TWI602607B - Flocculant mixture and flocculation method - Google Patents
Flocculant mixture and flocculation method Download PDFInfo
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- TWI602607B TWI602607B TW102118697A TW102118697A TWI602607B TW I602607 B TWI602607 B TW I602607B TW 102118697 A TW102118697 A TW 102118697A TW 102118697 A TW102118697 A TW 102118697A TW I602607 B TWI602607 B TW I602607B
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- coagulant
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- 239000000203 mixture Substances 0.000 title claims description 76
- 238000000034 method Methods 0.000 title claims description 31
- 230000016615 flocculation Effects 0.000 title 1
- 238000005189 flocculation Methods 0.000 title 1
- 239000000701 coagulant Substances 0.000 claims description 150
- 241000196324 Embryophyta Species 0.000 claims description 57
- 229920000642 polymer Polymers 0.000 claims description 55
- 239000011345 viscous material Substances 0.000 claims description 44
- 239000000725 suspension Substances 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000005345 coagulation Methods 0.000 claims description 24
- 230000015271 coagulation Effects 0.000 claims description 24
- 229920006318 anionic polymer Polymers 0.000 claims description 22
- 240000000491 Corchorus aestuans Species 0.000 claims description 17
- 235000011777 Corchorus aestuans Nutrition 0.000 claims description 17
- 235000010862 Corchorus capsularis Nutrition 0.000 claims description 17
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 16
- 238000005354 coacervation Methods 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 10
- 241001474374 Blennius Species 0.000 claims description 8
- -1 isomalt polysaccharide Chemical class 0.000 claims description 8
- 239000004317 sodium nitrate Substances 0.000 claims description 8
- 235000010344 sodium nitrate Nutrition 0.000 claims description 8
- 240000004507 Abelmoschus esculentus Species 0.000 claims description 7
- 241000219357 Cactaceae Species 0.000 claims description 7
- 240000008790 Musa x paradisiaca Species 0.000 claims description 7
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- 102000003886 Glycoproteins Human genes 0.000 claims description 6
- 108090000288 Glycoproteins Proteins 0.000 claims description 6
- 240000008955 Dioscorea japonica Species 0.000 claims description 5
- 235000005251 Dioscorea japonica Nutrition 0.000 claims description 5
- 241000233805 Phoenix Species 0.000 claims description 5
- 235000013399 edible fruits Nutrition 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 240000006394 Sorghum bicolor Species 0.000 claims description 4
- 235000011684 Sorghum saccharatum Nutrition 0.000 claims description 4
- 241001261506 Undaria pinnatifida Species 0.000 claims description 4
- 240000003243 Thuja occidentalis Species 0.000 claims description 3
- 235000008109 Thuja occidentalis Nutrition 0.000 claims description 3
- 239000008394 flocculating agent Substances 0.000 claims description 3
- 235000021108 sauerkraut Nutrition 0.000 claims description 3
- 229920001282 polysaccharide Polymers 0.000 claims description 2
- 239000005017 polysaccharide Substances 0.000 claims description 2
- 235000010439 isomalt Nutrition 0.000 claims 1
- 239000000905 isomalt Substances 0.000 claims 1
- HPIGCVXMBGOWTF-UHFFFAOYSA-N isomaltol Natural products CC(=O)C=1OC=CC=1O HPIGCVXMBGOWTF-UHFFFAOYSA-N 0.000 claims 1
- 239000002351 wastewater Substances 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 20
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- 230000000694 effects Effects 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
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- 229910052731 fluorine Inorganic materials 0.000 description 3
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 2
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- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 229920000855 Fucoidan Polymers 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- 244000020551 Helianthus annuus Species 0.000 description 2
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 241000207929 Scutellaria Species 0.000 description 2
- 244000300264 Spinacia oleracea Species 0.000 description 2
- 235000009337 Spinacia oleracea Nutrition 0.000 description 2
- 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 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 229920006317 cationic polymer Polymers 0.000 description 2
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- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
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- 235000011852 gelatine desserts Nutrition 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
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- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 240000002132 Beaucarnea recurvata Species 0.000 description 1
- 241000167854 Bourreria succulenta Species 0.000 description 1
- KBVFOJAXNDOKET-UHFFFAOYSA-N CC(CC)S(=O)(=O)O.C(C=C)N Chemical compound CC(CC)S(=O)(=O)O.C(C=C)N KBVFOJAXNDOKET-UHFFFAOYSA-N 0.000 description 1
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004155 Chlorine dioxide Substances 0.000 description 1
- 244000303965 Cyamopsis psoralioides Species 0.000 description 1
- 241000195955 Equisetum hyemale Species 0.000 description 1
- 229920002907 Guar gum Polymers 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
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 241000218657 Picea Species 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
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- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- 235000014680 Saccharomyces cerevisiae Nutrition 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
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- 125000002947 alkylene group Chemical group 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- DNEHKUCSURWDGO-UHFFFAOYSA-N aluminum sodium Chemical compound [Na].[Al] DNEHKUCSURWDGO-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- KXIZOZCXWLMMAZ-UHFFFAOYSA-N aniline;formaldehyde;hydrochloride Chemical compound Cl.O=C.NC1=CC=CC=C1 KXIZOZCXWLMMAZ-UHFFFAOYSA-N 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 235000019693 cherries Nutrition 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- 238000011278 co-treatment Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
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- 238000010411 cooking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 150000007973 cyanuric acids Chemical class 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
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- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229940014259 gelatin Drugs 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
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- 239000011941 photocatalyst Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
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- 229920000768 polyamine Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 229940080314 sodium bentonite Drugs 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229940080313 sodium starch Drugs 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 229940032147 starch Drugs 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000009777 vacuum freeze-drying Methods 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Landscapes
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Description
本發明係關於一種凝聚劑混合物及一種凝聚方法。 The present invention relates to a coagulant mixture and a coacervation process.
工業廢水之品質隨著時間及技術革新而發生變化,且需不斷優化用於廢水處理之方法。例如,在接到降低用於平面顯示器之玻璃基板之厚度之請求時,使用液態藥劑(諸如氫氟酸)拋光玻璃基板之量則會增加。然後,玻璃基板所排放的拋光廢水係極為濃,且據稱,該種廢水處理係困難。 The quality of industrial wastewater changes over time and technological innovations, and methods for wastewater treatment need to be continually optimized. For example, when a request to reduce the thickness of a glass substrate for a flat panel display is received, the amount of polishing the glass substrate using a liquid medicament such as hydrofluoric acid increases. Then, the polishing wastewater discharged from the glass substrate is extremely concentrated, and it is said that this kind of wastewater treatment is difficult.
自日本特許公開專利申請案第Hei 11-114313號得知一種含有黃花箭芝(mulukhiyah)、乾燥黃花箭芝及黃花箭芝抽出物中至少一者之凝聚劑。 A coagulant containing at least one of mulukhiyah, dried yellow arrow cherries, and scutellaria chinensis extract is known from Japanese Laid-Open Patent Application No. Hei 11-114313.
日本特許公開專利申請案第Hei 11-114313號中所揭示之凝聚劑可有效使一群懸浮顆粒凝聚。然而,存在對以更高性能凝聚濃廢水之凝聚劑之需求。 The coagulant disclosed in Japanese Laid-Open Patent Application No. Hei 11-114313 is effective for agglomerating a group of suspended particles. However, there is a need for a coagulant which concentrates concentrated wastewater with higher performance.
因此,希望提供一種以更高性能凝聚濃廢水之凝聚劑混合物及凝聚方法。 Therefore, it is desirable to provide a coagulant mixture and agglomeration method for condensing concentrated wastewater with higher performance.
根據本發明之一實施例,提供一種凝聚劑混合物,其包括由陰離子聚合物凝聚劑及/或非離子聚合物凝聚劑形成之聚合物凝聚劑及植物所衍生的水溶性黏性物質,其中(VC0/VC1)之值小於15,其中VC0係在將0.5質量%之聚合物凝聚劑溶解於電導率不超過200 μS/cm之水 中之時所得到之黏度,且VC1係在將0.5質量%之聚合物凝聚劑溶解於電導率不超過200 μS/cm之水中,並將2質量%之硝酸鈉溶解於其中之時所得到之黏度。 According to an embodiment of the present invention, there is provided a coagulant mixture comprising a polymer coagulant formed from an anionic polymer coagulant and/or a nonionic polymer coagulant and a water-soluble viscous substance derived from a plant, wherein The value of VC 0 /VC 1 ) is less than 15, wherein VC 0 is obtained by dissolving 0.5% by mass of the polymer coagulant in water having a conductivity of not more than 200 μS/cm, and VC 1 is The 0.5% by mass of the polymer coagulant is dissolved in water having a conductivity of not more than 200 μS/cm and a viscosity obtained by dissolving 2% by mass of sodium nitrate therein.
根據本發明之一實施例,提供一種凝聚方法,其包括將凝聚劑混合物添加至懸浮液(廢水)中,然後使該懸浮液中之顆粒凝聚並分離。應注意,該水溶性黏性物質係部份溶解於該懸浮液(廢水)中,且剩餘部份係分散於該懸浮液中。 According to an embodiment of the present invention, there is provided a coacervation method comprising adding a coagulant mixture to a suspension (waste water), and then coagulating and separating the particles in the suspension. It should be noted that the water-soluble viscous substance is partially dissolved in the suspension (waste water), and the remainder is dispersed in the suspension.
根據該實施例之凝聚劑混合物或根據該實施例之凝聚方法中之凝聚劑混合物(在下文中,在某些情況中統稱為「根據該實施例之凝聚劑混合物等」)包括由陰離子聚合物凝聚劑及/或非離子聚合物凝聚劑形成之聚合物凝聚劑及植物所衍生的水溶性黏性物質,且該聚合物凝聚劑之黏度性質係經定義。應注意,因為該聚合物凝聚劑及該植物所衍生的水溶性黏性物質可彼此相容,且可發揮各自性質作為協同作用,故即使添加量較小,亦可提高廢水處理期間之凝聚速率,並顯著改善在廢水處理後之上清液澄清度及在濾餅過濾後之濾液澄清度。此係由於該聚合物凝聚劑及該植物所衍生的水溶性黏性物質可針對具有各種粒徑或表面電位之污泥顆粒(膠體顆粒)發揮不同凝聚作用。因此,該種凝聚劑混合物呈現針對凝聚濃廢水(廢液)之較高性質,且可有利地用於各個領域,諸如廢水處理、液晶面板製造工廠、半導體裝置製造、電子裝置製造、電子組件製造、電氣裝置製造、電氣組件製造、造紙廠、水廠/下水道、發酵工業、造紙工業及土木工程及土木建築工程。應注意,因為(VC0/VC1)之值係小於15,故根據本發明之凝聚劑混合物等呈現優良凝聚性能。另一方面,若VC1之數值係小,亦即(VC0/VC1)之值不小於15,凝聚速率則過於緩慢。因此,該凝聚劑混合物之凝聚性能係不可接受。 The coagulant mixture according to this embodiment or the coagulant mixture in the coagulation method according to this embodiment (hereinafter, collectively referred to as "agglomerate mixture according to the embodiment" or the like in some cases) includes agglomeration by an anionic polymer. The polymer coagulant formed by the agent and/or the nonionic polymer coagulant and the water-soluble viscous substance derived from the plant, and the viscosity properties of the polymer coagulant are defined. It should be noted that since the polymer coagulant and the water-soluble viscous substance derived from the plant are compatible with each other and can exert their respective properties as a synergistic effect, the aggregation rate during the wastewater treatment can be improved even if the addition amount is small. And significantly improve the clarity of the supernatant after the wastewater treatment and the clarity of the filtrate after filtration of the filter cake. This is because the polymer coagulant and the water-soluble viscous substance derived from the plant can exert different agglomeration effects on sludge particles (colloidal particles) having various particle diameters or surface potentials. Therefore, such a coagulant mixture exhibits a high property against condensed concentrated wastewater (waste liquid), and can be advantageously used in various fields such as wastewater treatment, liquid crystal panel manufacturing factory, semiconductor device manufacturing, electronic device manufacturing, electronic component manufacturing. , electrical equipment manufacturing, electrical component manufacturing, paper mills, water plants / sewers, fermentation industry, paper industry and civil engineering and civil engineering. It should be noted that since the value of (VC 0 /VC 1 ) is less than 15, the coagulant mixture or the like according to the present invention exhibits excellent cohesive properties. On the other hand, if the value of VC 1 is small, that is, the value of (VC 0 /VC 1 ) is not less than 15, the aggregation rate is too slow. Therefore, the cohesive properties of the coagulant mixture are unacceptable.
根據以下針對如附圖中所說明之其最佳模式實施例之詳細描 述,本發明之此等及其他目標、特徵及優勢將變得更為明瞭。 Detailed description of the best mode embodiment thereof as illustrated in the accompanying drawings These and other objects, features and advantages of the present invention will become more apparent.
在下文中,本發明之實施例將基於實例加以說明。然而,本發明之實施例並不限於此等實例,且此等實例中之各種數值及材料僅係實例。應注意,說明將以下列順序給出。 Hereinafter, embodiments of the invention will be described based on examples. However, the embodiments of the present invention are not limited to the examples, and the various numerical values and materials in the examples are merely examples. It should be noted that the description will be given in the following order.
1.根據本發明之實施例之凝聚劑混合物及凝聚方法,一般說明 1. Coagulant mixture and coacervation method according to an embodiment of the present invention, general description
2.實例1(凝聚劑混合物及凝聚方法),其他 2. Example 1 (coagulant mixture and coacervation method), other
[根據本發明之實施例之凝聚劑混合物及凝聚方法,一般說明] [Coagulant Mixture and Coagulation Method According to Embodiment of the Present Invention, General Description]
根據該實施例之凝聚劑混合物等宜具有不超過60°之靜止角,有利地不超過50°,更有利地不超過40°。此處,靜止角係(例如)藉由經由在離具有預定直徑之圓桌上預定高度處之漏斗沈積粉末,並在必要時施以預定振動而形成之粉末堆(錐體)之三個斜面之角度之平均值。可以說,具有較小靜止角之凝聚劑混合物具有較優良流動性。若凝聚劑混合物具有超過60°之靜止角,該凝聚劑混合物之流動性則過低。因此,該凝聚劑混合物在溶解於水中之時會結塊,或例如,導致該凝聚劑混合物在廢水中出現結塊現象,因為其在廢水處理期間並非均勻分散在廢水中。因此,無法達到足夠的凝聚效果。此外,當混合該凝聚劑混合物之時,很容易致使由陰離子聚合物凝聚劑及/或非離子聚合物凝聚劑形成之聚合物凝聚劑與植物所衍生的水溶性黏性物質分離。應注意,靜止角可藉由利用市售粉末測試裝置(粉末測試儀)加以測量。 The coagulant mixture or the like according to this embodiment preferably has an angle of repose of no more than 60°, advantageously no more than 50°, more advantageously no more than 40°. Here, the angle of repose is, for example, three slopes of a powder pile (cone) formed by depositing powder through a funnel at a predetermined height from a table having a predetermined diameter, and applying a predetermined vibration if necessary. The average of the angles. It can be said that the coagulant mixture having a small angle of repose has a superior fluidity. If the coagulant mixture has an angle of repose of more than 60, the fluidity of the coagulant mixture is too low. Thus, the coagulant mixture will agglomerate upon dissolution in water or, for example, cause agglomeration of the coagulant mixture in the wastewater because it is not uniformly dispersed in the wastewater during wastewater treatment. Therefore, sufficient agglomeration effect cannot be achieved. Further, when the coagulant mixture is mixed, it is easy to cause the polymer coagulant formed of the anionic polymer coagulant and/or the nonionic polymer coagulant to be separated from the water-soluble viscous substance derived from the plant. It should be noted that the angle of repose can be measured by using a commercially available powder testing device (powder tester).
此外,在根據該實施例之凝聚劑混合物等(其包括上述有利形式)中,(聚合物凝聚劑/植物所衍生的水溶性黏性物質)之質量比係有利地20/1至1/20。 Further, in the coagulant mixture or the like according to this embodiment, which includes the above advantageous forms, the mass ratio of (polymer flocculant/plant-derived water-soluble viscous substance) is advantageously from 20/1 to 1/20. .
此外,在根據該實施例之凝聚劑混合物等(其包括上述有利形式)中,植物所衍生的水溶性黏性物質可呈以下任何一者之形式: Further, in the coagulant mixture or the like according to this embodiment, which includes the above advantageous forms, the water-soluble viscous substance derived from the plant may be in the form of any one of the following:
(a)醣蛋白(諸如果膠及褐藻醣膠(fucoidan))之形式 (a) Forms of glycoproteins (such as gelatin and fucoidan)
(b)醣蛋白(諸如黏蛋白)之形式 (b) a form of glycoprotein (such as mucin)
(c)含凝聚材料之形式 (c) Forms containing condensed materials
(d)包含至少一種選自由黃花箭芝、長蒴黃麻、黃麻、落葵、紅鳳菜、香蕉、秋葵、日本山藥、仙人掌、海草、裙帶菜之孢子葉及果囊馬尾藻組成之群之材料或其乾燥產品之形式。此處,含果膠或褐藻醣膠之材料之實例包含黃花箭芝、長蒴黃麻、黃麻、落葵、紅鳳菜、香蕉、秋葵、仙人掌、海草、裙帶菜之孢子葉及果囊馬尾藻,而含黏蛋白之材料之實例包含黃花箭芝、長蒴黃麻、黃麻、落葵、紅鳳菜、香蕉、秋葵、仙人掌、海草、裙帶菜之孢子葉及果囊馬尾藻。此外,所有(d)中所述材料均包含異元多醣及醣蛋白。 (d) comprising at least one selected from the group consisting of scutellaria chinensis, sorghum jute, jute, arborvitae, red phoenix, banana, okra, Japanese yam, cactus, seaweed, wakame spp. The material of the group or its dry product. Here, examples of the material containing pectin or fucoidan include spruce leaves and fruits of Huanghuajianzhi, Changchun jute, jute, Luokui, Hongfengcai, banana, okra, cactus, seaweed, wakame Saccharomyces cerevisiae, and examples of mucin-containing materials include Huanghuajianzhi, Changchun jute, jute, arborvitae, red phoenix, banana, okra, cactus, seaweed, sauerkraut spore leaf and fruit sac ponytail Algae. Further, all of the materials described in (d) contain an isomeric polysaccharide and a glycoprotein.
此外,在根據該實施例之凝聚方法(其包括上述有利形式)中,懸浮液(廢水)可具有不超過500 μS/cm之電導率。 Further, in the coagulation method according to this embodiment, which includes the above advantageous form, the suspension (waste water) may have a conductivity of not more than 500 μS/cm.
在根據該實施例(在下文中統一簡稱為「該實施例」)之凝聚劑混合物或凝聚方法(其包括上述有利形式)中,陰離子聚合物凝聚劑之實例包括聚丙烯醯胺之部份水解產物、丙烯醯胺與丙烯酸之共聚物、丙烯醯胺與丙烯酸金屬鹽之共聚物、(甲基)丙烯酸基聚合物、海藻酸鈉、瓜爾膠鈉鹽、羧甲基纖維素鈉鹽及澱粉鈉鹽。此處,(甲基)丙烯酸基聚合物之實例包括聚甲基丙烯醯胺之部份水解產物,丙烯酸或甲基丙烯酸與丙烯醯胺或甲基丙烯醯胺及其鹽之共聚物,丙烯酸或甲基丙烯酸、丙烯醯胺或甲基丙烯醯胺與2-丙烯醯胺-甲基丙烷磺酸、乙烯基磺酸或乙烯基甲基磺酸及其鹽之三元共聚物,及聚丙烯醯胺或聚甲基丙烯醯胺及其鹽之磺甲基化化合物。此外,非離子聚合物凝聚劑之實例包括聚丙烯醯胺、聚甲基丙烯醯胺、澱粉、瓜爾膠、明膠、聚 氧乙烯及聚氧丙烯。 In the coagulant mixture or coacervation method according to this embodiment (hereinafter collectively referred to as "this embodiment"), which includes the above advantageous forms, examples of the anionic polymer flocculant include a partial hydrolyzate of polyacrylamide , copolymer of acrylamide and acrylic acid, copolymer of acrylamide and metal acrylate, (meth)acrylic polymer, sodium alginate, sodium guar, sodium carboxymethylcellulose and sodium starch salt. Here, examples of the (meth)acryl-based polymer include a partial hydrolyzate of polymethacrylamide, a copolymer of acrylic acid or methacrylic acid with acrylamide or methacrylamide and a salt thereof, acrylic acid or Terpolymer of methacrylic acid, acrylamide or methacrylamide and 2-propenylamine-methylpropanesulfonic acid, vinylsulfonic acid or vinylmethanesulfonic acid and salts thereof, and polypropylene fluorene A sulfomethylated compound of an amine or polymethacrylamide and a salt thereof. Further, examples of the nonionic polymer coagulant include polyacrylamide, polymethacrylamide, starch, guar gum, gelatin, and poly Oxyethylene and polyoxypropylene.
此外,可使用作為該實施例中植物所衍生的水溶性黏性物質之原材料之原材料植物之葉子、莖、主幹、根、果實及花瓣中之任何部位。然而,特定言之,端看該原材料植物,宜使用(特定言之)葉子、莖、主幹及花朵之部位,或更特定言之,葉子及莖之部位,因為其等易於加工成粉末。該原材料植物之種植位置或其種植季節並無特定限制。該植物所衍生的水溶性黏性物質有利地呈乾燥產品之形式,其係藉由在低於100℃之溫度下乾燥原材料植物所得。在該原材料植物係在不低於100℃下加以乾燥之情況中,包含在該原材料植物中一類水溶性聚合物組分(具體言之,例如,聚合物異元多醣)會被熱劣化(例如,由於切斷該聚合物異元多醣之主鏈或側鏈而使分子量下降,由於分子內交聯而變得不溶、碳化反應所致)。結果,凝聚性能可有所下降。乾燥方法之實例包括曬乾、於陰涼處風乾、熱風乾、真空乾燥及冷凍乾燥。此外,在以低於100℃之溫度對該原材料植物加以乾燥之前或在乾燥的同時,使該原材料植物粉碎係有利。為進行粉碎,可使用常見粉碎機。 Further, any part of the leaves, stems, trunks, roots, fruits and petals of the raw material of the raw material which is a raw material of the water-soluble viscous substance derived from the plant in the embodiment can be used. However, in particular, it is preferable to use (in particular) the parts of the leaves, stems, stems and flowers, or more specifically, the leaves and stems, because they are easy to process into powders. There are no specific restrictions on the planting location of the raw plant or its growing season. The water-soluble viscous material derived from the plant is advantageously in the form of a dry product obtained by drying the raw material plants at a temperature below 100 °C. In the case where the raw plant plant is dried at not lower than 100 ° C, a water-soluble polymer component (specifically, for example, a polymer heteropolysaccharide) contained in the raw material plant may be thermally deteriorated (for example) The molecular weight is lowered by cutting the main chain or the side chain of the polymer heteropolysaccharide, and is insoluble due to intramolecular crosslinking, resulting in a carbonization reaction. As a result, the cohesive properties can be reduced. Examples of the drying method include drying, drying in a cool place, hot air drying, vacuum drying, and freeze drying. Further, it is advantageous to pulverize the raw material plant before drying the raw material plant at a temperature lower than 100 ° C or while drying. For comminution, a common pulverizer can be used.
在該實施例中,可使用事先已與例如以下凝聚助劑、無機凝聚劑及有機凝結劑組合之凝聚劑混合物。或者,該凝聚劑混合物可與其組合使用(亦即獨立地加入懸浮液中)。藉由使該凝聚劑混合物與此等製劑組合,或與其組合地使用該凝聚劑混合物,可進一步改善凝聚性質。在與無機凝聚劑一起使用之情況中,宜在將該無機凝聚劑添加至懸浮液中之後添加根據該實施例之凝聚劑混合物等。此外,在與有機凝結劑一起使用之情況中,宜在將該有機凝結劑添加至懸浮液中的同時或之後添加根據該實施例之該凝聚劑混合物等。 In this embodiment, a coagulant mixture which has been previously combined with, for example, the following coagulating aid, inorganic coagulant and organic coagulant may be used. Alternatively, the coagulant mixture can be used in combination therewith (i.e., separately added to the suspension). The coacervation properties can be further improved by combining the coagulant mixture with such formulations, or in combination with the coagulant mixture. In the case of being used together with the inorganic coagulant, it is preferred to add the coagulant mixture or the like according to this embodiment after the inorganic coagulant is added to the suspension. Further, in the case of use together with an organic coagulant, it is preferred to add the coagulant mixture or the like according to this embodiment at the same time as or after the addition of the organic coagulant to the suspension.
此處,凝聚助劑之實例包括消石灰、矽酸鈉、膨潤土及飛塵。此外,無機凝聚劑之實例包括硫酸鋁(明礬)、聚合氯化鋁(PAC)、鋁 酸鈉、硫酸亞鐵、氯化鐵、硫酸鐵、氯化綠礬、改性的鹼性硫酸鋁(LACS)及活性矽石。此外,有機凝結劑之實例包括氯化二甲基二烯丙基銨、烷基環氧氯丙烷縮合物、聚乙烯亞胺、二氯化烷烴(alkylene dichloride)與聚伸烷基聚胺之縮合產物、二氰胺-福馬林縮合物、鹽酸苯胺甲醛聚合物、聚六亞甲基硫脲乙酸酯及聚乙烯基苄基三甲基氯化銨。 Here, examples of the coagulating aid include slaked lime, sodium citrate, bentonite, and fly ash. Further, examples of the inorganic coagulant include aluminum sulfate (alum), polyaluminum chloride (PAC), aluminum Sodium, ferrous sulfate, ferric chloride, ferric sulfate, green chlorinated chloride, modified basic aluminum sulfate (LACS) and activated vermiculite. Further, examples of the organic coagulant include condensation of dimethyl diallyl ammonium chloride, alkyl epichlorohydrin condensate, polyethyleneimine, alkylene dichloride and polyalkylene polyamine. The product, dicyanamide-formalin condensate, aniline formaldehyde hydrochloride polymer, polyhexamethylene thiourea acetate and polyvinylbenzyltrimethylammonium chloride.
此外,根據該實施例之該凝聚劑混合物等可與螯合樹脂、螯合劑、活性碳、臭氧水、離子交換樹脂及離子交換膜、吸水樹脂、過氧化氫水、氯及液態氯、次氯酸鈉、二氧化氯、漂白粉、氯化異氰脲酸、矽藻土、光催化劑(諸如氧化鈦)、共處理劑(諸如生物處理劑)或類似物組合,或與其組合使用。 Further, the coagulant mixture or the like according to the embodiment may be combined with a chelating resin, a chelating agent, activated carbon, ozone water, an ion exchange resin, an ion exchange membrane, a water absorbing resin, hydrogen peroxide water, chlorine, liquid chlorine, sodium hypochlorite, Chlorine dioxide, bleaching powder, chlorinated isocyanuric acid, diatomaceous earth, photocatalyst (such as titanium oxide), a co-treatment agent (such as a biological treatment agent) or the like, or a combination thereof.
在某些情況中,可對作為根據該實施例之該凝聚劑混合物等之原材料之原材料植物進行酸處理及/或鹼處理。 In some cases, the raw material plants which are the raw materials of the coagulant mixture or the like according to the embodiment may be subjected to acid treatment and/or alkali treatment.
在根據該實施例之凝聚方法中,在將根據該實施例之該凝聚劑混合物等添加至懸浮液中之前,該根據該實施例之該凝聚劑混合物等係有利地呈溶解及分散(部份溶解,且剩餘部份被分散,同樣適用於下文)於水中之形式。然後,就將根據該實施例之該凝聚劑混合物等添加至懸浮液(廢水)中之方法而言,可直接將呈粉末形式之根據該實施例之該凝聚劑混合物等添加至該懸浮液中。然而,更為有利的是將溶解及分散於水中之根據該實施例之該凝聚劑混合物等添加至懸浮液中。該懸浮液中之顆粒在凝聚並分離後,可進行脫水處理。在脫水處理中,可使用常見脫水機。例如可使用壓濾機、真空脫水機、帶式壓榨脫水機、離心脫水機及螺桿壓機。 In the coagulation method according to this embodiment, the coagulant mixture or the like according to the embodiment is advantageously dissolved and dispersed (partially) before the coagulant mixture or the like according to the embodiment is added to the suspension. Dissolved, and the remainder is dispersed, the same applies to the form in water below. Then, in the method of adding the coagulant mixture or the like according to the embodiment to the suspension (waste water), the coagulant mixture or the like according to the embodiment may be directly added to the suspension in the form of a powder. . However, it is more advantageous to add the coagulant mixture or the like according to this embodiment to the suspension dissolved and dispersed in water. After the particles in the suspension are coagulated and separated, they can be subjected to dehydration treatment. In the dehydration treatment, a common dehydrator can be used. For example, a filter press, a vacuum dehydrator, a belt press dehydrator, a centrifugal dehydrator, and a screw press can be used.
根據該實施例之凝聚劑混合物等相對於該懸浮液之添加量依據目標懸浮液(廢水)之類型或與另一製劑之組合而有顯著差異。因此,藉由進行各種測試,便可測定添加量。然而,大約0.05 mg/l至200 mg/l(0.05 ppm至200 ppm),有利地0.1 mg/l至100 mg/l(0.1 ppm至100 ppm),更有利地0.5 mg/l至20 mg/l(0.5 ppm至20 ppm)可作為例子。若根據該實施例之凝聚劑混合物等之添加量過少,則可能無法達到有利凝聚效果。若添加量過大,則可降低凝聚效果。 The addition amount of the coagulant mixture or the like according to this embodiment with respect to the suspension is significantly different depending on the type of the target suspension (waste water) or the combination with another preparation. Therefore, the amount of addition can be determined by performing various tests. However, approximately 0.05 mg/l to 200 Mg/l (0.05 ppm to 200 ppm), advantageously 0.1 mg/l to 100 mg/l (0.1 ppm to 100 ppm), more advantageously 0.5 mg/l to 20 mg/l (0.5 ppm to 20 ppm) as an example. If the amount of the aggregating agent mixture or the like according to this embodiment is too small, a favorable agglomeration effect may not be obtained. If the amount added is too large, the agglomeration effect can be reduced.
可藉由在25℃及100 rpm下使用布氏(Brookfield)黏度計測量經溶解及分散成具有預定濃度之樣品獲得黏度。此外,可依據JIS K0130:2008測量電導率。此外,可依據JIS R9301-2-2:1999測量靜止角。 The viscosity can be obtained by dissolving and dispersing into a sample having a predetermined concentration by using a Brookfield viscometer at 25 ° C and 100 rpm. In addition, the conductivity can be measured in accordance with JIS K0130:2008. In addition, the angle of repose can be measured in accordance with JIS R9301-2-2:1999.
[實例1] [Example 1]
實例1係關於根據該實施例之凝聚劑混合物及凝聚方法。 Example 1 relates to a coagulant mixture and a coacervation method according to this embodiment.
根據實例1之凝聚劑混合物包括(A)由陰離子聚合物凝聚劑及/或非離子聚合物凝聚劑組成之聚合物凝聚劑,及(B)植物所衍生的水溶性黏性物質,其中(VC0/VC1)之值小於15,其中VC0係在將0.5質量%之聚合物凝聚劑溶解於電導率不超過200 μS/cm之水中之時所得到之黏度,且VC1係在將0.5質量%之聚合物凝聚劑溶解於電導率不超過200 μS/cm之水中,並將2質量%之硝酸鈉溶解於其中之時所得到之黏度。此處,廢水含有大量各類鹽。使此種廢水模式化,並將硝酸鈉(NaNO3)溶解於其中,以在某種程度上模擬廢水之狀態。 The coagulant mixture according to Example 1 comprises (A) a polymer coagulant composed of an anionic polymer coagulant and/or a nonionic polymer coagulant, and (B) a water-soluble viscous material derived from a plant, wherein (VC) The value of 0 /VC 1 ) is less than 15, wherein VC 0 is a viscosity obtained by dissolving 0.5% by mass of the polymer coagulant in water having a conductivity of not more than 200 μS/cm, and VC 1 is at 0.5. The mass% of the polymer coagulant is dissolved in water having a conductivity of not more than 200 μS/cm and a viscosity obtained by dissolving 2% by mass of sodium nitrate therein. Here, the wastewater contains a large variety of salts. This wastewater was modeled and sodium nitrate (NaNO 3 ) was dissolved therein to simulate the state of the wastewater to some extent.
此外,在根據實例1之凝聚方法中,將根據實例1之凝聚劑混合物添加至懸浮液中,並使該懸浮液中之顆粒凝聚並分離。 Further, in the coagulation method according to Example 1, the coagulant mixture according to Example 1 was added to the suspension, and the particles in the suspension were coagulated and separated.
在實例1中,就植物所衍生的水溶性黏性物質之原材料植物而言,使用黃花箭芝粉末、長蒴黃麻(葉子、莖、主幹、花朵及根)、黃麻(葉子及莖)及海草(葉子、莖及假根)之乾燥產品。此外,在比較實例1中,就形成凝聚劑混合物之原材料植物(在下文中稱為「添加劑」)而言,使用黃花箭芝粉狀產品、日本小松菜(葉子及莖)及菠菜 (葉子及莖)之乾燥產品。應注意,該黃花箭芝粉末與該黃花箭芝粉狀產品之粉碎方法及由此所得之粒徑有所不同。黃花箭芝粉末之粒徑平均為100目,而黃花箭芝粉狀產品在每個產品上有2目。 In Example 1, for the raw material plant of the water-soluble viscous substance derived from the plant, the arrow flower of the arrowhead, the jute (leaf, stem, trunk, flower and root), jute (leaf and stem) are used. And dry products of seaweed (leaves, stems and pseudo roots). Further, in Comparative Example 1, in the case of a raw material plant (hereinafter referred to as "additive") which forms a coagulant mixture, a powdered product of yellow arrow gum, Japanese komatsu (leaves and stems) and spinach are used. Dry product (leaves and stems). It should be noted that the powder of the arrowhead flower and the pulverization method of the powdered product of the arrowhead flower and the particle size obtained therefrom are different. The average particle size of Huanghua Jianzhi powder is 100 mesh, while the powdered product of Huanghuajianzhi has 2 mesh on each product.
然後,藉由熱風乾燥機使該等原材料植物在預定溫度下(但在低於100℃之溫度下)乾燥預定時間段,從而得到根據實例1之植物所衍生的水溶性黏性物質。該植物所衍生的水溶性黏性物質之水含量比係4.5質量%至25質量%,端看乾燥條件而定。對比較實例1之添加劑進行相同處理。然後,使用烹飪用食品處理器使由此而獲得之根據實例1之植物所衍生的水溶性黏性物質粉碎。亦對比較實例1之添加劑進行相同處理,黃花箭芝粉狀產品除外。 Then, the raw material plants are dried at a predetermined temperature (but at a temperature lower than 100 ° C) for a predetermined period of time by a hot air dryer, thereby obtaining a water-soluble viscous substance derived from the plant according to Example 1. The water-soluble viscous substance derived from the plant has a water content ratio of 4.5% by mass to 25% by mass, depending on drying conditions. The same treatment was carried out for the additive of Comparative Example 1. Then, the water-soluble viscous substance derived from the plant according to Example 1 thus obtained was pulverized using a food processor for cooking. The same treatment was also carried out for the additive of Comparative Example 1, except for the powdered product of Huanghuajianzhi.
就陰離子聚合物凝聚劑而言,使用市售聚丙烯醯胺之部份水解產物(陰離子聚合物凝聚劑A至陰離子聚合物凝聚劑H)。此外,就非離子聚合物凝聚劑而言,使用市售聚丙烯醯胺(非離子聚合物凝聚劑I)。應注意,該等陰離子聚合物凝聚劑A至陰離子聚合物凝聚劑H之部份水解之比例有所不同。具體言之,陰離子聚合物凝聚劑A中之部份水解之比例係3%,而按陰離子聚合物凝聚劑B、陰離子聚合物凝聚劑C、陰離子聚合物凝聚劑D、...次序之部份水解之比例愈高。陰離子聚合物凝聚劑H之部份水解之比例係100%。此外,非離子聚合物凝聚劑I之水解率係0%。各聚合物凝聚劑之黏度VC0及VC1之測量值(單位:10-3 Pa.s,厘泊),及(VC0/VC1)之值示於下表1中。然而,陰離子聚合物凝聚劑E至陰離子聚合物凝聚劑H之(VC0/VC1)之值不小於15,且因此,未滿足(VC0/VC1)之值係小於15之要求。 As the anionic polymer flocculating agent, a partial hydrolyzate (anionic polymer coagulant A to an anionic polymer coagulant H) of a commercially available polydecylamine is used. Further, as the nonionic polymer flocculating agent, a commercially available polypropylene decylamine (nonionic polymer coagulant I) is used. It should be noted that the proportion of partial hydrolysis of the anionic polymer coagulant A to the anionic polymer coagulant H is different. Specifically, the proportion of partial hydrolysis in the anionic polymer coagulant A is 3%, and the order of the anionic polymer coagulant B, the anionic polymer coagulant C, the anionic polymer coagulant D, ... The higher the proportion of hydrolysis. The proportion of partial hydrolysis of the anionic polymer coagulant H is 100%. Further, the hydrolysis rate of the nonionic polymer coagulant I was 0%. Each polymer coacervation agent of VC VC viscosity measurement value of 0 and 1 (unit: 10 -3 Pa.s, centipoise), and a value (VC 0 / VC 1) are shown in the Table 1. However, the anionic polymeric flocculant E to H of the anionic polymeric flocculant (VC 0 / VC 1) of not less than 15, and thus, is not satisfied (VC 0 / VC 1) of claim 15 is less than the value of the system.
黏度測量係以下列方式進行。具體言之,使用電導率不超過200 μS/cm之水(純水)。然後,藉由將0.5質量%之根據實例及比較實例之聚合物凝聚劑溶解於水中,測得黏度VC0。此外,藉由將0.5質量%之根據實例及比較實例之聚合物凝聚劑溶解於水中,並將2質量%之硝 酸鈉溶解其中,測得黏度VC1。使用布氏黏度計(由Toki Sangyo CO.,LTD製造)測量黏度。更具體言之,將樣品之溫度調節為25℃,並在100 rpm之轉速下測量黏度。 Viscosity measurement was performed in the following manner. Specifically, water (pure water) having a conductivity of not more than 200 μS/cm is used. Then, the viscosity VC 0 was measured by dissolving 0.5% by mass of the polymer coagulant according to the examples and the comparative examples in water. Further, the viscosity VC 1 was measured by dissolving 0.5% by mass of the polymer coagulant according to the examples and the comparative examples in water and dissolving 2% by mass of sodium nitrate therein. The viscosity was measured using a Brookfield viscometer (manufactured by Toki Sangyo Co., LTD). More specifically, the temperature of the sample was adjusted to 25 ° C, and the viscosity was measured at a rotation speed of 100 rpm.
表2顯示用於實例1-A至實例1-Q之陰離子聚合物凝聚劑及非離子聚合物凝聚劑對植物所衍生的水溶性黏性物質之質量比(聚合物凝聚劑/植物所衍生的水溶性黏性物質)。此外,表3顯示用於比較實例1-A至比較實例1-O之陰離子聚合物凝聚劑及陽離子聚合物凝聚劑對添加劑之質量比(聚合物凝聚劑/添加劑)。應瞭解,(聚合物凝聚劑/植物所衍生的水溶性黏性物質)之質量比或(聚合物凝聚劑/添加劑)之質量比在表2及表3中係由「混合比」表示。 Table 2 shows the mass ratio of the anionic polymer coagulant and the nonionic polymeric coagulant used in the examples 1-A to the examples 1-Q to the water-soluble viscous material derived from the plant (polymer coagulant/plant derived) Water-soluble viscous substance). Further, Table 3 shows the mass ratio (polymer coagulant/additive) of the anionic polymer coagulant and the cationic polymer coagulant to the additive for comparison of Examples 1-A to Comparative Examples 1-O. It is to be understood that the mass ratio of (polymer flocculant/water-soluble viscous substance derived from plant) or the mass ratio of (polymer flocculant/additive) is expressed by "mixing ratio" in Tables 2 and 3.
就用於凝聚評估之懸浮液(廢水)而言,使用以下懸浮液。具體言之,「半導體廢水A」係藉由對由液晶面板製造廠排放之含氟廢水進行pH調節及初級凝聚處理所得到之廢水。應注意,該「半導體廢水A」之pH係7.49,懸浮固體(SS)量係13 mg/l,且電導率係2470 μS/cm。此外,「半導體廢水B」係藉由對不同於該半導體廢水A之由液晶面板製造廠排放之含氟廢水進行pH調節及初級凝聚處理所得到之廢水。應注意,該「半導體廢水B」之pH係7.96,懸浮固體(SS)量係17 mg/l,且電導率係2690 μS/cm。此外,「半導體廢水C」係藉由對不同於該半導體廢水A及該半導體廢水B之由液晶面板製造廠排放 之含氟廢水進行pH調節及初級凝聚處理所得到之廢水。應注意,該「半導體廢水C」之pH係7.52,懸浮固體(SS)量係9 mg/l,且電導率係2230 μS/cm。 For the suspension (waste water) used for the coagulation evaluation, the following suspensions were used. Specifically, "semiconductor wastewater A" is a wastewater obtained by pH adjustment and primary coagulation treatment of fluorine-containing wastewater discharged from a liquid crystal panel manufacturer. It should be noted that the "semiconductor wastewater A" has a pH of 7.49, a suspended solids (SS) amount of 13 mg/l, and a conductivity of 2470 μS/cm. Further, the "semiconductor wastewater B" is a wastewater obtained by pH-adjusting and primary agglomeration treatment of fluorine-containing wastewater discharged from a liquid crystal panel manufacturer different from the semiconductor wastewater A. It should be noted that the "semiconductor wastewater B" has a pH of 7.96, a suspended solids (SS) amount of 17 mg/l, and a conductivity of 2690 μS/cm. In addition, "semiconductor wastewater C" is discharged by a liquid crystal panel manufacturer different from the semiconductor wastewater A and the semiconductor wastewater B. The wastewater obtained by pH adjustment and primary coagulation treatment of the fluorine-containing wastewater. It should be noted that the "semiconductor wastewater C" has a pH of 7.52, a suspended solids (SS) amount of 9 mg/l, and a conductivity of 2230 μS/cm.
就評估凝聚作用之方法而言,使用以下方法。具體言之,將80 ml用於凝聚評估之各懸浮液傾倒於具有瓶塞之100 ml量筒中。然後,藉由量液吸管將根據實例及比較實例之凝聚劑混合物等添加至用於凝聚評估之懸浮液中,以便具有預定濃度(關於固體含量當量之數值,參見表2及表3)。接下來,立即藉由上下翻轉10次對該量筒進行攪拌,此後容許靜置。然後,測量懸浮顆粒之沈降速率。應注意,沈降速率係基於凝聚界面由60 ml之位置下降至40 ml之位置之時間段來計算。此外,藉由目測檢查評估上清液在靜置3分鐘後之澄清度。上述測量結果示於表2及表3中。目測檢查結果中之「○」表示上清液係澄清,「△」表示上清液有點渾濁,而「×」表示上清液係渾濁。 For the method of evaluating cohesion, the following method is used. Specifically, 80 ml of each suspension for coagulation evaluation was poured into a 100 ml graduated cylinder with a stopper. Then, a coagulant mixture or the like according to the examples and the comparative examples was added to the suspension for coagulation evaluation by a measuring liquid pipette so as to have a predetermined concentration (for the value of the solid content equivalent, see Table 2 and Table 3). Next, the cylinder was immediately stirred by turning it upside down 10 times, and thereafter allowed to stand. Then, the sedimentation rate of the suspended particles was measured. It should be noted that the sedimentation rate is calculated based on the time period in which the agglomeration interface is lowered from the position of 60 ml to the position of 40 ml. In addition, the clarity of the supernatant after standing for 3 minutes was evaluated by visual inspection. The above measurement results are shown in Table 2 and Table 3. The "○" in the visual inspection result indicates that the supernatant was clarified, "△" indicates that the supernatant was a little cloudy, and "X" indicates that the supernatant was cloudy.
在實例1-A至1-Q中,各凝聚劑混合物之靜止角係不超過60°,(VC0/VC1)之值係小於15,且(聚合物凝聚劑/植物所衍生的水溶性黏性物質)之質量比係20/1至1/20。然後,將根據實例1-A至1-Q之凝聚劑混合物注入用於凝聚評估之懸浮液中,並加以攪拌。將該等凝聚劑混合物溶解及分散於用於凝聚評估之懸浮液中,並使污泥沈澱,從而致使上清液沈降。因此,證實該等凝聚劑混合物具有優良凝聚性能。 In Examples 1-A to 1-Q, the angle of repose of each coagulant mixture is not more than 60°, and the value of (VC 0 /VC 1 ) is less than 15, and (the polymer flocculant/plant-derived water solubility) The mass ratio of the viscous substance is 20/1 to 1/20. Then, the coagulant mixture according to Examples 1-A to 1-Q was injected into the suspension for coagulation evaluation and stirred. The coagulant mixture is dissolved and dispersed in a suspension for coagulation evaluation, and the sludge is precipitated, thereby causing the supernatant to settle. Therefore, it was confirmed that the coagulant mixtures have excellent cohesive properties.
另一方面,在比較實例1-A、比較實例1-B、比較實例1-C及比較實例1-D中,(VC0/VC1)之值不小於15,上清液有點渾濁或係渾濁,沈降速率係緩慢,且凝聚性能係不可接受。 On the other hand, in Comparative Example 1-A, Comparative Example 1-B, Comparative Example 1-C, and Comparative Example 1-D, the value of (VC 0 /VC 1 ) was not less than 15, and the supernatant was somewhat cloudy or turbid. Turbidity, the sedimentation rate is slow, and the cohesive properties are unacceptable.
此外,在比較實例1-E中,因為使用黃花箭芝粉狀產品,故靜止角之值超過60°。將凝聚劑混合物注入用於凝聚評估之懸浮液中,並加以攪拌。然後,該凝聚劑混合物在用於凝聚評估之懸浮液中結塊,上清液係渾濁,未得到沈降速率之數據,且凝聚性能係不可接受。 Further, in Comparative Example 1-E, since the powdery product of the arrowhead was used, the value of the angle of repose exceeded 60°. The coagulant mixture was injected into the suspension for coagulation evaluation and stirred. Then, the coagulant mixture was agglomerated in the suspension for coagulation evaluation, the supernatant was cloudy, no sedimentation rate data was obtained, and the coagulation performance was unacceptable.
此外,在比較實例1-F中,並未使用植物所衍生的水溶性黏性物質,上清液有點渾濁,沈降速率係緩慢,且凝聚性能係不可接受。 Further, in Comparative Example 1-F, the water-soluble viscous substance derived from the plant was not used, the supernatant was somewhat cloudy, the sedimentation rate was slow, and the aggregation property was unacceptable.
此外,在比較實例1-G至比較實例1-J中,(聚合物凝聚劑/植物所衍生的水溶性黏性物質)之質量比並不在20/1至1/20範圍內,上清液有點渾濁,沈降速率係緩慢,且凝聚性能係不可接受。此外,在比較實例1-K中,凝聚劑混合物等相對於懸浮液之添加量係極小。另一方面,在比較實例1-L中,凝聚劑混合物等相對於懸浮液之添加量係極大,上清液有點渾濁或係渾濁,沈降速率係緩慢,且凝聚性能係不可接受。 Further, in Comparative Example 1-G to Comparative Example 1-J, the mass ratio of (polymer flocculant/plant-derived water-soluble viscous substance) was not in the range of 20/1 to 1/20, and the supernatant was It is a bit turbid, the sedimentation rate is slow, and the cohesive properties are unacceptable. Further, in Comparative Example 1-K, the addition amount of the coagulant mixture or the like with respect to the suspension was extremely small. On the other hand, in Comparative Example 1-L, the addition amount of the coagulant mixture or the like with respect to the suspension was extremely large, the supernatant was somewhat cloudy or turbid, the sedimentation rate was slow, and the aggregation property was unacceptable.
在比較實例1-M中,使用陽離子聚合物凝聚劑,上清液係渾濁,沈降速率係緩慢,且凝聚性能係不可接受。 In Comparative Example 1-M, a cationic polymer coagulant was used, the supernatant was cloudy, the sedimentation rate was slow, and the cohesive properties were unacceptable.
在比較實例1-N至比較實例1-O中,使用日本小松菜及菠菜替代 植物所衍生的水溶性黏性物質,上清液有點渾濁,沈降速率係緩慢,且凝聚性能係不可接受。 In Comparative Example 1-N to Comparative Example 1-O, using Japanese Komatsu and Spinach instead Water-soluble viscous substances derived from plants, the supernatant is a bit turbid, the sedimentation rate is slow, and the cohesive properties are unacceptable.
如上所述,根據實例1之凝聚劑混合物包括由陰離子聚合物凝聚劑及/或非離子聚合物凝聚劑形成之聚合物凝聚劑及植物所衍生的水溶性黏性物質,且該聚合物凝聚劑之性質係經定義。因此,該種凝聚劑混合物具有針對凝聚濃廢水(廢液)之較高性質,且可有利地用於各個領域,諸如廢水處理、半導體裝置製造、電子裝置製造、電子組件製造、電氣裝置製造、電氣組件製造、造紙廠、水廠/下水道、發酵工業、造紙工業及土木工程及土木建築工程。 As described above, the coagulant mixture according to Example 1 includes a polymer coagulant formed of an anionic polymer coagulant and/or a nonionic polymer coagulant, and a water-soluble viscous substance derived from a plant, and the polymer coagulant The nature is defined. Therefore, such a coagulant mixture has a higher property against condensed concentrated wastewater (waste liquid), and can be advantageously used in various fields such as wastewater treatment, semiconductor device manufacturing, electronic device manufacturing, electronic component manufacturing, electrical device manufacturing, Electrical component manufacturing, paper mills, water plants/sewers, fermentation industry, paper industry and civil engineering and civil engineering.
雖然已基於有利實例對本發明之實施例進行描述,但本發明之實施例並不限於此等實例及所能作出的各種修改。在實例中,植物所衍生的水溶性黏性物質之原材料植物係單獨使用。然而,視情況藉由以組合方式使用該植物所衍生的水溶性黏性物質之原材料植物可達到類似凝聚性能。 Although the embodiments of the present invention have been described on the basis of advantageous embodiments, the embodiments of the present invention are not limited to the examples and various modifications that can be made. In the examples, the plant material of the water-soluble viscous material derived from the plant is used alone. However, similar agglomeration properties can be achieved by using a raw material plant of a water-soluble viscous substance derived from the plant in a combined manner.
應注意,本發明亦可採用以下組態。 It should be noted that the present invention can also adopt the following configuration.
[1]<<凝聚劑混合物>>一種凝聚劑混合物,其包含:由陰離子聚合物凝聚劑及/或非離子聚合物凝聚劑組成之聚合物凝聚劑;及植物所衍生的水溶性黏性物質,其中(VC0/VC1)之值小於15,其中VC0係在將0.5質量%之聚合物凝聚劑溶解於電導率不超過200 μS/cm之水中之時所得到之黏度,且VC1係在將0.5質量%之聚合物凝聚劑溶解於電導率不超過200 μS/cm之水中,並將2質量%之硝酸鈉溶解於其中之時所得到之黏度。 [1] <<Coagulant Mixture>> A coagulant mixture comprising: a polymer coagulant composed of an anionic polymer coagulant and/or a nonionic polymer coagulant; and a water-soluble viscous substance derived from a plant Wherein the value of (VC 0 /VC 1 ) is less than 15, wherein VC 0 is a viscosity obtained by dissolving 0.5% by mass of the polymer coagulant in water having a conductivity of not more than 200 μS/cm, and VC 1 The viscosity obtained by dissolving 0.5% by mass of the polymer coagulant in water having a conductivity of not more than 200 μS/cm and dissolving 2% by mass of sodium nitrate therein.
[2]如[1]之凝聚劑混合物,其中該凝聚劑混合物具有不超過60°之靜止角。 [2] The coagulant mixture according to [1], wherein the coagulant mixture has an angle of repose of not more than 60°.
[3]如[1]或[2]之凝聚劑混合物,其中(該聚合物凝聚劑/該植物所衍生的水溶性黏性物質)之質量比係20/1至1/20。 [3] The coagulant mixture according to [1] or [2], wherein the mass ratio of the polymer coagulant/water-soluble viscous substance derived from the plant is from 20/1 to 1/20.
[4]如[1]至[3]中任一項之凝聚劑混合物,其中該植物所衍生的水溶性黏性物質包括至少一種選自由黃花箭芝、長蒴黃麻、黃麻、落葵、紅鳳菜、香蕉、秋葵、日本山藥、仙人掌、海草、裙帶菜之孢子葉及果囊馬尾藻組成之群之材料。 [4] The coagulant mixture according to any one of [1] to [3] wherein the water-soluble viscous substance derived from the plant comprises at least one selected from the group consisting of arrowhead, sorghum, jute, jute, and sunflower , red phoenix, banana, okra, Japanese yam, cactus, seaweed, sauerkraut spores and fruit sacs.
[5]如[1]至[3]中任一項之凝聚劑混合物,其中該植物所衍生的水溶性黏性物質包含異元多醣。 [5] The coagulant mixture according to any one of [1] to [3] wherein the water-soluble viscous substance derived from the plant comprises an allopolysaccharide.
[6]如[1]至[3]中任一項之凝聚劑混合物,其中該植物所衍生的水溶性黏性物質包醣蛋白。 [6] The coagulant mixture according to any one of [1] to [3] wherein the water-soluble viscous substance derived from the plant is glycoprotein.
[7]如[1]至[3]中任一項之凝聚劑混合物,其中該植物所衍生的水溶性黏性物質包括凝聚材料。 [7] The coagulant mixture according to any one of [1] to [3] wherein the water-soluble viscous substance derived from the plant comprises a cohesive material.
[8]<<凝聚方法>>一種凝聚方法,其包括:將凝聚劑混合物添加至懸浮液中,該凝聚劑混合物包含:由陰離子聚合物凝聚劑及/或非離子聚合物凝聚劑組成之聚合物凝聚劑,及植物所衍生的水溶性黏性物質,其中(VC0/VC1)之值小於15,其中VC0係在將0.5質量%之聚合物凝聚劑溶解於電導率不超過200 μS/cm之水中之時所得到之黏度,且VC1係在將0.5質量%之聚合物凝聚劑溶解於電導率不超過200 μS/cm之水中,並將2質量%之硝酸鈉溶解於其中之時所得到之黏度;及使該懸浮液中之顆粒凝聚並分離。 [8] <<Coagulation method>> A coacervation method comprising: adding a coagulant mixture to a suspension, the coagulant mixture comprising: an aggregation consisting of an anionic polymer coagulant and/or a nonionic polymer coagulant a coagulant, and a water-soluble viscous substance derived from a plant, wherein (VC 0 /VC 1 ) has a value of less than 15, wherein VC 0 is dissolved in a 0.5% by mass polymer coagulant at a conductivity of not more than 200 μS. Viscosity obtained in water of /cm, and VC 1 is dissolved in 0.5% by mass of a polymer coagulant in water having a conductivity of not more than 200 μS/cm, and 2% by mass of sodium nitrate is dissolved therein The viscosity obtained at the time; and the particles in the suspension are coagulated and separated.
[9]如[8]之凝聚方法,其中該凝聚劑混合物具有不超過60°之靜止角。 [9] The coagulation method according to [8], wherein the coagulant mixture has an angle of repose of not more than 60°.
[10]如[8]或[9]之凝聚方法,其中(該聚合物凝聚劑/該植物所衍生的水溶性黏性物質)之質量比係20/1至1/20。 [10] The coagulation method according to [8] or [9], wherein the mass ratio of the polymer coagulant/water-soluble viscous substance derived from the plant is from 20/1 to 1/20.
[11]如[8]至[10]中任一項之凝聚方法,其中該懸浮液具有不低於500 μS/cm之電導率。 [11] The coagulation method according to any one of [8] to [10] wherein the suspension has a conductivity of not less than 500 μS/cm.
[12]如[8]至[11]中任一項之凝聚方法,其中該植物所衍生的水溶性黏性物質包括至少一種選自由黃花箭芝、長蒴黃麻、黃麻、落葵、紅鳳菜、香蕉、秋葵、日本山藥、仙人掌、海草、裙帶菜之孢子葉及果囊馬尾藻組成之群之材料。 [12] The coagulation method according to any one of [8] to [11] wherein the water-soluble viscous substance derived from the plant comprises at least one selected from the group consisting of arrowhead, sorghum, jute, jute, and sunflower. Red Fengcai, banana, okra, Japanese yam, cactus, seaweed, spore leaves of wakame and the group of horsetail algae.
[13]如[8]至[11]中任一項之凝聚方法,其中該植物所衍生的水溶性黏性物質包含異元多醣。 [13] The coagulation method according to any one of [8] to [11] wherein the water-soluble viscous substance derived from the plant comprises an allopolysaccharide.
[14]如[8]至[11]中任一項之凝聚方法,其中該植物所衍生的水溶性黏性物質包醣蛋白。 [14] The coagulation method according to any one of [8] to [11] wherein the plant is derived from a water-soluble viscous substance glycoprotein.
[15]如[8]至[11]中任一項之凝聚方法,其中該植物所衍生的水溶性黏性物質包括凝聚材料。 [15] The coagulation method according to any one of [8] to [11] wherein the water-soluble viscous substance derived from the plant comprises a coacervate material.
本發明包含與2012年6月28日於日本專利局(Japan Patent Office)申請之日本優先權專利申請案JP 2012-145018中所揭示有關之標的物,該案之全部內容以引用的方式併入。 The present invention contains subject matter related to that disclosed in Japanese Patent Application No. JP 2012-145018, filed on Jun. .
熟習此項技術者應瞭解,只要依據設計要求及其他因素,可在申請專利範圍範圍及其等效項之範圍內進行各種修改、組合、子組合及變更。 Those skilled in the art should understand that various modifications, combinations, sub-combinations and changes can be made within the scope of the scope of the claims and the equivalents thereof.
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| WO2016063745A1 (en) * | 2014-10-24 | 2016-04-28 | サンノプコ株式会社 | Viscoelasticity-adjusting agent |
| CN104355385A (en) * | 2014-10-27 | 2015-02-18 | 无锡伊佩克科技有限公司 | Industrial wastewater purification flocculant and preparation method thereof |
| CN104556335B (en) * | 2015-01-28 | 2016-10-05 | 山东大学 | A kind of graft modified natural polymer flocculant and its preparation method and application |
| JP6062986B2 (en) * | 2015-03-20 | 2017-01-18 | デクセリアルズ株式会社 | Filtration aid and filtration treatment method |
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