CN113526781A - Treatment and recycling system and process for vegetable oil saponin wastewater - Google Patents
Treatment and recycling system and process for vegetable oil saponin wastewater Download PDFInfo
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- CN113526781A CN113526781A CN202010324050.0A CN202010324050A CN113526781A CN 113526781 A CN113526781 A CN 113526781A CN 202010324050 A CN202010324050 A CN 202010324050A CN 113526781 A CN113526781 A CN 113526781A
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- 239000002351 wastewater Substances 0.000 title claims abstract description 89
- 238000000034 method Methods 0.000 title claims abstract description 43
- 239000001397 quillaja saponaria molina bark Substances 0.000 title claims abstract description 34
- 229930182490 saponin Natural products 0.000 title claims abstract description 34
- 150000007949 saponins Chemical class 0.000 title claims abstract description 34
- 230000008569 process Effects 0.000 title claims abstract description 32
- 238000004064 recycling Methods 0.000 title claims abstract description 27
- 235000015112 vegetable and seed oil Nutrition 0.000 title abstract description 25
- 239000008158 vegetable oil Substances 0.000 title abstract description 25
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 63
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 62
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 61
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 27
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- -1 sodium fatty acid Chemical class 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 500
- 238000001223 reverse osmosis Methods 0.000 claims description 171
- 238000000909 electrodialysis Methods 0.000 claims description 125
- 238000001914 filtration Methods 0.000 claims description 81
- 238000004519 manufacturing process Methods 0.000 claims description 69
- 229910052698 phosphorus Inorganic materials 0.000 claims description 61
- 239000011574 phosphorus Substances 0.000 claims description 61
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 60
- 238000000605 extraction Methods 0.000 claims description 36
- 239000013505 freshwater Substances 0.000 claims description 36
- 238000002425 crystallisation Methods 0.000 claims description 25
- 238000011033 desalting Methods 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 230000008025 crystallization Effects 0.000 claims description 24
- 238000010612 desalination reaction Methods 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 239000012528 membrane Substances 0.000 claims description 18
- 238000005374 membrane filtration Methods 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- 239000011575 calcium Substances 0.000 claims description 13
- 239000012267 brine Substances 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 10
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 8
- 239000012141 concentrate Substances 0.000 claims description 7
- 230000008020 evaporation Effects 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 230000004087 circulation Effects 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 229920002492 poly(sulfone) Polymers 0.000 claims description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 4
- 239000000344 soap Substances 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 239000010773 plant oil Substances 0.000 claims description 3
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 3
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 239000013535 sea water Substances 0.000 claims description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 3
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 3
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 abstract description 94
- 235000014113 dietary fatty acids Nutrition 0.000 abstract description 18
- 239000000194 fatty acid Substances 0.000 abstract description 18
- 229930195729 fatty acid Natural products 0.000 abstract description 18
- 241001465754 Metazoa Species 0.000 abstract description 6
- 239000001488 sodium phosphate Substances 0.000 abstract description 6
- 229910000162 sodium phosphate Inorganic materials 0.000 abstract description 6
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 abstract description 6
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 abstract description 5
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 abstract description 5
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 abstract description 5
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 abstract description 5
- 239000005642 Oleic acid Substances 0.000 abstract description 5
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 abstract description 5
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 abstract description 5
- 239000011734 sodium Substances 0.000 abstract description 5
- 229910052708 sodium Inorganic materials 0.000 abstract description 5
- 229910001425 magnesium ion Inorganic materials 0.000 abstract description 4
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 abstract description 2
- 230000001180 sulfating effect Effects 0.000 abstract description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 32
- 235000011187 glycerol Nutrition 0.000 description 31
- 229910052799 carbon Inorganic materials 0.000 description 14
- 150000004665 fatty acids Chemical class 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 239000003921 oil Substances 0.000 description 13
- 235000019198 oils Nutrition 0.000 description 13
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 11
- CMDGQTVYVAKDNA-UHFFFAOYSA-N propane-1,2,3-triol;hydrate Chemical compound O.OCC(O)CO CMDGQTVYVAKDNA-UHFFFAOYSA-N 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 239000002699 waste material Substances 0.000 description 11
- 239000002686 phosphate fertilizer Substances 0.000 description 10
- 241000196324 Embryophyta Species 0.000 description 9
- 229910052791 calcium Inorganic materials 0.000 description 9
- 230000020477 pH reduction Effects 0.000 description 9
- 238000010586 diagram Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000001506 calcium phosphate Substances 0.000 description 7
- 239000008235 industrial water Substances 0.000 description 7
- 239000010865 sewage Substances 0.000 description 7
- 239000003337 fertilizer Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 6
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 5
- 229910001424 calcium ion Inorganic materials 0.000 description 5
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 description 5
- 238000002306 biochemical method Methods 0.000 description 4
- 229910000389 calcium phosphate Inorganic materials 0.000 description 4
- 235000011010 calcium phosphates Nutrition 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000012452 mother liquor Substances 0.000 description 4
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 4
- 238000004065 wastewater treatment Methods 0.000 description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 235000019730 animal feed additive Nutrition 0.000 description 3
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 description 3
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 3
- 235000019700 dicalcium phosphate Nutrition 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 235000019691 monocalcium phosphate Nutrition 0.000 description 3
- 229910000150 monocalcium phosphate Inorganic materials 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000009395 breeding Methods 0.000 description 2
- 230000001488 breeding effect Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 235000015097 nutrients Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 206010033799 Paralysis Diseases 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000017531 blood circulation Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- KMQAPZBMEMMKSS-UHFFFAOYSA-K calcium;magnesium;phosphate Chemical compound [Mg+2].[Ca+2].[O-]P([O-])([O-])=O KMQAPZBMEMMKSS-UHFFFAOYSA-K 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229940126601 medicinal product Drugs 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011268 retreatment Methods 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
- C01P2006/82—Compositional purity water content
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—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
- C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides a treatment and recycling system and a process for vegetable oil saponin wastewater. The system and the process for treating and recycling the vegetable oil saponin wastewater are mainly suitable for treating and recycling the wastewater generated by sulfating the vegetable oil saponin, and can also be applied to the treatment of animal oleic acid wastewater. The waste water produced by the vegetable oil saponin after being sulfated is characterized by high hardness, high suspended matter, high salt content and high COD, and the main components in the waste water are sodium sulfate, sodium phosphate, sodium fatty acid, sulfuric acid, glycerol, calcium magnesium ions and the like.
Description
Technical Field
The invention belongs to the technical field of industrial water saving, and particularly relates to a recycling system and a recycling process for plant oil saponin waste water treatment.
Background
The waste water of the vegetable oil soap horn is the waste water produced after the vegetable oil soap horn is acidified by sulfuric acid, and the waste water is characterized by high hardness, high suspended matter, high salt content and high COD, and the main components in the waste water are sodium sulfate, sodium phosphate, sodium fatty acid, sulfuric acid, glycerin, calcium magnesium ions and the like. The kinds of vegetable oil saponin include: soybean oil saponin, peanut oil saponin, rapeseed oil saponin, palm oil saponin, olive oil saponin, and the like.
Saponin is a by-product produced in the process of making oil from plants. The crude oil is subjected to an alkalization deacidification process to obtain the saponin, the saponin is also a production raw material of industrial fatty acid, the acidified oil can be obtained by adding concentrated sulfuric acid into the saponin, and simultaneously, an acidified oil wastewater is generated in the production process.
The nature of the acidified oil is fatty acid, which contains fatty acid, pigment, non-acidified triglyceride, etc. Industrial fatty acid can be produced by taking the acidified oil as a raw material, and saponin acidified oil wastewater can be generated in the production process.
The existing method for treating the waste water generated by vegetable oil saponin after sulfuric acid acidification mainly comprises a biochemical method and an evaporation method.
The biochemical method is used for discharging the wastewater after reaching the standard after the wastewater is completely treated, the method has the advantages that the requirement on temperature control is strict, the requirement on salinity in water is also strict, the phenomena of system paralysis and unqualified treatment effect are frequently encountered in operation, meanwhile, the occupied area for treating the wastewater is large, and a large number of water tanks are required to be built.
The evaporation method is to evaporate all the wastewater, the generated steam is condensed and then sent to a sewage plant for retreatment or enters a biochemical system for treatment, and the concentrated solution after evaporation enriches most salt ions, glycerin and the like in the wastewater, and belongs to waste. Meanwhile, because the hardness of water is high, the evaporator is easy to be blocked and needs to be cleaned frequently.
The main components of the wastewater are sodium sulfate, sodium phosphate, sodium fatty acid, sulfuric acid, glycerol, calcium and magnesium ions and the like, through physical and chemical sub-analysis of each substance in the water, the invention adopts different water treatment technologies to extract the production raw materials (fatty acid and glycerol) in the wastewater, the sodium sulfate and the calcium phosphate, and the generated purified water can be reused as industrial water or boiler water. Therefore, not only is a regenerated water source obtained, but also available production raw materials are extracted, and the waste wastewater is recycled. The invention belongs to a zero discharge system and has great significance for the current water treatment technology.
Phosphorus, which is one of the three elements of a fertilizer, is one of 17 elements essential to living bodies, is called "three major nutrient elements" of plants together with nitrogen and potassium, is one of essential important nutrient elements for living bodies, and has important significance for the survival and development of human beings.
The calcium hydrogen phosphate as feed is an important component in feed industry, and is mixed with a certain proportion of feed calcium hydrogen phosphate, in which the phosphorus is an important element for metabolism and maintaining physiological function in animal body, and the element is called "life element", and the calcium is an important component for forming skeleton and tooth, and can promote blood circulation, and can maintain the conduction property of nerve under the activation action of some enzymes in body, and can play an important role in regulating muscle flexibility, normal osmotic pressure of capillary vessel and acid-base balance in body. In recent years, with the rapid development of agriculture and animal husbandry in China, large-scale and intensive breeding industry, breeding industry and feed processing industry are developing at an unprecedented speed, the demand of domestic markets for feed-grade calcium hydrophosphate is increasing, and the development prospect of calcium hydrophosphate is extremely wide. Therefore, the knowledge and understanding of calcium hydrogen phosphate is very important.
The raw material source of phosphorus mainly depends on phosphate ore, the problems of non-regenerability of the phosphate ore resource, too fast consumption rate of the phosphorus resource and sustainable development of the phosphorus resource become important resource problems which are concerned all over the world, and the shortage of the phosphorus resource not only causes serious threat to agricultural production and promotes the rapid rise of grain price, but also causes the non-regenerability of renewable resources. The discharge of a large amount of low-concentration phosphorus-containing wastewater results in a great loss of resources. Therefore, the method effectively recovers the phosphorus from the phosphorus-containing wastewater and has important significance in the technical field of wastewater treatment.
The acidic oil wastewater has great influence on the subsequent treatment process if not removed due to high suspended matters and oil content. The existing pretreatment system is not particularly ideal for the treatment effect of the wastewater with high suspended matters and oil, and the problems of rapid membrane flux reduction, incapability of recovering flux after cleaning and the like often occur. The filter unit of the invention can effectively solve the problems.
Disclosure of Invention
Based on the background technology, the invention provides a method for extracting sodium sulfate from waste water generated after vegetable oil saponin is sulfated and other sodium sulfate waste water, wherein the sodium sulfate is mainly applied to the manufacture of water glass, porcelain glaze, paper pulp, refrigerating mixing agent, detergent, drying agent, dye diluent, analytical chemical reagent, medicinal products, feed and the like. The desalting unit and the sodium sulfate extracting unit can effectively extract sodium sulfate in water in the form of sodium sulfate decahydrate. The technical scheme is as follows:
the invention provides a treatment and recycling system of vegetable oil saponin wastewater, which comprises a filtering unit, a desalting unit, a phosphorus extraction unit and a sodium sulfate extraction unit;
the filtering unit comprises a pretreatment device and a membrane filtering device;
the desalting unit comprises an electrodialysis water inlet tank, an electrodialysis device I, an electrodialysis water production tank I and an electrodialysis concentrated water tank I.
The phosphorus extraction unit comprises a dosing reaction device and a filtering device; the sodium sulfate extracting unit comprises a crystallization kettle and a centrifuge;
the sodium sulfate extracting unit comprises a crystallization kettle and a centrifuge;
the pretreatment device is communicated with an inlet of a membrane filtration device, a water outlet of the membrane filtration device is communicated with a water inlet of an electrodialysis water inlet tank, a water outlet of the electrodialysis water inlet tank is communicated with a water inlet of an electrodialysis device I, a strong brine outlet of the electrodialysis device I is communicated with a water inlet of an electrodialysis strong brine tank I, and a fresh water outlet of the electrodialysis device I is communicated with a water inlet of an electrodialysis precipitation water tank I;
the water outlet of the electrodialysis concentrated water tank I is communicated with the water inlet of a dosing reaction device, the outlet of the dosing reaction device is communicated with the water inlet of a filtering device, the water outlet of the filtering device is communicated with the water inlet of a crystallization kettle, and the water outlet of the crystallization kettle is communicated with the water inlet of a centrifuge;
or the water outlet of the electrodialysis concentrated water tank I is communicated with the water inlet of the crystallization kettle, the water outlet of the crystallization kettle is communicated with the water inlet of the centrifuge, the water outlet of the centrifuge is communicated with the water inlet of the dosing reaction device, and the outlet of the dosing reaction device is communicated with the water inlet of the filtering device;
and the centrifugate of the centrifuge or the filtrate of the filtering device enters an electrodialysis water inlet tank. The sodium sulfate unit can be matched with a desalting unit to be independently used in other treatment systems of wastewater containing sodium sulfate.
Based on the technical scheme, preferably, the treatment and reuse system further comprises a COD concentration unit; the COD concentration unit comprises a reverse osmosis device I, a reverse osmosis concentrated water tank I, a reverse osmosis water production tank I, an electrodialysis device II, an electrodialysis concentrated water tank II, an electrodialysis water production tank II, a reverse osmosis device II and a reverse osmosis concentrated water tank II;
the water outlet of the electrodialysis water production tank I is communicated with the water inlet of the reverse osmosis device I; a concentrated water outlet of the reverse osmosis device I is communicated with a water inlet of the reverse osmosis concentrated water tank I; a fresh water outlet of the reverse osmosis device I is communicated with a water inlet of the reverse osmosis water production tank I; the water outlet of the reverse osmosis concentrated water tank I is communicated with the water inlet of the electrodialysis device II; a concentrated water outlet of the electrodialysis device II is communicated with an inlet of the electrodialysis concentrated water tank II; a fresh water outlet of the electrodialysis device II is communicated with a water inlet of the reverse osmosis device II; and a concentrated water outlet of the reverse osmosis device II is communicated with a water inlet of the reverse osmosis concentrated water tank II. In the COD concentration unit of this application, reverse osmosis unit I still replaces other enrichment facility that have the same function, for example: an evaporative concentrator may be employed.
Based on the technical scheme, preferably, the water outlet of the electrodialysis concentrated water tank II is communicated with the water inlet of the electrodialysis water inlet tank; the fresh water outlet of the reverse osmosis device II is communicated with the water inlet of the reverse osmosis water production tank I.
Based on the technical scheme, preferably, the treatment and reuse system further comprises a COD treatment unit; the COD treatment unit is a high-grade anaerobic tower or an evaporator or directly used as a carbon source; the high-grade anaerobic tower is an IC anaerobic tower;
the water outlet of the reverse osmosis concentrated water tank II is communicated with the water inlet of the high-grade anaerobic tower; the effluent of the high-grade anaerobic tower returns to the filtering unit;
or the water outlet of the reverse osmosis concentrated water tank II is communicated with the water inlet of the evaporator. The high-concentration COD treatment unit has three methods: the first is direct use as a carbon source; the second is to enter a high-grade anaerobic tower to produce methane; the third is to extract valuable products by distillation according to the difference of physicochemical properties of the organic substances providing COD.
Based on the technical scheme, preferably, the treatment and recycling system further comprises an advanced treatment unit; the advanced treatment unit comprises a secondary reverse osmosis device, a secondary reverse osmosis water production tank, a tertiary reverse osmosis device and a tertiary reverse osmosis water production tank;
the water outlet of the reverse osmosis water production tank I is communicated with the water inlet of the secondary reverse osmosis device; a fresh water outlet of the second-stage reverse osmosis device is communicated with a water inlet of the second-stage reverse osmosis water production tank; the water outlet of the second-stage reverse osmosis water production tank is communicated with the water inlet of the third-stage reverse osmosis device.
Based on the technical scheme, preferably, a concentrated water outlet of the secondary reverse osmosis device is communicated with a water inlet of the electrodialysis water production tank I; and a concentrated water outlet of the third-stage reverse osmosis device is communicated with a water inlet of the reverse osmosis water production tank I.
Based on the technical scheme, preferably, the pretreatment device is a filtering device, and the filtering method comprises membrane filtration, filter pressing of a filter press, filtration of a candle filter and filtration of a centrifugal machine;
the membrane filtering device is an organic membrane filtering device or an inorganic membrane filtering device; the organic membrane material is at least one of Polyacrylonitrile (PAN), Polysulfone (PSF), Polytetrafluoroethylene (PTFE), Polyethersulfone (PES), Polystyrene (PS), polyvinylidene fluoride (PVDF) or polyvinyl chloride (PVC); the inorganic film material is silicon carbide or ceramic;
the membrane filtering device is a flat plate type, a roll type or a curtain type;
the membrane filtering device is of an external pressure type or an internal pressure type;
the reverse osmosis type used in the reverse osmosis device I and the reverse osmosis device II has no special requirement, and any reverse osmosis device can be used, including: common reverse osmosis, Disc Tube Reverse Osmosis (DTRO), seawater desalination reverse osmosis, and the like.
The filtration method of the phosphorus extraction unit filtration device comprises membrane filtration, filter pressing of a filter press, filtration of a candle filter and filtration of a centrifuge; the filtration precision of the filter device is 1-20 μm.
The system of the invention does not need to extract high-concentration COD solution as carbon source, crude glycerol and methane. The COD concentration unit, the high concentration COD treatment unit and the advanced treatment unit are not required to be used. The produced water after the desalting unit is directly treated by a conventional biochemical system and then is discharged after reaching the standard.
The invention also provides a treatment system and a treatment process of the vegetable oil saponin wastewater, and the system is used and comprises the following steps:
(1) the wastewater enters a filtering unit to remove impurities;
(2) the effluent of the filtering unit enters a desalting unit for treatment, the concentrated water of the desalting unit enters a phosphorus extraction unit for phosphorus extraction, then enters a sodium sulfate extraction unit for sodium sulfate extraction, and the centrifugate of the sodium sulfate extraction unit enters an electrodialysis water inlet tank; or the concentrated water of the desalting unit enters a sodium sulfate extracting unit and then enters a phosphorus extracting unit, and the filtrate of the phosphorus extracting unit enters an electrodialysis water inlet tank;
(3) fresh water of the desalination unit enters a COD concentration unit, fresh water of a reverse osmosis device I and fresh water of a reverse osmosis device II in the COD concentration unit enter an advanced treatment unit for treatment, and concentrated water of the COD concentration unit enters a COD treatment unit for anaerobic methanogenesis or evaporative concentration; the produced water of the COD treatment unit returns to the front end of the filtering unit for treatment; the steam after evaporation and concentration is utilized or condensed to be used as reuse water;
(4) the concentrated water separated by the secondary reverse osmosis device returns to the water inlet of the reverse osmosis device I of the COD concentration unit for continuous circulation treatment;
the process comprises the following steps: adding concentrated sulfuric acid into vegetable oil soap horns for acidification to prepare acidified oil wastewater, storing the acidified oil wastewater in an acidification tank, enabling the wastewater in the acidification tank to firstly enter a pretreatment device of a filtering unit, separating large-particle suspended matters in the wastewater, and enabling effluent to enter a membrane filtering device to remove residual suspended matters in water and residual fatty acid in the water;
the effluent of the filtration unit enters an electrodialysis device I of the desalination unit for treatment, strong brine produced by the electrodialysis device I enters a phosphorus extraction unit for treatment, and desalted water produced by the electrodialysis device I has the conductivity of 1000 mus/cm and enters a COD concentration unit for further treatment; adding a recovery agent into strong brine of the electrodialysis device I, allowing the strong brine to enter a filtering device after contact reaction to separate phosphorus-containing solids mainly containing calcium hydrophosphate, allowing filtrate to enter a crystallization kettle of a sodium sulfate extraction unit, performing freeze crystallization at a temperature ranging from-3 ℃ to-5 ℃, allowing mixed liquid discharged from the crystallization kettle to enter a centrifugal machine, separating sodium sulfate crystals, returning the centrifugal liquid to an electrodialysis water inlet tank of a desalination unit, mixing the centrifugal liquid with produced water of the filtering unit, and allowing the mixed liquid to enter a system for circulation treatment; the reverse osmosis unit I of the COD concentration unit separates the desalinated water from the desalination unit into concentrated water with high COD and fresh water with COD removed. Fresh water of the reverse osmosis device I enters the advanced treatment unit for continuous treatment, concentrated water of the reverse osmosis device I enters the electrodialysis device II for re-desalination, and concentrated brine of the electrodialysis device II returns to an electrodialysis water inlet tank of the desalination unit for re-circulation treatment; the desalted water of the electrodialysis device II enters the reverse osmosis device II to continuously concentrate COD, and the fresh water of the reverse osmosis device II and the fresh water of the reverse osmosis device I are mixed and then enter the advanced treatment unit for continuous treatment; the concentrated water of the reverse osmosis device II is glycerol water containing about 10% of glycerol, and if the 10% glycerol water is used as a carbon source, the glycerol water can be directly used; if 10% of glycerol water is used as a raw material for producing methane, concentrated water of the reverse osmosis device II is sent to a high-grade anaerobic tower for treatment, the produced methane can be used as energy, and effluent of the anaerobic tower returns to the front end of the filtering unit and is mixed with inlet water for circular treatment. If 10% glycerol water is used for preparing the industrial crude glycerol, the concentrated water of the reverse osmosis device II is sent to an evaporator for continuous concentration, the steam can be directly recycled, or the concentrated water is used as recycled water after condensation, and the concentrated solution is the industrial crude glycerol. The second-stage reverse osmosis device of the advanced treatment unit receives fresh water produced by the COD concentrated water unit, and concentrated water separated by the second-stage reverse osmosis device returns to a water inlet of a reverse osmosis device I of the COD concentrated unit to be continuously subjected to circulating treatment; fresh water of the second-stage reverse osmosis device enters the third-stage reverse osmosis device for continuous treatment, concentrated water of the third-stage reverse osmosis device returns to a water inlet of the second-stage reverse osmosis device for continuous circulation treatment, and the fresh water of the third-stage reverse osmosis device can be used as reuse water. The conductivity of the effluent of the secondary reverse osmosis device is less than 100 mu s/cm, COD is less than 100mg/L, ammonia nitrogen is less than 1mg/L, and total phosphorus is less than 1mg/L, so that the effluent can be reused as production water. Meanwhile, the second-level reverse osmosis produced water can be treated by a third-level reverse osmosis device to ensure that the conductivity is less than 20 mu s/cm and the COD is less than 10mg/L, and then the water can be used as boiler water.
The electrodialysis device, reverse osmosis device or other devices used in the invention are commercially available, wherein the reverse osmosis device for the COD concentration unit can be common reverse osmosis or disc-tube reverse osmosis (DTRO) or seawater desalination reverse osmosis. Electrodialysis device i and electrodialysis device ii are preferably of the application numbers: 201620007937.6, named as electrically driven membrane desalination unit, is prepared by feeding water into the electrodialysis device from fresh water side and concentrated water side simultaneously, and transferring salt ions to the concentrated water side.
Based on the above technical solution, preferably, the conductivity of the desalted water of the electrodialysis device of the desalting unit is preferably treated to 1000 μ s/cm, and the conductivity of the concentrated brine is preferably concentrated to 150000 μ s/cm.
Based on the technical scheme, preferably, for the treatment of the acidified oil wastewater, the recycling agent can be selected from sodium hydroxide, sodium oxide, calcium hydroxide, calcium oxide, magnesium hydroxide, magnesium oxide, potassium hydroxide, potassium oxide and the like, if the concentration of calcium ions in water is greater than that of phosphorus in other phosphorus-containing wastewater, the recycling agent can be selected arbitrarily, and if the content of the calcium ions is low, the recycling agent containing the calcium ions needs to be selected;
it is to be emphasized that: the recycling agent A needs to be pure white and has no impurities, otherwise, the obtained phosphorus-containing solid is not pure white. If there is no particular requirement on the color of the phosphorus-containing solid, the recycle agent may be selected to have a relatively low purity.
Based on the technical scheme, preferably, the electrodialysis concentrated water is subjected to contact reaction with a recycling agent and then is separated by a filtering device to obtain phosphorus-containing solid with the water content of 30-40%; the extracted phosphorus mainly exists in the form of calcium hydrophosphate, and is a high-quality calcium magnesium phosphate fertilizer and an animal feed additive. Meanwhile, the extracted phosphorus can also be used as a material for brick firing and a fireproof material for an interlayer of a fireproof door.
Based on the above technical scheme, preferably, the adding amount of the reclaiming agent is adjusted by the pH value of the reaction. The pH is 6-10, where cost performance is highest. The yield of phosphorus-containing solids increases with increasing pH, but the amount of recycle agent required increases with higher pH. A corresponding relatively low pH control may reduce the dosage, but the yield of phosphorus-containing solids is relatively low.
Based on the technical scheme, the contact reaction time of the wastewater of the phosphorus extraction unit and the recycling agent A is preferably 20-60 min.
The positions of the phosphorus extraction unit and the desalination unit can be interchanged.
Based on the technical scheme, the crystallization temperature of the sodium sulfate extracting unit is preferably controlled to be-3 ℃ to-5 ℃. The solubility of the sodium sulfate at 0 ℃ is 4.9 percent, and the solubility at 20 ℃ is 19.5 percent, so when the salt content in the electrodialysis concentrated water reaches about 15 percent, the sodium sulfate can be extracted by freezing crystallization, and the crystallized mother liquor can flow back to the water inlet of the desalting unit; the extracted sodium sulfate is sodium sulfate decahydrate, and pure sodium sulfate solid can be obtained by drying. The sodium sulfate extracting unit can also be matched with the desalting unit to be independently used in other treatment systems of the wastewater containing sodium sulfate.
Based on the technical scheme, preferably, the conductivity of the effluent treated by the secondary reverse osmosis device is 100 mu s/cm, COD is less than 100mg/L, ammonia nitrogen is less than 1mg/L, and total phosphorus is less than 1 mg/L; the conductivity of the produced water of the three-stage reverse osmosis device is less than 80 mu s/cm, and the COD is less than 10 mg/L. If the water produced by the second-stage reverse osmosis device can meet the recycling requirement, the third-stage reverse osmosis treatment is not needed. If the requirement for reuse water is higher, a reverse osmosis device can be added and connected in series behind the third pole reverse osmosis device.
The electrodialysis device of the desalting unit can only separate the ionic components in water, and COD exists in a non-ionic state in water, so that the COD in the water after the wastewater passes through the electrodialysis device is basically unchanged;
the COD concentration unit adopts a reverse osmosis device to isolate COD mainly containing glycerol and residual salt in water on the concentrated water side of the reverse osmosis device, then adopts an electrodialysis device to desalt the water further to ensure that the glycerol content in the water is purer, and uses the reverse osmosis device again to concentrate the water to ensure that the glycerol content in the concentrated water reaches more than 10 percent.
The concentrated water with high COD concentrated by the COD concentration unit is subjected to a series of processes, so that the water mainly contains glycerol which is micromolecular COD and is easy to degrade biochemically. Therefore, the high-concentration COD treatment unit provides three treatment methods, namely direct carbon source preparation, anaerobic methane production and evaporation glycerol preparation.
The first treatment mode of the high-concentration COD treatment unit is to be used as a carbon source in a sewage plant or other biochemical systems. The glycerol is micromolecular COD, belongs to COD which is easy to be biodegraded, and the salinity of the water treated by the desalting unit and the COD concentration unit is very low, so the glycerol can be directly provided for a sewage plant to be used as a carbon source;
the second treatment mode of the high-concentration COD treatment unit is to enter a high-grade anaerobic tower for treatment and methane production, and the high-grade anaerobic tower is preferably an IC anaerobic tower and can also be other forms of anaerobic devices. The IC anaerobic reactor is an efficient multi-stage internal circulation reactor, and the sludge-water mixture in the reactor is fully mixed by the generated methane to improve the COD degradation efficiency. The produced methane is stored and then used as energy. The produced water returns to the front end of the filtering unit for circular treatment.
The third treatment mode of the high-concentration COD treatment unit is to adopt an evaporator to continuously concentrate the high-COD concentrated water, and valuable products are extracted by distillation according to the difference of physicochemical properties of organic substances providing COD. The raw water in the system is the wastewater generated by sulfating vegetable oil saponin, so the high COD concentrated water is 10% glycerol water, and crude glycerol with higher concentration can be obtained after distillation. The steam generated by the evaporator can be directly reused as steam or cooled and reused as reuse water. The evaporator is preferably an MVR evaporator, but may be other types of evaporation devices.
According to the invention, through the physical and chemical properties of various substances in the wastewater, the vegetable oil saponin is subjected to purification treatment of the wastewater generated by acidification with sulfuric acid, and simultaneously, the components are separated and purified, so that the aim of zero emission is achieved.
Compared with the traditional treatment process, the system can reuse the treated water as industrial water or boiler water; and the water treated by the traditional process is discharged into a sewage station or a river. And the stability and reliability of the system are stronger. Meanwhile, the system can extract phosphate fertilizer, sodium sulfate, crude glycerol, methane and carbon source in the wastewater, and can bring additional value. Meanwhile, the system is a physical and chemical method, and a large number of water pools do not need to be built; the system has modularized equipment, small occupied space and easy daily operation and maintenance.
The invention provides a treatment and recycling system and a process for vegetable oil saponin wastewater, but the treatment and recycling system and the process do not mean that the treatment and recycling process can be directly used in all projects;
similarly, the invention can be applied to the treatment of the animal oleic acid wastewater as the physical and chemical properties of the animal oleic acid wastewater are similar to those of the plant oleic acid oil wastewater. However, it should be emphasized that when the system provided by the invention is applied to the treatment of animal oleic acid wastewater, the system needs to be slightly modified according to the actual water quality, but the treatment idea is the same as the main process. The waste water produced by the vegetable oil saponin after being sulfated has the characteristics of high hardness, high suspended matters, high salt content and high COD. After the vegetable oil saponin is acidified by sulfuric acid, the lower layer waste liquid is yellow and opaque, the COD is 30000-40000mg/L, and the conductivity is 60000-80000 mu s/cm. The main components comprise sodium sulfate, sodium phosphate, sodium fatty acid, sulfuric acid, glycerol, calcium and magnesium ions and the like. COD in the waste liquid is mainly contributed by fatty acid, fatty sodium and glycerol, and concentrated sulfuric acid is adopted in the acidification demulsification process, so that salt in the waste liquid mainly comprises sodium sulfate, and a certain amount of sodium phosphate is also contained in water, and the total content of the sodium sulfate and the sodium phosphate in the waste liquid is 5-7%; the hardness of the wastewater is higher, generally 6000-9000mg/L, and the hardness of the wastewater mainly takes monocalcium phosphate as the main component because the wastewater is acidic; the waste liquid also contains a certain amount of fatty acid and suspended matters, and the raw materials are separated and extracted by different processes through analyzing the physical and chemical properties of the main components of the waste liquid so as to achieve the dual purposes of extracting the raw materials and purifying the water quality.
Advantageous effects
(1) After the wastewater treatment system provided by the invention is treated, the conductivity of produced water is less than 20 mu s/cm, COD is less than 10mg/L, hardness is 0mg/L, ammonia nitrogen is less than 10mg/L, and phosphorus is less than 1mg/L, and then the produced water can be used as boiler water. Meanwhile, phosphorus in the wastewater can be extracted in the form of calcium hydrophosphate to be used as a phosphate fertilizer or an animal feed additive; extracting sodium sulfate in the wastewater to be used as industrial sodium sulfate; the method comprises the following steps of purifying COD in the wastewater to the standard of industrial crude glycerol, or purifying COD in the wastewater to the standard of a carbon source which can be used as a sewage plant, or treating the COD in the wastewater to the standard of direct anaerobic methane production, or treating the COD in the wastewater to the standard of direct entering a biochemical system.
(2) At present, there are two main methods for treating the wastewater globally, one is evaporation method, and the other is biochemical method. The hardness of the wastewater is high, and is generally about 6000-9000 mg/L. Fouling can easily occur if the process enters the evaporation system, which affects the efficiency of the evaporator, and the evaporator is cleaned frequently and the operation cost is high. Meanwhile, the salt content in the wastewater is too high, so that the wastewater cannot directly enter a biochemical system for treatment, and the living environment of microorganisms in a normal biochemical system ensures that the conductivity is lower than 20000 mu s/cm. Most of the processes for treating such wastewater by biochemical methods are used by dilution or evaporation, which results in increased cost and undesirable operation of wastewater treatment. The treatment system provided by the invention does not have the problems, the treatment system provided by the invention mostly adopts a physical method, phosphorus and salt in the wastewater are extracted by the filtration of a membrane and the division of electrochemical technology, the salinity in the water can be effectively reduced, and the high COD in the wastewater can be converted into a utilizable energy source by matching with the methanogenesis method in the high-concentration COD treatment unit, so that the resource recovery and zero emission can be realized.
Drawings
FIG. 1 is a flow diagram of one of the processing systems of the present invention;
FIG. 2 is a flow diagram of another processing system of the present invention;
FIG. 3 is a flow diagram of one of the processes of the present invention;
FIG. 4 is another process flow diagram of the present invention;
FIG. 5 is a flow chart of another processing system of the present invention;
FIG. 6 is another process flow diagram of the present invention;
in the figure: 0-raw water tank, A-filtration unit, B-desalination unit, C-phosphorus extraction unit, D-sodium sulfate extraction unit, E-COD concentration unit, F-high concentration COD treatment unit, G-advanced treatment unit, H-biochemical system, 1-pretreatment device, 2-membrane filtration device, 3-electrodialysis water inlet tank, 4-electrodialysis device I, 5-electrodialysis concentrated water tank I, 6-recovery agent, 7-dosing reaction device, 8-filtration device, 9-phosphate fertilizer, 10-crystallization kettle, 11-centrifuge, 12-sodium sulfate, 13-precipitation water tank I, 14-reverse osmosis device I, 15-reverse osmosis concentrated water tank I, 16-electrodialysis device II, 17-electrodialysis concentrated water tank II, 18-electrodialysis water production tank II, 19-reverse osmosis device II, 20-reverse osmosis concentrated water tank II, 21-carbon source, 22-anaerobic tower, 23-methane, 24-anaerobic water production, 25-evaporator, 26-crude glycerol, 27-steam, 28-reverse osmosis water production tank I, 29-second-stage reverse osmosis device, 30-second-stage reverse osmosis water production tank, 31-third-stage reverse osmosis device and 32-third-stage reverse osmosis water production.
Detailed Description
Example 1
FIG. 1 is a flow chart of one embodiment of the present invention. The waste water is lower layer waste liquid of vegetable oil saponin which is acidized by sulfuric acid, is yellow and opaque, has COD of 40000mg/L, conductivity of 80000 mu s/cm, salt content of 6 percent and hardness of 8000mg/L, and also contains a certain amount of fatty acid and suspended matters. Waste water generated after vegetable oil saponin is sulfated and acidified is stored in a raw water tank 0, and the waste water in the raw water tank 0 firstly enters a filtering unit to remove suspended matters and residual fatty acid in water; the effluent of the filtering unit A enters a desalting unit B, salt ions mainly comprising sodium sulfate and monocalcium phosphate in the wastewater are transferred to the concentrated water side of the desalting unit B, and the conductivity of the desalted fresh water enters a COD concentration unit E at about 1000 mus/cm for continuous treatment; the phosphorus extraction unit C receives the concentrated water from the desalting unit B, extracts phosphorus in the water in a form of calcium hydrophosphate and calcium phosphate as main materials to be used as a phosphate fertilizer or an animal feed additive for sale or use, and the extracted phosphate fertilizer contains more than 18 percent of phosphorus pentoxide and is a high-quality phosphate fertilizer; the effluent of the phosphorus extraction unit C enters a sodium sulfate extraction unit D, sodium sulfate in water is extracted in the form of sodium sulfate decahydrate, the sodium sulfate can be directly sold and used or dried and then sold and used, the purity of the extracted sodium sulfate is over 90 percent, and mother liquor after the extraction of the sodium sulfate returns to a water inlet of a desalination unit B for circular treatment; the COD concentration unit E receives the fresh water from the desalination unit B, and concentrates COD mainly comprising glycerol in the water to the concentrated water side of the COD concentration unit E, and the concentrated water is 10% glycerol water; the water produced by the COD concentration unit E enters an advanced treatment unit G for continuous treatment, the conductivity of the water produced after the treatment of the advanced treatment unit G is less than 100 mu s/cm, the COD is less than 100mg/L, the ammonia nitrogen is less than 1mg/L, and the total phosphorus is less than 1mg/L, so that the water can be reused as industrial water or boiler water; the high-concentration COD treatment unit F receives the concentrated water from the COD concentration unit E, and the concentrated water can be used as a carbon source for a sewage plant after being treated by the high-concentration COD treatment unit F, or methane is produced for a boiler, or industrial crude glycerol is produced for sale. When high COD concentrated water is adopted for anaerobic methanogenesis, the effluent of the high-concentration COD treatment unit F is recycled before returning to the filtering unit.
Example 2
FIG. 2 is a flow chart of another processing system of the present invention. The waste water is lower layer waste liquid of vegetable oil saponin which is acidized by sulfuric acid, is yellow and opaque, has COD of 40000mg/L, conductivity of 80000 mu s/cm, salt content of 6 percent and hardness of 8000mg/L, and also contains a certain amount of fatty acid and suspended matters. Waste water generated after vegetable oil saponin is sulfated and acidified is stored in a raw water tank 0, and the waste water in the raw water tank 0 firstly enters a filtering unit to remove suspended matters and residual fatty acid in water; the water discharged from the filtering unit A enters a phosphorus extraction unit C, phosphorus in the water is extracted in the form of calcium hydrophosphate and calcium phosphate to be sold or used as a phosphate fertilizer, and the content of the extracted phosphate fertilizer phosphorus pentoxide can reach more than 12%; the effluent of the phosphorus extraction unit C enters a desalination unit B, salt ions mainly comprising sodium sulfate in the wastewater are transferred to the concentrated water side of the desalination unit B, the conductivity of the desalinated fresh water is 1000 mus/cm, and the desalinated fresh water enters a COD concentration unit E for continuous treatment; the sodium sulfate extraction unit D receives the concentrated water from the desalination unit B, sodium sulfate in the water is extracted in the form of sodium sulfate decahydrate, the purity of the extracted sodium sulfate is more than 90%, the sodium sulfate can be directly sold and used or dried and then sold and used, and mother liquor after the sodium sulfate extraction is returned to a water inlet of the desalination unit B for circular treatment; the COD concentration unit E receives the fresh water from the desalination unit B and concentrates COD mainly comprising glycerol in the water to the concentrated water side of the COD concentration unit E; the produced water of the COD concentration unit E enters an advanced treatment unit G for continuous treatment, the conductivity of the produced water treated by the advanced treatment unit G is less than 100 mu s/cm, the COD is less than 100mg/L, the ammonia nitrogen is less than 1mg/L, and the total phosphorus is less than 1mg/L, so that the produced water can be reused as industrial water or boiler water; the high-concentration COD treatment unit F receives the concentrated water from the COD concentration unit E, and the concentrated water can be used as a carbon source for a sewage plant after being treated by the high-concentration COD treatment unit F, or methane is produced for a boiler, or industrial crude glycerol is produced for sale. When high COD concentration anaerobic methanogenesis is adopted, the effluent of the high concentration COD treatment unit F returns to the filtering unit for circular treatment.
Example 3
FIG. 3 shows a process flow diagram of the present invention. The acidification tank 0 is communicated with a water inlet of the pretreatment device 1, a water outlet of the pretreatment device 1 is communicated with a water inlet of a membrane filtration device 2, a water outlet of the membrane filtration device 2 is communicated with a water inlet of an electrodialysis water inlet tank 3, a water outlet of the electrodialysis water inlet tank 3 is communicated with a water inlet of an electrodialysis device I4, fresh water produced by the electrodialysis device I4 is communicated with a water inlet of an electrodialysis production water tank I13, concentrated water of the electrodialysis device I4 is communicated with a water inlet of an electrodialysis concentrated water tank I5, a water outlet of the electrodialysis concentrated water tank I5 is communicated with a water inlet of a dosing reaction device 7, a dosing port of a recycling agent 6 is communicated with a dosing port of the dosing reaction device 7, a water outlet of the dosing reaction device 7 is communicated with a water inlet of a filtration device 8, phosphate fertilizer 9 separated by the filtration device 8 is separately collected and stored, and a water outlet of the filtration device 8 is communicated with a water inlet of a crystallization kettle 10, the water outlet of the crystallization kettle 10 is communicated to the water inlet of the centrifuge 11, the sodium sulfate 12 separated by the centrifuge 11 is separately collected and stored, and the water outlet of the centrifuge 11 is communicated to the water inlet of the electrodialysis water inlet tank 3. The water outlet of the electrodialysis water production tank I13 is communicated with the water inlet of the reverse osmosis device I14, the water production port of the reverse osmosis device I14 is communicated with the water inlet of the reverse osmosis water production tank I28, and the concentrated water port of the reverse osmosis device I14 is communicated with the water inlet of the reverse osmosis concentrated water tank I15. The water outlet of the reverse osmosis concentrated water tank I15 is communicated to the water inlet of the electrodialysis device II16, the fresh water produced by the electrodialysis device II16 is communicated to the water inlet of the electrodialysis production water tank II18, and the concentrated water of the electrodialysis device II16 is communicated to the water inlet of the electrodialysis concentrated water tank II 17. The water outlet of the electrodialysis concentrated water tank II17 is communicated to the water inlet of the electrodialysis water inlet tank 3. The water outlet of the electrodialysis water production tank II18 is communicated to the water inlet of the reverse osmosis device II19, and the water produced by the reverse osmosis device II19 is communicated to the water inlet of the reverse osmosis water production tank I28. The water outlet of the reverse osmosis water production tank I28 is communicated to the water inlet of the secondary reverse osmosis device 29, the water production port of the secondary reverse osmosis device 29 is communicated to the water inlet of the secondary reverse osmosis water production tank 30, and the concentrated water of the secondary reverse osmosis device 29 is communicated to the water inlet of the reverse osmosis water production tank I13. The water outlet of the second-stage reverse osmosis water production tank 30 is communicated to the water inlet of the third-stage reverse osmosis device 31, and the water produced by the third-stage reverse osmosis device 31 can be reused as industrial water or boiler water and is connected to a position needing water. The concentrated water of the third-stage reverse osmosis device 31 is communicated to the water inlet of the reverse osmosis water production tank I28.
When 10% glycerol water is used as the carbon source 21, concentrated water in the reverse osmosis concentrated water tank II20 can be directly and independently collected and stored; when 10% glycerol is adopted to produce methane, a water outlet of the reverse osmosis concentrated water tank II20 is communicated to a water inlet of the anaerobic tower 22, anaerobic produced water 24 is communicated to a water inlet of the pretreatment device 1, and methane 23 produced by the anaerobic tower 22 is separately collected for use; when 10% glycerol water is used for preparing the industrial crude glycerol, a water outlet of the reverse osmosis concentrated water tank II20 is communicated to a water inlet of the evaporator 25, steam 27 generated by the evaporator 25 can be directly used or condensed to be recycled as reuse water, and a concentrated solution generated by the evaporator 25 is the industrial crude glycerol 26.
Example 4
Fig. 4 shows another process flow diagram of the present invention. An acidification tank is communicated with a water inlet of a pretreatment device 1, a water outlet of the pretreatment device 1 is communicated with a water inlet of a membrane filtration device 2, a water outlet of the membrane filtration device 2 is communicated with a water inlet of a reaction tank 7, a chemical adding port of a recycling agent 6 is communicated with a chemical adding port of the reaction tank 7, a water outlet of the reaction tank 7 is communicated with a water inlet of a filtration device 8, phosphate fertilizers 9 separated by the filtration device 8 are separately collected and stored, a water outlet of the filtration device 8 is communicated with a water inlet of an electrodialysis water inlet tank 3, a water outlet of the electrodialysis water inlet tank 3 is communicated with a water inlet of an electrodialysis device I4, fresh water produced by the electrodialysis device I4 is communicated with a water inlet of an electrodialysis production water tank I14, concentrated water of the electrodialysis device I4 is communicated with a water inlet of an electrodialysis concentrated water tank I5, a water outlet of the electrodialysis concentrated water tank I5 is communicated with a water inlet of a water outlet crystallization kettle 10, and a water outlet of the crystallization kettle 10 is communicated with a water inlet of a centrifuge 11, the sodium sulfate 12 separated by the centrifuge 11 is separately collected and stored, and the water outlet of the centrifuge 11 is communicated to the water inlet of the electrodialysis water inlet tank 3. The water outlet of the electrodialysis water production tank I13 is communicated with the water inlet of the reverse osmosis device I14, the water production port of the reverse osmosis device I14 is communicated with the water inlet of the reverse osmosis water production tank I28, and the concentrated water port of the reverse osmosis device I14 is communicated with the water inlet of the reverse osmosis concentrated water tank I15. The water outlet of the reverse osmosis concentrated water tank I15 is communicated to the water inlet of the electrodialysis device II16, the fresh water produced by the electrodialysis device II16 is communicated to the water inlet of the electrodialysis production water tank II18, and the concentrated water of the electrodialysis device II16 is communicated to the water inlet of the electrodialysis concentrated water tank II 17. The water outlet of the electrodialysis concentrated water tank II17 is communicated to the water inlet of the electrodialysis water inlet tank 3. The water outlet of the electrodialysis water production tank II18 is communicated to the water inlet of the reverse osmosis device II19, and the water produced by the reverse osmosis device II19 is communicated to the water inlet of the reverse osmosis water production tank I28. The water outlet of the reverse osmosis water production tank I28 is communicated to the water inlet of the secondary reverse osmosis device 29, the water production port of the secondary reverse osmosis device 29 is communicated to the water inlet of the secondary reverse osmosis water production tank 30, and the concentrated water of the secondary reverse osmosis device 29 is communicated to the water inlet of the reverse osmosis water production tank I13. The water outlet of the second-stage reverse osmosis water production tank 30 is communicated to the water inlet of the third-stage reverse osmosis device 31, and the water produced by the third-stage reverse osmosis device 31 can be reused as industrial water or boiler water and is connected to a position needing water. The concentrated water of the third-stage reverse osmosis device 31 is communicated to the water inlet of the reverse osmosis water production tank I28.
When 10% glycerol water is used as the carbon source 21, concentrated water in the reverse osmosis concentrated water tank II20 can be directly and independently collected and stored; when 10% glycerol is adopted to produce methane, a water outlet of the reverse osmosis concentrated water tank II20 is communicated to a water inlet of the anaerobic tower 22, anaerobic produced water 24 is communicated to a water inlet of the pretreatment device 1, and methane 23 produced by the anaerobic tower 22 is separately collected for use; when 10% glycerol water is used for preparing the industrial crude glycerol, a water outlet of the reverse osmosis concentrated water tank II20 is communicated to a water inlet of the evaporator 25, steam 27 generated by the evaporator 25 can be directly used or condensed to be recycled as reuse water, and a concentrated solution generated by the evaporator 25 is the industrial crude glycerol 26.
Example 5
FIG. 5 is a flow chart of an inventive processing system. The waste water is lower layer waste liquid of vegetable oil saponin which is acidized by sulfuric acid, is yellow and opaque, has COD of 40000mg/L, conductivity of 80000 mu s/cm, salt content of 6 percent and hardness of 8000mg/L, and also contains a certain amount of fatty acid and suspended matters. Waste water generated after vegetable oil saponin is sulfated and acidified is stored in a raw water tank 0, and the waste water in the raw water tank 0 firstly enters a filtering unit to remove suspended matters and residual fatty acid in water; the effluent of the filtering unit A enters a desalting unit B, salt ions mainly comprising sodium sulfate and monocalcium phosphate in the wastewater are transferred to the concentrated water side of the desalting unit B, and the conductivity of the desalted fresh water enters a biochemical system H at 1000-5000 mu s/cm for continuous treatment and then reaches the standard to be discharged; the phosphorus extraction unit C receives the concentrated water from the desalting unit B, phosphorus in the water is extracted mainly in the form of calcium hydrophosphate and calcium phosphate, and the content of the extracted phosphorus fertilizer, namely phosphorus pentoxide can reach more than 12 percent and the phosphorus fertilizer is sold or used as a phosphorus fertilizer; the effluent of the phosphorus extraction unit C enters a sodium sulfate extraction unit D, sodium sulfate in water is extracted in the form of sodium sulfate decahydrate, the purity of the extracted sodium sulfate is over 90 percent, the sodium sulfate can be directly sold and used or dried and then sold and used, and mother liquor after the sodium sulfate is extracted returns to a water inlet of the desalination unit B for circular treatment;
example 6
FIG. 6 shows a process flow diagram of the present invention. The acidification tank is communicated with the water inlet of the pretreatment device 1, the water outlet of the pretreatment device 1 is communicated with the water inlet of the membrane filtration device 2, the water outlet of the membrane filtration device 2 is communicated with the water inlet of the electrodialysis water inlet tank 3, the water outlet of the electrodialysis water inlet tank 3 is communicated with the water inlet of the electrodialysis device I4, the fresh water produced by the electrodialysis device I4 is communicated with the water inlet of the electrodialysis production water tank I14, the concentrated water of the electrodialysis device I4 is communicated with the water inlet of the electrodialysis concentrated water tank I5, the water outlet of the electrodialysis concentrated water tank I5 is communicated with the water inlet of the reaction tank 7, the medicine adding port of the recycling agent 6 is communicated with the medicine adding port of the reaction tank 7, the water outlet of the reaction tank 7 is communicated with the water inlet of the filtration device 8, the phosphate fertilizer 9 separated by the filtration device 8 is separately collected and stored, the water outlet of the filtration device 8 is communicated with the water inlet of the crystallization kettle 10, the water outlet of the crystallization kettle 10 is communicated with the water inlet of the centrifuge 11, the sodium sulfate 12 separated by the centrifuge 11 is separately collected and stored, and the water outlet of the centrifuge 11 is communicated to the water inlet of the electrodialysis water inlet tank 3. The water outlet of the electrodialysis water production tank I13 is communicated to the biochemical system H for treatment and then is discharged after reaching the standard.
Claims (10)
1. The utility model provides a system for treating and recycling waste water which characterized in that: comprises a filtering unit, a desalting unit, a phosphorus extraction unit and a sodium sulfate extraction unit;
the filtering unit comprises a pretreatment device and a membrane filtering device;
the desalting unit comprises an electrodialysis water inlet tank, an electrodialysis device I, an electrodialysis concentrated water tank I and an electrodialysis production water tank I;
the phosphorus extraction unit comprises a dosing reaction device and a filtering device;
the sodium sulfate extracting unit comprises a crystallization kettle and a centrifuge;
the pretreatment device is communicated with an inlet of a membrane filtration device, a water outlet of the membrane filtration device is communicated with a water inlet of an electrodialysis water inlet tank, a water outlet of the electrodialysis water inlet tank is communicated with a water inlet of an electrodialysis device I, a strong brine outlet of the electrodialysis device I is communicated with a water inlet of an electrodialysis strong brine tank I, and a fresh water outlet of the electrodialysis device I is communicated with a water inlet of an electrodialysis precipitation water tank I;
the water outlet of the electrodialysis concentrated water tank I is communicated with the water inlet of a dosing reaction device, the outlet of the dosing reaction device is communicated with the water inlet of a filtering device, the water outlet of the filtering device is communicated with the water inlet of a crystallization kettle, and the water outlet of the crystallization kettle is communicated with the water inlet of a centrifuge;
or the water outlet of the electrodialysis concentrated water tank I is communicated with the water inlet of the crystallization kettle, the water outlet of the crystallization kettle is communicated with the water inlet of the centrifuge, the water outlet of the centrifuge is communicated with the water inlet of the dosing reaction device, and the outlet of the dosing reaction device is communicated with the water inlet of the filtering device;
and the centrifugate of the centrifuge or the filtrate of the filtering device enters an electrodialysis water inlet tank.
2. The treatment and reuse system according to claim 1, further comprising a COD concentration unit; the COD concentration unit comprises a reverse osmosis device I, a reverse osmosis concentrated water tank I, a reverse osmosis water production tank I, an electrodialysis device II, an electrodialysis concentrated water tank II, an electrodialysis water production tank II, a reverse osmosis device II and a reverse osmosis concentrated water tank II;
the water outlet of the electrodialysis water production tank I is communicated with the water inlet of the reverse osmosis device I; a concentrated water outlet of the reverse osmosis device I is communicated with a water inlet of the reverse osmosis concentrated water tank I; a fresh water outlet of the reverse osmosis device I is communicated with a water inlet of the reverse osmosis water production tank I; the water outlet of the reverse osmosis concentrated water tank I is communicated with the water inlet of the electrodialysis device II; a concentrated water outlet of the electrodialysis device II is communicated with an inlet of the electrodialysis concentrated water tank II; a fresh water outlet of the electrodialysis device II is communicated with a water inlet of the reverse osmosis device II; and a concentrated water outlet of the reverse osmosis device II is communicated with a water inlet of the reverse osmosis concentrated water tank II.
3. The treatment and recycling system according to claim 2, wherein a water outlet of the electrodialysis concentrate tank II is communicated with a water inlet of the electrodialysis water inlet tank; the fresh water outlet of the reverse osmosis device II is communicated with the water inlet of the reverse osmosis water production tank I.
4. The treatment and reuse system according to claim 3, further comprising a COD treatment unit; the COD treatment unit is a high-grade anaerobic tower or an evaporator; the high-grade anaerobic tower is an IC anaerobic tower;
the water outlet of the reverse osmosis concentrated water tank II is communicated with the water inlet of the high-grade anaerobic tower; the effluent of the high-grade anaerobic tower returns to the filtering unit;
or the water outlet of the reverse osmosis concentrated water tank II is communicated with the water inlet of the evaporator.
5. The treatment and reuse system according to claim 3, further comprising a depth treatment unit; the advanced treatment unit comprises a secondary reverse osmosis device, a secondary reverse osmosis water production tank, a tertiary reverse osmosis device and a tertiary reverse osmosis water production tank;
the water outlet of the reverse osmosis water production tank I is communicated with the water inlet of the secondary reverse osmosis device; a fresh water outlet of the second-stage reverse osmosis device is communicated with a water inlet of the second-stage reverse osmosis water production tank; the water outlet of the second-stage reverse osmosis water production tank is communicated with the water inlet of the third-stage reverse osmosis device.
6. The treatment and reuse system according to claim 5, wherein the concentrate outlet of the secondary reverse osmosis device is communicated with the water inlet of the electrodialysis water production tank I; and a concentrated water outlet of the third-stage reverse osmosis device is communicated with a water inlet of the reverse osmosis water production tank I.
7. The treatment and recycling system according to claim 2, wherein the pretreatment device is a filtration device, and the filtration method is membrane filtration, filter pressing of a filter press, filtration of a candle filter, and filtration of a centrifuge;
the membrane filtering device is an organic membrane filtering device or an inorganic membrane filtering device; the organic membrane material is at least one of Polyacrylonitrile (PAN), Polysulfone (PSF), Polytetrafluoroethylene (PTFE), Polyethersulfone (PES), Polystyrene (PS), polyvinylidene fluoride (PVDF) or polyvinyl chloride (PVC); the inorganic film material is silicon carbide or ceramic;
the membrane filtering device is a flat plate type, a roll type or a curtain type;
the membrane filtering device is of an external pressure type or an internal pressure type;
the reverse osmosis device I and the reverse osmosis device II are disc tube type reverse osmosis (DTRO) or seawater desalination reverse osmosis;
the filtration method of the phosphorus extraction unit filtration device comprises membrane filtration, filter pressing of a filter press, filtration of a candle filter and filtration of a centrifuge; the filtration precision of the filter device is 1-20 μm.
8. A process for treating wastewater using the treatment and reuse system according to any one of claims 1 to 7, comprising the steps of:
(1) the wastewater enters a filtering unit to remove impurities;
(2) the effluent of the filtering unit enters a desalting unit for treatment, the concentrated water of the desalting unit enters a phosphorus extraction unit for phosphorus extraction, then enters a sodium sulfate extraction unit for sodium sulfate extraction, and the centrifugate of the sodium sulfate extraction unit enters an electrodialysis water inlet tank; or the concentrated water of the desalting unit enters a sodium sulfate extracting unit and then enters a phosphorus extracting unit, and the filtrate of the phosphorus extracting unit enters an electrodialysis water inlet tank;
(3) fresh water of the desalination unit enters a COD concentration unit, fresh water of a reverse osmosis device I and fresh water of a reverse osmosis device II in the COD concentration unit enter an advanced treatment unit for treatment, and concentrated water of the COD concentration unit enters a COD treatment unit for anaerobic methanogenesis or evaporative concentration; the produced water of the COD treatment unit returns to the front end of the filtering unit for treatment; the steam after evaporation and concentration is utilized or condensed to be used as reuse water;
(4) the concentrated water separated by the second-stage reverse osmosis device returns to the water inlet of the reverse osmosis device I of the COD concentration unit for continuous circulation treatment.
9. The process according to claim 8,
the wastewater is plant oil soap horn wastewater, is wastewater obtained by acidifying plant oil saponin through sulfuric acid, and has COD of 30000-40000mg/L, electric conductivity of 60000-80000 mu s/cm and salt content of 50000-70000 mg/L;
the conductivity of the fresh water produced by the desalting unit is 1000 mu s/cm, and the conductivity of the concentrated brine is 150000 mu s/cm;
the process of the phosphorus extraction unit comprises the following steps: adding a recycling agent into the wastewater to regulate the pH value, then carrying out contact reaction, and filtering and separating out phosphorus-containing solids;
the process of the sodium sulfate extracting unit comprises the following steps: controlling the temperature of the crystallization kettle to be-5 ℃ to-3 ℃, and feeding the mixed liquid discharged from the crystallization kettle into a centrifuge to separate sodium sulfate crystals.
10. The process of claim 9, wherein the recovery agent is sodium hydroxide, sodium oxide, calcium hydroxide, calcium oxide, magnesium hydroxide, magnesium oxide, potassium hydroxide, potassium oxide; when the recycling agent is sodium hydroxide, sodium oxide, magnesium hydroxide, magnesium oxide, potassium hydroxide or potassium oxide, Ca in the phosphorus-containing wastewater2+The content of Ca in the phosphorus-containing wastewater is required to meet the requirement2+The concentration of (b) needs to be greater than the concentration of phosphorus;
the pH is 6-10; the contact reaction time is 20-60 min.
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| JP2003290775A (en) * | 2002-04-01 | 2003-10-14 | Japan Organo Co Ltd | Method and apparatus for treating desalted waste water |
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| CN109665659A (en) * | 2019-03-01 | 2019-04-23 | 大连波美科技有限公司 | A kind of the treatment for reuse system and technique of soybean liquefaction waste water |
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2020
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2003290775A (en) * | 2002-04-01 | 2003-10-14 | Japan Organo Co Ltd | Method and apparatus for treating desalted waste water |
| KR20050012875A (en) * | 2005-01-13 | 2005-02-02 | 아쿠아셀 주식회사 | A water reclamation and reuse system with an equipment for removing TDS |
| CN103588345A (en) * | 2012-08-14 | 2014-02-19 | 罗代洪 | Chemical recycling method for treating phosphorus-containing wastewater from electrode foil production |
| CN106007128A (en) * | 2016-07-28 | 2016-10-12 | 毛强平 | Treatment method for phosphorus-containing oily wastewater |
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