waste water from graphite production.
A treatment method of graphite product production wastewater comprises the following steps:
first step of pretreatment
S1.1, feeding the production wastewater into a lime milk reaction tank, adding lime milk and calcium chloride, stirring for reaction, adjusting the pH of the production wastewater to 6-9 to generate sludge and primary treatment liquid, and feeding primary precipitate to a filter press;
s1.2, sequentially adding a defluorinating agent, a flocculating agent and PMA into the primary treatment liquid for defluorination, coagulation and flocculation reactions to obtain sludge and flocculated wastewater, and conveying the sludge to a sludge concentration tank;
s1.3, filtering the flocculated wastewater by quartz sand and activated carbon to obtain pretreated wastewater with the salt content of 7000-;
second step of desalting treatment
S2.1, sequentially carrying out primary security filtration and primary reverse osmosis treatment on the pretreated wastewater, sequentially carrying out secondary security filtration and secondary reverse osmosis treatment on the obtained primary RO concentrated water, sequentially carrying out tertiary security filtration and tertiary reverse osmosis treatment on the obtained secondary RO concentrated water to obtain tertiary RO concentrated water, and simultaneously feeding fresh water obtained by each stage of reverse osmosis into a fresh water tank;
s2.2, feeding the three-level RO concentrated water into an MVR evaporation system for solid-liquid evaporation separation.
The defluorinating agent is any one of phosphate, aluminum sulfate and aluminum salt.
The flocculant is PAC, namely polyaluminium chloride.
The PAM is polyacrylamide.
The dosage of the flocculant is 9-11kg/1028m3Waste water from graphite production.
The dosage of the PAM is 8-10kg/1028m3Waste water from graphite production.
The dosage of the defluorinating agent is 400-500kg/1028m3Waste water from graphite production.
And the salt content of the first-stage RO concentrated water obtained by the first-stage reverse osmosis is 15000-17500 mg/L.
The first-stage reverse osmosis treatment adopts an ultra-low pressure composite RO membrane.
And the salt content of the secondary RO concentrated water obtained by the secondary reverse osmosis is 30000-35000 mg/L.
The second-stage reverse osmosis treatment adopts a seawater desalination membrane.
The salt content of the concentrated water of the third-level RO concentrated water is 60000-70000 mg/L.
Has the advantages that:
the method for treating the graphite production wastewater achieves the purposes that the effluent quality is stable, all pollutants reach the discharge standard, the water quality reaches the IV-class standard of GB 3838-doped 2002 and the direct discharge standard of GB 30484-doped 2013, wherein the TN and SS contents are both lower than the direct discharge limit value of GB 30484-doped 2013, and simultaneously, the wastewater treatment cost and the equipment maintenance cost are greatly reduced.
According to the invention, lime milk and calcium chloride are firstly utilized to carry out stirring reaction with production wastewater, wherein the lime milk can neutralize acid in the wastewater, and meanwhile, the calcium chloride can improve the settling property of calcium fluoride, so that the removal rate of fluoride ions is increased.
The PAC and the defluorinating agent are added, so that the fluoride ions can be further removed, and particularly, when the defluorinating agent contains aluminum sulfate, coprecipitation can be generated, so that more fluoride ions can be removed; and PAM is added at the same time, so that the complex of flocculation and precipitation can carry out coagulation reaction, and suspended matters are effectively removed.
According to the invention, the ultra-low pressure composite reverse osmosis membrane is adopted for primary reverse osmosis treatment, most inorganic salts, organic matters and microorganisms are effectively removed, and the seawater desalination membrane is adopted for secondary reverse osmosis treatment, so that the problems of poor quality of RO produced water, reduced water yield and membrane blockage caused by the conventional reverse osmosis membrane are effectively prevented, and thus, any reverse osmosis membrane material can be used as the tertiary reverse osmosis membrane without being limited, and the service life of the tertiary reverse osmosis membrane is ensured.
The invention adopts the MVR evaporation crystallization device to carry out evaporation crystallization on the RO concentrated solution of the wastewater, separate out the concentrated solution by crystallization and recycle the waste salt of crystallization.
Drawings
FIG. 1: flow chart of pretreatment system in example 3;
FIG. 2: flow chart of desalination treatment System in example 3
Detailed Description
The following is a detailed description of the embodiments of the present invention, but the present invention is not limited to these embodiments, and any modifications or substitutions in the basic spirit of the embodiments are included in the scope of the present invention as claimed in the claims.
Example 1
A treatment method of graphite product production wastewater comprises the following steps:
first step of pretreatment
S1.1 lime milk reaction: feeding the production wastewater into a lime milk reaction tank, adding lime milk and calcium chloride, stirring for reaction, adjusting the pH of the production wastewater to 6-9 to generate sludge and primary treatment liquid, and feeding the sludge to a filter press;
s1.2, defluorination, coagulation and flocculation reaction: conveying the primary treatment liquid to a defluorination reaction tank, adding a defluorination agent for defluorination reaction, conveying sludge obtained by defluorination to a filter press, conveying defluorination waste water to a coagulation reaction tank, adding PAC (polyaluminium chloride) for coagulation reaction, conveying sludge obtained by coagulation to the filter press, conveying coagulation waste water to a flocculation reaction tank, adding PMA (polymethyl methacrylate) for flocculation reaction, conveying sludge obtained by flocculation to a sewage filter press, and overflowing the flocculation waste water into an intermediate water tank;
s1.3, filtering: lifting the flocculated wastewater from the intermediate water tank to a quartz sand filter for filtration treatment, and then carrying out filtration treatment by an activated carbon filter to obtain pretreated wastewater with the concentrated water salt content of 7000-;
s1.4, returning filtrate obtained by sewage treatment by a filter press to an adjusting tank for secondary treatment;
second step of desalting treatment
S2.1, three-level security-reverse osmosis treatment: sequentially carrying out primary security filtration and primary reverse osmosis treatment on the pretreated wastewater, sequentially carrying out secondary security filtration and secondary reverse osmosis treatment on the primary RO concentrated water with the concentrated water salt content of 15000-;
s2.2 MVR evaporation: feeding the three-stage RO concentrated water into an MVR evaporation system for solid-liquid evaporation separation;
the first-stage reverse osmosis adopts an 8-inch ultra-low pressure composite RO membrane;
the second-stage reverse osmosis adopts a seawater desalination membrane.
Example 2
1.1 the method of example 1 is adopted to treat high-salt wastewater generated in the pickling purification and acid mist spraying sections of graphite in 2 ten thousand tons of high-purity graphite and expanded graphite production workshops of a new graphite material company, wherein the high-salt wastewater and the water quality of drainage are shown in table 1:
TABLE 1
Note: indexes such as pH, COD, NH3-N, TP content of the discharged water execute IV standard of GB 3838-2002, indexes such as TN and SS content execute direct discharge standard of water pollutant discharge limit value of newly-built enterprises in GB 30484-2013;
1.2 the dosage of the medicament is as follows: 500kg/d of defluorinating agent (phosphate), 150kg/d of CaO and CaCl250kg/d, PAC 10.0kg/d, PAM 10.0 kg/d;
1.3 operational Effect
The detection conditions of the effluent quality of each step are shown in table 2:
TABLE 2
As can be seen from Table 4, the indexes of the primary RO effluent, the secondary RO effluent and the tertiary RO effluent are all superior to the IV-class standard of GB 3838-plus-2002, wherein the TN and SS contents are both lower than the direct discharge limit of the water pollutants of the newly-built enterprises in Table 3 of GB 30484-plus-2013, and the pollutants can be directly discharged.
Example 3
An operation system of the treatment method of the graphite product production wastewater of the embodiment 1 is built in a certain factory, in particular to a treatment system of the graphite product production wastewater, which comprises a pretreatment and desalination treatment system; the pretreatment system comprises a wastewater adjusting tank, a lime milk reaction tank, a defluorination reaction tank, a coagulation reaction tank, a flocculation reaction tank, an intermediate water tank, a quartz sand filter and an activated carbon filter (detailed as figure 1) which are connected in sequence according to a wastewater conveying route; the desalination treatment system comprises a primary security filter, a primary high-pressure pump, a primary RO device, a primary RO concentrated water tank, a secondary booster pump, a secondary security filter, a secondary high-pressure pump, a secondary RO device, a secondary RO concentrated water tank, a tertiary booster pump, a tertiary security filter, a tertiary high-pressure pump, a tertiary RO device, a concentrated water tank, a concentrated water pump and MVR evaporation which are connected in sequence according to a wastewater conveying route (detailed shown in figure 2);
pretreatment system structures and design parameters are shown in table 3:
TABLE 3
The main components and design parameters of the desalination treatment system are shown in Table 4:
TABLE 4
And (3) cost analysis:
the total investment of the project is 1206 ten thousand yuan, wherein the equipment cost is 554 ten thousand yuan, the civil engineering cost is 500 ten thousand yuan, and other costs (design, installation, debugging and the like) are 152 ten thousand yuan.
And calculating the operation cost (including electricity charge, medicament charge, sludge treatment charge, equipment depreciation charge and maintenance charge).
2) Electric charge: the total installed capacity of the wastewater treatment device is 492.1kw, the operation capacity is 459.4kw, the daily power consumption is 11025.6kw.h, the electricity price is calculated according to 0.8 yuan/(kw.h), the demand coefficient is 0.85, the power consumption cost is 7497.40 yuan/d, and the reduced cost is 27.29 yuan/m3。
3) The cost of the medicament: the dosage according to example 2 amounted to 1200 yuan/d in terms of charge, which was 1.16 yuan/m3。
4) Sludge treatment cost: the calculated sludge yield is 10kg/m3The sludge treatment cost is 900 yuan/t, and the reduced cost is 9.0 yuan/m3。
5) Equipment depreciation cost: equipment depreciation cost (fixed asset original value-expected net residual value)/(expected age of use, month 12). Wherein the original value of the fixed asset is 554 ten thousand yuan; the predicted net residual value is 27.7 ten thousand yuan multiplied by the original value of the fixed asset; the expected usage for 20 years is 21929 yuan per month, and the reduced cost is 0.71 yuan/m3。
6) Maintenance cost: the total investment cost of the equipment is calculated according to 554 ten thousand yuan, the system is calculated according to 300 days in one year, the average investment is 18466 yuan each day, the equipment maintenance is paid according to 1 percent, and the reduced cost is 0.18 yuan/m3。
7) The running costs roughly amount to: the total running cost of water treatment containing sludge treatment is 39.74 yuan/m3。
Example 4
1.1, adopting the method of example 1 to treat high-salt wastewater generated in a graphite acid cleaning purification and acid mist spraying section in a production workshop of 2 ten thousand tons of high-purity graphite and expanded graphite produced by a new graphite material company every year, wherein the high-salt wastewater and the water quality of drainage are shown in table 1;
1.2 the dosage of the medicament is as follows: the defluorinating agent (aluminum sulfate) is 400kg/d, CaO is 153kg/d, CaCl253kg/d, PAC 11.0kg/d, PAM 9.0 kg/d;
1.3 operational Effect
The detection conditions of the effluent quality of each step are shown in table 5:
TABLE 5
Example 5
1.1, adopting the method of example 1 to treat high-salt wastewater generated in a graphite acid cleaning purification and acid mist spraying section in a production workshop of 2 ten thousand tons of high-purity graphite and expanded graphite produced by a new graphite material company every year, wherein the high-salt wastewater and the water quality of drainage are shown in table 1;
1.2 the dosage of the medicament is as follows: the defluorinating agent (aluminium salt) is 450kg/d, CaO is 148kg/d, CaCl248kg/d, PAC 9.0kg/d, PAM 8.0 kg/d;
1.3 operational Effect
The detection conditions of the effluent quality of each step are shown in table 6:
TABLE 6
Comparative example 1
The high-salinity wastewater with the same drainage and water quality in the example 2 is treated, the treatment method is that on the basis of the example 1, only lime milk is added in the pretreatment, and the dosage of the medicament is the same as that in the example 2; the results are shown in Table 7:
TABLE 7
Claims (10)
1. A treatment method of graphite product production wastewater is characterized by comprising pretreatment and desalination treatment; the pretreatment sequentially comprises the steps of lime milk reaction, defluorination reaction, coagulation reaction, flocculation reaction, quartz sand filtration and active carbon filtration; the desalting treatment sequentially comprises three stages of reverse osmosis treatment and MVR evaporation; the reverse osmosis treatment comprises security filtration.
2. The method for treating waste water from the production of graphite products as claimed in claim 1, wherein the lime milk is reacted and the used agents are lime milk and calcium chloride.
3. The method for treating wastewater from graphite production as claimed in claim 2, wherein the lime milk is 153kg/1028m in CaO of 148-3Waste water from graphite production.
4. The method for treating waste water produced in graphite product production according to claim 3, wherein the amount of calcium chloride is 48-53kg/1028m3Waste water from graphite production.
5. The method for treating waste water from the production of graphite products as claimed in claim 1, comprising the steps of:
first step of pretreatment
S1.1, feeding the production wastewater into a lime milk reaction tank, adding lime milk and calcium chloride, stirring for reaction, adjusting the pH of the production wastewater to 6-9 to generate sludge and primary treatment liquid, and feeding primary precipitate to a filter press;
s1.2, sequentially adding a defluorinating agent, a flocculating agent and PMA into the primary treatment liquid for defluorination, coagulation and flocculation reactions to obtain sludge and flocculated wastewater, and conveying the sludge to a sludge concentration tank;
s1.3, filtering the flocculated wastewater by quartz sand and activated carbon to obtain pretreated wastewater with the salt content of 7000-;
second step of desalting treatment
S2.1, sequentially carrying out primary security filtration and primary reverse osmosis treatment on the pretreated wastewater, sequentially carrying out secondary security filtration and secondary reverse osmosis treatment on the obtained primary RO concentrated water, sequentially carrying out tertiary security filtration and tertiary reverse osmosis treatment on the obtained secondary RO concentrated water to obtain tertiary RO concentrated water, and simultaneously feeding fresh water obtained by each stage of reverse osmosis into a fresh water tank;
s2.2, feeding the three-level RO concentrated water into an MVR evaporation system for solid-liquid evaporation separation.
6. The method for treating waste water from the production of graphite products as claimed in claim 5, wherein said fluorine removing agent is any one of phosphate, aluminum sulfate and aluminum salt.
7. The method of claim 5, wherein the flocculating agent is PAC (polyaluminium chloride).
8. The method for treating waste water produced in graphite product production according to claim 1, wherein the amount of the flocculant is 9-11kg/1028m3Waste water from graphite production.
9. The method for treating wastewater generated in graphite product production according to claim 1, wherein the amount of PAM is 8-10kg/1028m3Waste water from graphite production.
10. The method for treating wastewater generated in graphite product production as claimed in claim 1, wherein the amount of the fluorine removal agent is 400-500kg/1028m3GraphiteWaste water of product production.
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