TW312685B - - Google Patents
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經濟部中央標準局員工消費合作社印裝 S126S5 Α7 Β7 五、發明説明(1) SI明之領城 本發明係闞於含丹寧聚合物之姐合物及使用彼等供淨化 水之方法。 筇明之背蜃 河水、湖水或地下水等之生水通常包含懸浮物。懋浮物 必須藉淨化除去Μ提供缠用於家庭及工業之水。懸浮物可 由僅由重力而不假借外力可沉降的大固體及不可沉降的物 質(時常呈膠態)所構成。懸浮物質之去除通常藉凝聚、 絮凝及沉積所完成。上述三種方法被稱為習知淨化法(參 照 Betz Handbook of Industrial Water Conditioning, 9th Edition, 1991, Betz Laboratories, Inc.,Printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs S126S5 Α7 Β7 V. Description of the invention (1) The leading city of SI This invention is a method of purifying water in the sister compound containing tannin polymer. The raw water of rivers, lakes or groundwater usually contains suspended solids. The buoyant matter must be purified to remove the water provided by M to be used in homes and industries. Suspended matter can be composed of large solids that can only be settled by gravity without using external force and non-settable materials (often colloidal). The removal of suspended material is usually done by coagulation, flocculation and sedimentation. The above three methods are called the conventional purification method (see Betz Handbook of Industrial Water Conditioning, 9th Edition, 1991, Betz Laboratories, Inc.,
Trevose, PA, pages 23 through 30)。 自然發生的懸浮粒子主要被負充電。水溶性有機陽離子 聚合物如聚胺及聚二烯丙基二甲基铵氯化物通常被用來淨 化具有高濁度(大於60 NTU,漘度測定的濁度軍位)之水 。於低濁度水(低於60 NTU)中,當水僅用陽離子聚合物 處理時,通常沒有足夠微粒形成可沉降絮凝物。無櫬凝聚 劑如硫酸鋁、聚合氛化鋁、硫酸鐵、氛化锇及铝酸納被替 代使用。此等無機凝聚劑相當便宜,且通常對淨化水有效 。然而,其傾向產生體積大的淤泥而很難脫水。又,該無 機凝聚劑僅在特定pH範圍内有效,因此在處理時需要通當 的水之pH調整。另外,所處理水中殘餘鐵及鋁離子會影響 下游操作如冷卻及锄爐處理,當水被最後排出時,亦會造 成健康及環境上問題。 —4 — 本紙張尺度適用中國國家標準(CNS ) Μ規格(210X297公釐) 83· 3.10,000 I. · I I I 裝 I j I I ί 訂 i—κ n ^ i (請先閲讀背面之注意^項再填寫本頁) 經濟部中央標準局員工消費合作社印製 3^26qs A7 _- __ 五、發明説明(2 ) 水溶性/分敗性三聚氰胺甲醛樹脂已被用來淨化低濁度 水,但樹脂内之殘餘甲醛會引起操作及處理上之困難。本 發明之目的為提供一種有效的淨化水之方法而不會導致無 機凝聚劑及三聚氰胺甲醛樹脂之缺點。 %昍夕廐沭 本發明提供一種姐合物•其製備方法及使用姐合物供淨 化水之方法。姐合物包含藉乙烯系不飽和單賭與丹寧聚合 獲得之水溶性/水分散性含丹寧聚合物。 有Μ抟g之說明 美國專利 4,558,080 ; 4,734,216 及 4,781,839 揭示一 種藉丹寧與胺基化合物及醛在酸性條件下反懕所得之丹寧 糸聚合物作為絮凝劑。該製法箱要在反應時小心監視pH值 及中間粘度以防配料膠凝。產物之長期安定性及殘餘胺與 甲醛於溶液中之量會造成操作上問題。 美國專利4,990,270揭示一種增稠劑,藉丙烯醯胺及陽 雜子單體與水不溶性木質素於氛化鈣/二甲基亞®溶液接 枝共聚合而製成。該程序十分複雜並需要沉澱於丙酮内及 過》K及滲透分析K單維產物。所得物霣被用於增加的油 回收。 .r· 窃明之洚佃銳明 本發明提供一種含有含丹寧聚合物質之姐合物。本發明 亦提供製備含丹寧聚合物之方法及使用聚合物供各種水處 理之方法。 丹寧,亦稱為丹寧酸,發生於葉子、樹枝、樹皮及許多 —· 5 一 (請先閲讀背面之注意r項再填寫本頁) 裝. 訂 線 本紙張尺度適用中II國家揉準(CNS ) A4规格(210X297公釐) 83. 3.10,000 A7 B7 經济部中央橾準局員工消费合作杜印装 i、發明説明(3 ) 植物之水果。如 Α. Ρίζζί於"Condensed Tannin for AdhesiveS' * Ind. Eng. Chen. Prod. Res. Dev. 1982, 21 pages 359-369所揭示,天然丹寧可為”可水解 ”丹寧及"縮合”丹寧。丹寧之组成及结構視來源及萃取方 法而不同,但實驗式结構被提供為C7eHe2〇4e ,許多0H基 接至芳族環。本發明所用之丹寧為縮合丹寧型*包括但不 囿限於自Quebracho,Minosa及Sumac所衍生者。然而, 可水解丹寧亦被期待在本發明之範圃內。 本發明係W於一種水溶性或水分敗性含丹寧聚合物姐合 物*包含下式: Tannin-[H-C-A] 其中,H為非離子單體,C為陽離子單體及A為陰離子單 體,H之莫耳X為〇至60¾ ,(:之莫耳χ為30至100¾:而A 之莫耳%為〇至30¾ ,但聚合物内之全部莫耳S;為1〇〇35。 陽離子單體選自一含有乙烯系不飽和季銨、辚或锍雔子 之族群。典型陽離子單體為二烷基胺基烷基(甲基)丙烯 醯胺、二烷基胺基烷基(甲基)丙烯酸_及二烯丙基二烷 基銨氛化物之季銨鹽。 # 酸之胺 烯酯基 丙乙甲 於基二 限胺酸 囿基烯 不乙丙 但二 、 括酸酯 包烯乙 ,丙基 群、胺 族鹽基 一 季甲 自氛二 選基酸 係甲烯 體之丙 單酯、 子乙鹽 離基酸 陽胺硫 佳基基 較乙甲 二二 本紙張尺度逋用中國國家標準(cNs)从说格(210x297公釐) 83. 3.10,000 (請先閱讀背面之注意事項再填寫本頁) .裝 訂 3l£6〇5 a7 B7 經濟部中央標準局員工消費合作杜印製 五、發明説明(4) 基乙酯、甲基丙烯酸二甲基胺基乙酯、二甲基胺基丙基甲 基丙烯醯胺、二甲基胺基丙基丙烯醢胺、二烯丙基二甲基 銨氯化物及二烯丙基二乙基銨氛化物。最佳陽離子單體為 丙烯酸二乙基胺基乙睹之甲基氛季鹽。 陰離子單體選自含乙烯系不飽和羧酸或磺酸官能基之族 群。此等軍體包括但不囿限於丙烯酸、甲丙烯酸、乙烯乙 酸、分解烏頭酸、順丁烯二酸、烯丙基乙酸、苯乙烯磺酸 、2-丙烯胺基-2-甲基丙烷磺酸(AMPS®)及3-烯丙氧基 -2-羥基丙烷磺酸及其鹽。較佳之陰離子單體為丙烯酸。 非離子單體選自乙烯系不飽和非離子軍體之族群*其包 含但不囿限於丙烯醢胺、甲基丙烯醢胺、N-羥甲基丙烯醢 胺、N,N-二甲基-丙烯醯胺;低碳烷(Ct-Ce)酯包括乙酸 乙烯酯、丙烯酸甲酯、丙烯酸乙酯及甲基丙烯酸甲酯;羥 基化低碳烷(Ci-Ce)酯包括丙烯酸羥基乙酯、丙烯酸羥基 丙酯及甲基丙烯酸羥基乙酯;烯丙基縮水甘油醚;及聚乙 二醇之乙氧基化烯丙基醚•聚丙二酵及丙氧基化丙烯酸酯 。較佳非離子單體為烯丙基縮水甘油醚及丙烯醢胺。 所得含丹寧聚合物包含10至80重量5K丹寧、20至90重量 陽離子軍體、0至30重量非離子單體及0至20重量* 陰雄子單體,但其限制條件為,所得含丹寧聚合物仍為水 溶性或水分散性,且陽離子、非離子及陰離子單體及丹寧 之全部重量S!高達100S:。較好是,當陽雛子單體與陰離子 單體於含丹寧聚合物内圼現一起時,陽離子單體包含較陰 離子單體更多的重量S!。於僅呈現有陽雔子單體之較佳具 -7- (請先閲讀背面之注意事項再填寫本頁) 裝. 訂 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 83. 3.10,000 經濟部中央樣準局員工消費合作社印製 A7 _B7_五、發明説明(5 ) 體例中,丹寧-陽離子單體共聚物包含50/5 0重最!1ί及 30/70重量!ϋ丹寧及陽離子單體。 所得含丹寧聚合物之數目平均分子量並不重要,只要其 仍為水溶性或水分敗性即可。含丹寧聚合物可藉混合所欲 單體與丹寧並藉由溶液、沉澱或乳液聚合技術以自由基引 發劑引發而製備。可使用習知引發劑如偶氮化合物、遇硫 酸鹽、遇氧化物及氧化堪原偶合劑。較佳引發劑為2,2’偶 氮雙(2-甲胖基丙烷)二氫氛化物(V-50*自Wako化學公 司可得)及第三丁基氫過氣化物/間二硫化钠( t-BHP/NaMBS)。此等或其他引發劑可在聚合終止時加入K 進一步與任何殘餘單體反應。 鐽轉移劑如醇、胺、甲酸或硫酵化合物可被用來調整聚 合物之分子量。所得聚合物可藉已知技術包括沉澱等單離 ,或聚合物可被簡單地用於其水溶液中。 反應溫度並不重要,通常發生在20°與100 t:之間,較 佳為40°至70 t。反應混合物之pH值亦不重要,通常範圍 為2.0至8.0 。所得含丹寧聚合物之待街[為C-13 H MR,布汝 克菲(Brookfield)粘度之百分比固體。 所得含丹寧聚合物應K其所欲目的充分之量加入欲處理 之水性糸統内。此量大部份視希望處理之特定水性系統而 定,並可被該等變數如濁度、pH、溫度、水量及存於糸統 内污染物之類型所影響。含丹寧聚合物在廣泛範圃之pH值 下為有效且應證實在任何水處理尋求之水性系統之pH值下 為有效者。 裝 訂 4' (請先閲讀背面之注意事項再填寫本頁) —8 一 本紙張尺度適用中國國家揉準(CNS > A4規格(2丨0X297公嫠) 83. 3.10,000 312685 Α7 Α7 Β7 經濟部中央標準局員工消費合作杜印製 五、發明説明() 本發明之含丹寧聚合物證實可用於各種遭受不同污染物 之水性系统而極遴於減少濁度、顔色及水性系统之淨化如 流人的水及廢水系统。粘土、粉砂、细分之有機及無機物 及微生物皆會增加濁度。顔色之性質最常膠凝而造成有櫬 物質如腐質酸及其他自植物性物質瀝漶之化合物。 本發明範圍内之廢水系统包括來自工業之初级及油狀廢 水糸统,包括但不囿限於精煉、石化、化學、網锇、輻磨 、汽車、坊嫌及肉類食品加工工業。此等系统内之污染物 為有機及無機污染物,其包括但不囿限於可沉降及不可沉 降的固塘、油、脂、沉澱的金屬及脂肪與蛋白質類物質。 含丹寧聚合物可被加入有待淨化之水性系統内*其量之 範圍對每百萬份水約為0.1份至約100份。聚合物可以連 續或間敗方式加入純粹或於水溶液中之水性系統内。 聚合絮凝劑如聚丙烯醯胺及丙烯醢胺與丙烯酸之共聚物 及其他凝聚劑如明礬、氛化鐵、粘土、沸石、活性碳等可 與含丹寧聚合物结合使用,Μ減少濁度及頭色並改良澄清 度。 热悉此技藝者可知許多應用,其中此等含丹寧聚合物會 發現實用性。此等實用性包括但不囿限於廢水處理應用如 來自化學工廠、精製廠及紙漿造紙廠之廢水、流入水之淨 化、去色、二次水淨化、油狀廢水處理、含蛋白質廢水、 造紙(例如,保留及排水肋劑)、蛋白質回收、乳化斷裂 、淤泥脫水、上游過濾器之淨化、水平流動之淨化等。 為了更清楚顧示本發明,展琨下列數據。下列實例被包 -9 — (請先閲讀背面之注意事項再填寫本頁) -裝, 訂 線 本紙張尺度適用中國國家標準(CNS ) Α4規格(210Χ297公釐) 813.10,000Trevose, PA, pages 23 through 30). Naturally occurring suspended particles are mainly negatively charged. Water-soluble organic cationic polymers such as polyamines and polydiallyldimethylammonium chloride are commonly used to purify water with high turbidity (greater than 60 NTU, measured by the degree of turbidity). In low turbidity water (below 60 NTU), when the water is treated only with cationic polymers, there are usually not enough particles to form settleable flocs. Non-condensing coagulants such as aluminum sulfate, polymeric aluminum oxychloride, iron sulfate, osmium oxychloride, and sodium aluminate are used instead. These inorganic coagulants are quite cheap and are generally effective for purifying water. However, it tends to produce bulky sludge and is difficult to dehydrate. In addition, the inorganic coagulant is effective only in a specific pH range, so it is necessary to adjust the pH of the water during treatment. In addition, the residual iron and aluminum ions in the treated water will affect downstream operations such as cooling and hoe furnace treatment. When the water is finally discharged, it will also cause health and environmental problems. —4 — This paper scale is applicable to the Chinese National Standard (CNS) Μ specification (210X297mm) 83 · 3.10,000 I. · III Pack I j II ί order i—κ n ^ i (please read the notes on the back ^ (Fill in this page) 3 ^ 26qs A7 _- __ Printed by the Employees ’Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (2) Water-soluble / point-lost melamine formaldehyde resin has been used to purify low-turbidity water, but the resin The residual formaldehyde in it will cause difficulties in handling and handling. The object of the present invention is to provide an effective method of purifying water without causing the disadvantages of inorganic coagulant and melamine formaldehyde resin. % 昍 夕 廐 Shu The present invention provides a sister compound, its preparation method and the method of using the sister compound to purify water. The sister compound contains a water-soluble / water-dispersible tannin-containing polymer obtained by polymerizing ethylene-based unsaturated monomer and tannin. There is a description of Μ 抟 g US patents 4,558,080; 4,734,216 and 4,781,839 disclose a tanninite polymer obtained by inversion of tannin with amine compounds and aldehydes under acidic conditions as a flocculant. The process box should carefully monitor the pH value and intermediate viscosity during the reaction to prevent the ingredients from gelling. The long-term stability of the product and the amount of residual amine and formaldehyde in the solution can cause operational problems. U.S. Patent No. 4,990,270 discloses a thickener made by graft copolymerization of acrylamide and cationic monomers with water-insoluble lignin in a solution of calcium chloride / dimethylmethylene®. This procedure is very complicated and requires precipitation in acetone and single-dimensional products of K and permeation analysis K. The resulting product is used for increased oil recovery. .r · Ming Ming Zhi Dian Rui Ming The present invention provides a sister compound containing a tannin-containing polymer substance. The present invention also provides a method of preparing a polymer containing tannin and a method of using the polymer for various water treatments. Tannin, also known as tannin, occurs in leaves, branches, bark and many — 5 1 (please read the note r on the back before filling in this page). Packing. The paper size of the book is applicable to II countries. (CNS) A4 specification (210X297mm) 83. 3.10,000 A7 B7 Central Ministry of Economic Affairs, Ministry of Economic Affairs staff consumption cooperation du printing i, invention description (3) Fruits of plants. As disclosed by Α. Ρίζζί " Condensed Tannin for AdhesiveS '* Ind. Eng. Chen. Prod. Res. Dev. 1982, 21 pages 359-369, natural tannin can be "hydrolyzable" tannin and " condensation " The composition and structure of tannin are different depending on the source and extraction method, but the experimental structure is provided as C7eHe2〇4e, and many 0H groups are connected to the aromatic ring. The tannin used in the present invention is a condensed tannin type * including However, it is not limited to those derived from Quebracho, Minosa, and Sumac. However, hydrolyzable tannins are also expected to be within the scope of the present invention. The present invention is based on a water-soluble or water-degradable tannin-containing polymer. The substance * contains the following formula: Tannin- [HCA] where H is a non-ionic monomer, C is a cationic monomer and A is an anionic monomer, the mole X of H is 0 to 60¾, (: the mole χ is 30 To 100¾: while the mole% of A is from 0 to 30¾, but the total mole S in the polymer; is 10035. The cationic monomer is selected from one containing ethylenically unsaturated quaternary ammonium, oxonium or sulfonium Ethnic groups. Typical cationic monomers are dialkylaminoalkyl (meth) acrylamide, dialkylamine Alkyl (meth) acrylic acid _ and diallyl dialkyl ammonium quaternary ammonium salt. # Amino acid ester propyl ethyl methyl acid in the base of the two-diamine amino acid ethyl ene is not ethyl propylene but two, including The acid esters include vinyl, propyl group, amine group base, one-quaternary methylene self-ambient diacid, the propylene monoester of the methylene body, the subethyl salt, and the ionic acid sulfanyl base group are better than those of ethyl dimethyl dichloride. The standard uses the Chinese National Standards (cNs) from the grid (210x297 mm) 83. 3.10,000 (please read the notes on the back before filling out this page). Staple 3l £ 6〇5 a7 B7 Employee of Central Bureau of Standards, Ministry of Economic Affairs Consumer Cooperation Du Printed V. Description of the invention (4) Ethyl ethyl ester, dimethyl amino ethyl methacrylate, dimethyl amino propyl methacrylamide, dimethyl aminopropyl propyl propyl amide , Diallyl dimethyl ammonium chloride and diallyl diethyl ammonium chloride. The best cationic monomer is methyl quaternary salt of acrylic acid diethylamino ethyl ethyl. The anionic monomer is selected from Ethylene-based unsaturated carboxylic acid or sulfonic acid functional group. These military bodies include but are not limited to acrylic acid, methacrylic acid, ethylene Acid, decomposition of aconitic acid, maleic acid, allyl acetic acid, styrene sulfonic acid, 2-propenylamino-2-methylpropanesulfonic acid (AMPS®) and 3-allyloxy-2-hydroxyl Propane sulfonic acid and its salts. The preferred anionic monomer is acrylic acid. The non-ionic monomer is selected from the group of ethylenically unsaturated non-ionic military bodies * which includes but is not limited to propylene amide, methacryl amine, N- Hydroxymethylacrylamide, N, N-dimethyl-acrylamide; lower alkyl (Ct-Ce) esters include vinyl acetate, methyl acrylate, ethyl acrylate and methyl methacrylate; low hydroxylation Carboal (Ci-Ce) esters include hydroxyethyl acrylate, hydroxypropyl acrylate and hydroxyethyl methacrylate; allyl glycidyl ether; and ethoxylated allyl ether of polyethylene glycol • polypropylene Yeast and propoxylated acrylate. Preferred nonionic monomers are allyl glycidyl ether and allylamine. The resulting tannin-containing polymer contains 10 to 80 weight 5K tannin, 20 to 90 weight cationic military body, 0 to 30 weight nonionic monomer, and 0 to 20 weight * Yin and Xiong monomer, but the limitation is that the resulting content contains The tannin polymer is still water-soluble or water-dispersible, and the total weight of cationic, nonionic and anionic monomers and tannin S! Up to 100S :. Preferably, when the caterpillar monomer and the anionic monomer are present together in the tannin-containing polymer, the cationic monomer contains more weight S than the anionic monomer. It is better to show only the best one with yang carambola -7- (please read the precautions on the back before filling in this page). The size of this paper is applicable to China National Standard (CNS) A4 (210X297mm) 83 . 3.10,000 A7 _B7_ printed by the Employee Consumer Cooperative of the Central Prototype Bureau of the Ministry of Economic Affairs 5. Description of the invention (5) In the style, the tannin-cationic monomer copolymer contains 50/5 0 weight and 30/70 weight ! ϋDanning and cationic monomers. The number average molecular weight of the resulting tannin-containing polymer is not important as long as it is still water-soluble or water-insoluble. Tannin-containing polymers can be prepared by mixing the desired monomers with tannin and initiating with free radical initiators by solution, precipitation or emulsion polymerization techniques. Conventional initiators such as azo compounds, sulfates, oxides, and oxidative coupling agents can be used. Preferred initiators are 2,2 'azobis (2-methylfatty propane) dihydrogenate (V-50 * available from Wako Chemical Company) and the third butyl hydroperoxide / sodium metadisulfide (T-BHP / NaMBS). These or other initiators can be added at the end of the polymerization to further react with any residual monomers. A transfer agent such as alcohol, amine, formic acid, or sulfur fermentation compound can be used to adjust the molecular weight of the polymer. The resulting polymer can be isolated by known techniques including precipitation or the like, or the polymer can be simply used in its aqueous solution. The reaction temperature is not important and usually occurs between 20 ° and 100 t: preferably 40 ° to 70 t. The pH of the reaction mixture is also unimportant, and usually ranges from 2.0 to 8.0. The resulting tannin polymer-containing treated street [is C-13 H MR, Brookfield viscosity percent solids. The resulting tannin-containing polymer should be added to the aqueous system to be treated in a sufficient amount for its intended purpose. This amount depends largely on the specific aqueous system that you wish to treat, and can be affected by such variables as turbidity, pH, temperature, water volume, and the type of contaminants stored in the system. Tannin-containing polymers are effective at a wide range of pH values and should prove effective at the pH of any aqueous system sought by water treatment. Binding 4 '(please read the precautions on the back before filling in this page) —8 One paper size is suitable for China National Standard (CNS & A4 specifications (2 丨 0X297)) 83. 3.10,000 312685 Α7 Α7 Β7 Economy Printed by the Ministry of Standards and Administration of the Ministry of Consumer Affairs. 5. Description of the invention () The tannin-containing polymer of the present invention has been confirmed to be used in various aqueous systems that suffer from different contaminants and is highly selected for reducing turbidity, color and purification of aqueous systems such as Flowing water and wastewater systems. Clay, silt, finely divided organic and inorganic substances, and microorganisms all increase turbidity. The nature of the color is most often gelled, causing leaching substances such as humic acid and other self-planting substances The compounds in the scope of the present invention include waste water systems from industry, including primary and oily waste water systems, including but not limited to refining, petrochemicals, chemistry, osmium, radiant mills, automobiles, workshops, and meat food processing industries. The pollutants in these systems are organic and inorganic pollutants, which include but are not limited to solid ponds, oil, fat, precipitated metals and fats and protein that can be settled or not The polymer containing tannin can be added to the aqueous system to be purified * The amount ranges from about 0.1 part to about 100 parts per million water. The polymer can be added purely or in aqueous solution continuously or intermittently In water-based systems. Polymeric flocculants such as polypropylene amide and copolymers of acrylic amide and acrylic acid, and other coagulants such as alum, iron, clay, zeolite, activated carbon, etc. can be used in combination with tannin-containing polymers Reduce turbidity and head color and improve clarity. Those skilled in the art will know many applications, among which these tannin-containing polymers will find practicality. Such practicality includes but is not limited to wastewater treatment applications such as from chemical plants, Wastewater from refineries and pulp and paper mills, purification of inflow water, decolorization, secondary water purification, oily wastewater treatment, protein-containing wastewater, papermaking (eg, retention and drainage rib agents), protein recovery, emulsification fracture, sludge dewatering , Purification of upstream filters, purification of horizontal flow, etc. In order to more clearly observe the present invention, the following data is displayed. The following examples are included -9 — (Please read the back of the first Please fill in this page before you pay attention to it) -Installation, Threading This paper scale is applicable to China National Standard (CNS) Α4 specification (210Χ297mm) 813.10,000
經濟部中央標準局貝工消费合作社印製 五、發明説明(7 ) 括以例示本發明,但不應用來囿限本發明之範圍。 製備含丹寧聚合物之實驗程序 管例1 一設有縮合器、溫度計、氮入口及機械攪拌器之反應燒 瓶裝填有51.0 g縮合丹寧(Quebracho類型)及204.0 g 去離子水。然後將3. 5 g 50J;苛性驗及3.76 g烯丙基縮水 甘油醚(AGE)加入丹寧溶液中。將此溶液加熱至50Ό並維 持7小時。FT-IR顯示無吸附帶對應於AGE之殘餘環氧基 Ο g例2 實例1之所得丹寧/AGE溶液藉硫酸調整至pH 6.8。然 後在60Ϊ:下,將含0.39 g 2,2’偶氮雙(2-甲胖基丙烷) 二氫氯化物(V-50)於2.4 g去離子水内之引發劑溶液加 入124 g溶液中。然後,將含57.2 g二甲基胺基乙基乙酸 酯甲基氛化物quat (AETAC’ 80¾)及1,1 g丙稀酸(AA)之 單體溶液於5小時内逐漸加入燒瓶中。 在單體加入完成前加入另外引發劑溶液。之後,讓聚合 物隔夜。加入更多引發劑Μ完成反應。所得聚合物之结構 由C-13 N MR證實。所得含丹寧聚合物溶液具有布汝克菲粘 度為 1070 〇口5在27.3*:固體(25(:)° g m ^ 使用如實例2所述之裝置及程序,60.5 g 80¾ AETAC及 1.2 g AA被用來與79 g丹寧/ AGE溶液聚合。所得含丹寧 一 1 0 一 本纸張尺度適用中國國家揉準(CNS)A4規格(210x297公4) 83. 3.10,000 — — — — — — — — 裝— I I I I 訂 線 * (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印裝 312685 at B7 五、發明説明(8 ) 聚合物溶液具有布汝克菲粘度為243 cps在24.5X固體( 25C) 〇 窨例4 使用如實例2所述之裝置、程序及試劑裝填,32.50 g AGE /丹寧溶液被用來與AETAC及AA聚合。所得溶液具有 布汝克菲粘度為81 cps在21.8%固體(25C)。 當例Η 使用類似於寊例3所述之装置及程序•除了此次ΑΑ未被 用來反應。溶液pH在聚合前藉硫酸被調整至6.5。60.5 g 80¾ AETAC及79 g丹寧/AGE溶液被用來聚合。所得聚合 物溶液具有布汝克菲粘度為1050 cps在26.9«固體( 25C) 〇 管例(U7 使用如萁例5所述之程序Μ製備不同重量比之丹寧/ AETAC聚合物。所得聚合物溶液之姐合物及物理性被示於 表I及11。 窗例8 將 60.5 g AETAC (80¾)及 1.2 s ΑΑ在 60Ρ 下於 4.5 小時 内逐漸加入127.5 g丹寧溶液(20¾固體)內。將V-50射 入反應容器内Μ引發聚合過程。 所得含丹寧聚合物溶液之结構由C-13 NMR所證實。所得 聚合物溶液具有布汝克菲粘度為583 cps在35.5¾固體( 25 0 〇 窗俐9 — 11 — 本紙張尺度適用中國國家揉準(CNS ) A4規格(210X297公釐) 83. 3.10,000 裝 訂 备 (請先閱讀背面之注意事項再填寫本頁)Printed by the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (7) The examples are included to illustrate the invention, but should not be used to limit the scope of the invention. Experimental Procedure for Preparation of Tannin-Containing Polymer Tube Example 1 A reaction flask equipped with a condensator, thermometer, nitrogen inlet, and mechanical stirrer was filled with 51.0 g of condensed tannin (Quebracho type) and 204.0 g of deionized water. Then 3.5 g 50J; causticity test 3.76 g allyl glycidyl ether (AGE) was added to the tannin solution. This solution was heated to 50 ° C and maintained for 7 hours. FT-IR showed no adsorption band corresponding to the residual epoxy groups of AGE Οg Example 2 The resulting tannin / AGE solution of Example 1 was adjusted to pH 6.8 by sulfuric acid. Then at 60Ϊ :, add an initiator solution containing 0.39 g of 2,2 'azobis (2-methylfattypropane) dihydrochloride (V-50) in 2.4 g of deionized water to 124 g of solution . Then, a monomer solution containing 57.2 g of dimethylaminoethyl acetate methyl chlorate quat (AETAC '80¾) and 1,1 g of acrylic acid (AA) was gradually added to the flask over 5 hours. Add additional initiator solution before the monomer addition is complete. After that, let the polymer overnight. Add more initiator M to complete the reaction. The structure of the resulting polymer was confirmed by C-13 N MR. The resulting tannin-containing polymer solution had a Brookfield viscosity of 1070. Port 5 at 27.3 *: solid (25 (:) ° gm ^ using the apparatus and procedure described in Example 2, 60.5 g 80¾ AETAC and 1.2 g AA It is used to polymerize with 79 g of tannin / age solution. The resulting paper contains tannin 1 0. The paper size is suitable for China National Standardization (CNS) A4 specification (210x297 g. 4) 83. 3.10,000 — — — — — — — — — 装 — IIII Stranding * (please read the notes on the back before filling in this page) Printed by the Central Bureau of Economic Affairs Employee Consumer Cooperative 312685 at B7 V. Description of the invention (8) The polymer solution has Bruker Viscosity is 243 cps at 24.5X solid (25C). Example 4 Using the equipment, procedures and reagents as described in Example 2, 32.50 g AGE / tannin solution was used to polymerize with AETAC and AA. The resulting solution had a Bru The Kefir viscosity is 81 cps at 21.8% solids (25C). When Example Η uses a device and procedure similar to that described in Example 3 except that this time ΑΑ was not used for reaction. The pH of the solution was adjusted to 6.5.5 60.5 g 80¾ AETAC and 79 g tannin / AGE solution were used for polymerization. The resulting polymer solution had a Brookfield viscosity of 1050 cps at 26.9 «Solid (25C). The tube (U7 used the procedure described in Example 5 to prepare tannin / AETAC polymers of different weight ratios. The resulting polymer The sister compound and physical properties of the solution are shown in Tables I and 11. Window Example 8 60.5 g of AETAC (80¾) and 1.2 s ΑΑ were gradually added to 127.5 g of tannin solution (20¾ solids) at 60P over 4.5 hours. Injection of V-50 into the reaction vessel initiates the polymerization process. The structure of the resulting tannin-containing polymer solution is confirmed by C-13 NMR. The resulting polymer solution has a Brookfield viscosity of 583 cps at 35.5¾ solid (25 0 〇 窗 俐 9 — 11 — The size of this paper is applicable to the Chinese National Standard (CNS) A4 (210X297mm) 83. 3.10,000 binding equipment (please read the precautions on the back before filling this page)
i、發明説明(9 ) 經濟部中央標準局員工消f合作社印製 使用如實例8所述之類似程序製備丹寧/ AETAC/AA聚 合物溶液。所得聚合物溶液具有布汝克菲粘度為754 cps 在 35.6¾ 固體(25C)。 »例1 0 使用如實例8所述類似程序製備丹寧/ AETAC溶液。使 用V-50作為引發劑,將64.5 g AETAC (80¾)與127.5 g丹 寧溶液(203!固體)反懕。所得聚合物溶液具有布汝克菲 粘度為625 〇口3在35.2»固體(25〇。 窗俐1 1 使用類似於實例10所述程序,M V-50作為引發劑將 47.8 g 80!K AETAC與127.5 s丹寧溶液(20S:固體)反應 。所得聚合物之结構由C-13 NMR證實。聚合物溶液具有布 汝克菲粘度為323 cps在33.33:固體(25C)。 管俐Ί 2 使用類似於實例11所述之装置及程序,Mimosa型之丹寧 被用於反應中。所得溶液具有布汝克菲粘度為109 CPS在 36.3¾ 固體(25C)。 啻例及1 d 使用如實例11所述之類似装置及程序,不同來源之 Mimosa型丹寧被用於反應。 啻例1 R 此實例中,氧化谡原對之第三丁基氫過氧化物(t-BHP )/間二硫化納(HaMBS)被用來作引發劑。將22.1 g丹寧 (Mimosa型)、64.5 g 80¾ AETAC 在 55t:下裝人一含有 -12- (請先Μ讀背面之注意事項再填寫本頁) •裝.i. Description of the invention (9) Printed by the Employees ’Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. A similar procedure as described in Example 8 was used to prepare tannin / AETAC / AA polymer solutions. The resulting polymer solution had a Brookfield viscosity of 754 cps at 35.6¾ solids (25C). »Example 1 0 A tannin / AETAC solution was prepared using a similar procedure as described in Example 8. Using V-50 as an initiator, 64.5 g of AETAC (80¾) and 127.5 g of tannin solution (203! Solid) were inverted. The resulting polymer solution had a Brookfield viscosity of 625. Port 3 in 35.2 »solid (25〇. Window Li 1 1 using a procedure similar to that described in Example 10, M V-50 as an initiator will 47.8 g 80! K AETAC Reacted with 127.5 s tannin solution (20S: solid). The structure of the obtained polymer was confirmed by C-13 NMR. The polymer solution had a Brookfield viscosity of 323 cps at 33.33: solid (25C). Guan Li Ί 2 Use Similar to the apparatus and procedure described in Example 11, tannins of the Mimosa type were used in the reaction. The resulting solution had a Brookfield viscosity of 109 CPS at 36.3¾ solids (25C). Examples and 1 d were used as in Example 11 In the similar equipment and procedures described, Mimosa-type tannins from different sources were used for the reaction. Example 1 R In this example, the third butyl hydroperoxide (t-BHP) / meta disulfide of the original hydrogen oxide was used. Nano (HaMBS) is used as an initiator. 22.1 g tannin (Mimosa type), 64.5 g 80¾ AETAC at 55t: the downloader contains -12- (please read the precautions on the back before filling this page) • Install.
、1T 線 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 83. 3. !0,〇〇〇 經濟部中央標準局員工消費合作杜印製 3 芯 6S5 A7 B7 五、發明説明() 42.7 g去離子水之反應器中。然後,將20g 4X t-BPH及 20 g 6¾ NaMBS在50-55 t:下於5.5小時内逐漸装人溶液 中。溶液在冷卻前保持在50t:歷30分鐘。在最後稀釋後· 所得聚合物溶液具有布汝克菲粘度為173 cpS在31.2¾固 體(25C)。 窗例1 6 使用如實例15所述類似程序,Quebracho丹寧被用於反 應中。所得溶液具有布汝克菲粘度為133 cpS在32.5¾固 體(25C) ° 苜俐17, 18, 19及 20 使用如實例15所述類似程序Μ製備不同重量比之丹寧/ AETAC聚合物。 n m ?.} 使用類似於實例15所述之程序,但31.0 s 80¾ AETAC及 7.7 g 52*;丙烯醮胺(AM)被用來與38.7 g丹寧共聚合。所 得溶液具有布汝克菲粘度為459 cps在31. 2¾:固體(25C) 〇 管例2?· 使用類似於實例15之程序,將1439份AETAC (80!«)在 45C下與1151份丹寧(Mimosa型)於水溶液内反應。68份 t-BHP及189份間二硫化納(20¾)被用作引發劑。所得溶 液具有布汝克菲粘度為1150〇?5在37.2!«固體(25〇。 富俐2 3 使用類似於實例22之程序,將4400份AETAC (80S;)與 —1 3 一 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 83. 3.10,000 (請先M讀背面之注意事項再填寫本頁) •裝. 訂 經濟部中央榡準局員工消費合作杜印製 叱6S5 A7 ____ B7 五、發明説明(1Ί ) 3520份丹寧(Minosa型)於水溶液內反應。所得溶液具有 布汝克菲粘度為409 cps在38.2S!固體(25C)。 ίΗ » m Μ實質上符合美國專利4,558,080之實例1之程序製備 丹寧/單乙酵胺/甲醛物質。所得產物具有粘度為20 0 cps (40.5S;固體)(在 pH為 2.4 下)。 表I及II槪述所得含丹寧聚合物之姐合物及物理性。、 1T line paper size is applicable to China National Standard (CNS) A4 specification (210X297mm) 83. 3. 0, 〇〇〇 Ministry of Economic Affairs Central Standards Bureau employee consumption cooperation du printing 3 core 6S5 A7 B7 V. Description of invention () 42.7 g deionized water in the reactor. Then, 20g 4X t-BPH and 20 g 6¾ NaMBS were gradually filled into the solution under 50-55 t: 5.5 hours. The solution was kept at 50t before cooling: for 30 minutes. After the last dilution · The resulting polymer solution has a Brookfield viscosity of 173 cpS at 31.2¾ solids (25C). Window Example 16 Using a similar procedure as described in Example 15, Quebracho tannin was used in the reaction. The resulting solution had a Brookfield viscosity of 133 cpS at 32.5¾ solids (25C) ° Alfalfa 17, 18, 19 and 20. A similar procedure M as described in Example 15 was used to prepare tannin / AETAC polymers in different weight ratios. n m?.} uses a procedure similar to that described in Example 15, but with 31.0 s 80¾ AETAC and 7.7 g 52 *; propylene amine (AM) was used to copolymerize with 38.7 g tannin. The resulting solution has a Brookfield viscosity of 459 cps at 31. 2¾: solid (25C). Example 2? Using a procedure similar to that of Example 15, 1439 parts of AETAC (80! «) At 45C and 1151 parts of Dan Ning (Mimosa type) reacts in aqueous solution. 68 parts of t-BHP and 189 parts of sodium disulfide (20¾) were used as initiators. The resulting solution has a Brookfield viscosity of 1150 〇5 in 37.2! «Solid (25〇. Fuli 2 3 using a procedure similar to Example 22, 4400 parts AETAC (80S;) and -1 3 a paper size Applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) 83. 3.10,000 (please read the notes on the back before filling in this page) • Packed. Ordered by the Central Bureau of Economics of the Ministry of Economic Affairs, the consumer cooperation cooperation is printed by Du Du. 6S5 A7 ____ B7 5. Description of the invention (1Ί) 3520 parts of tannin (Minosa type) reacted in aqueous solution. The resulting solution has a Brookfield viscosity of 409 cps at 38.2S! Solid (25C). ΊΗ »m Μ substantially The tannin / monoacetamide / formaldehyde material was prepared according to the procedure of Example 1 of US Patent 4,558,080. The resulting product had a viscosity of 200 cps (40.5S; solid) (at a pH of 2.4). Table I and II The sister compound containing tannin polymer and its physical properties.
S_I 含丹寧聚合物之姐合物 實例1-11及15-21為Quebracho丹寧 實例12-24及22-23為Mimosa丹寧 實例 號齡 姐合物 mm% 2 丹寧 / (AETAC/AA/AGE) 33.1/(62.9/1.6/2.4) 3 丹寧 / (AETAC/AA/AGE) 23.2/(73.3/1.8/1.7) 4 丹寧 / (AETAC/AA/AGE) 11.1/(86.0/2.1/0.8) 5 丹寧 / (AETAC/AGE) 32.2/(65.4/2.4) 6 丹寧/ (AETAC/AGE) 22.5/(75.8/1.7) 7 丹寧 / (AETAC/AGE) 10.8/(88.4/0.8) 8 丹寧 / (AETAC/AGE) 34/ (64.4/1.6) 9 丹寧 / (AETAC/AA) 34/ (64.4/1.6) 10 丹寧/AETAC 33.1/66.9 11 丹寧/AETAC 40/60 -14- 本紙張尺度適用中國國家標準(CNS ) Μ規格(210X297公釐) 83. 3.10,000 I 裝 訂 線 (請先閲讀背面之注意事項再填寫本頁) A7 B7 五、發明説明(12) 12 丹寧/AETAC 33.1/66.9 13 丹寧/AETAC 33 . 1/66.9 14 丹寧/AETAC 33.1/66.9 15 丹寧/AETAC 30/70 16 丹寧/AETAC 30/70 17 丹寧/AETAC 40/60 18 丹寧/AETAC 50/50 19 丹寧/AETAC 50/50 20 丹寧/AETAC 55/45 21 丹寧 / (AETAC/AM) 50/(40/10) 22 丹寧/AETAC 50/50 23 丹寧/AETAC 50/50 AETAC 為二甲基胺基乙基丙烯 酸酯甲基氯化物 (請先閲讀背面之注意事項再填寫本頁) AA為丙烯酸 AGE為烯丙基縮水甘油醚 AM為丙烯醢胺 經濟部中央標準局員工消費合作社印製 -15- 83. 3. 10,000 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明(13 ) m__a 含丹寧聚合物之物理性 Ϊ_Μ_ 姐合物 固髏% 布汝克菲 枯麻(Γ D S ) 2 丹寧 MAETAC/AA/AGE) 27.3 4.0 1070 3 丹寧 /(AETAC/AA/AGE) 24.5 3.5 243 4 丹寧 / (AETAC/AA/AGE) 21.8 3.1 81 5 丹寧 / (AETAC/AGE) 26.9 4.6 1050 6 丹寧 / (AETAC/AGE) 24.4 4.4 151 7 丹寧 / (AETAC/AGE) 21.8 4.0 89 8 丹寧 / (AETAC/AGE) 35 . 5 3.4 583 9 丹寧 WAETAC/AA) 35.6 3.2 754 10 丹寧/AETAC 35.2 4.0 625 11 丹寧/AETAC 33.3 4.0 323 12 丹寧/AETAC 36.3 3.6 109 13 丹寧/AETAC 36.4 3.6 204 14 丹寧/AETAC 36 . 3 3.5 238 15 丹寧/AETAC 31.2 1.8 173 16 丹寧/AETAC 32 . 5 2.2 133 17 丹寧/AETAC 33.2 2.3 148 18 丹寧/AETAC 31.8 2.4 118 19 丹寧/AETAC 33.5 2.8 180 20 丹寧/AETAC 32.1 2.2 189 21 丹寧 /(AETAC/AM) 31.2 2.4 459 裝 訂 線 (請先閱讀背面之注意事項再填寫本茛) -16- 83. 3. 10,000 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 經濟部中央橾準局員工消費合作社印製 312685 at B7 五、發明说明(14) 22 丹寧 /AETAC 37.2 2.2 1150 23 丹寧 /AETAC 38.2 2.5 407 比較例: 丹寧/胺/甲醛 40.5 2.4 200 AETAC =二甲基胺基乙基丙烯酸酯之甲基氛季鹽 AA=丙烯酸 AGE =烯丙基縮水甘油醚 AM =丙稀睡胺 比較例=美國專利4,558,080 ,實例1之聚合物 功眈 > 試醏 為了顯示本發明含丹寧聚合物對降低濁度及顔色之功效 ,使用來自美國河流之合成河水及水樣品作為試驗基材, 進行淨化水之試驗。 合成河水基材包含蒸雔水、試劑级化學品(CaC〇3及 MgC03 )及天然產生之粘土及腐質酸。其被製備成具有下 列姐合物,其極接近典型低介質濁度之河水之姐合物。 濁度=8-10 ΝΤϋ 全部懸浮固體=30 mg/1 真色度=25 Pt-Co顔色單位 pH= 7.0S_I Examples of sister compounds containing tannin polymers 1-11 and 15-21 are Quebracho tannins examples 12-24 and 22-23 are Mimosa tannin example number age sister compounds mm% 2 tannins / (AETAC / AA / AGE) 33.1 / (62.9 / 1.6 / 2.4) 3 tannin / (AETAC / AA / AGE) 23.2 / (73.3 / 1.8 / 1.7) 4 tannin / (AETAC / AA / AGE) 11.1 / (86.0 / 2.1 / 0.8) 5 tannin / (AETAC / AGE) 32.2 / (65.4 / 2.4) 6 tannin / (AETAC / AGE) 22.5 / (75.8 / 1.7) 7 tannin / (AETAC / AGE) 10.8 / (88.4 / 0.8) 8 Denim / (AETAC / AGE) 34 / (64.4 / 1.6) 9 Denim / (AETAC / AA) 34 / (64.4 / 1.6) 10 Denim / AETAC 33.1 / 66.9 11 Denim / AETAC 40/60 -14 -This paper scale is applicable to the Chinese National Standard (CNS) Μ specification (210X297 mm) 83. 3.10,000 I binding line (please read the precautions on the back before filling this page) A7 B7 5. Description of the invention (12) 12 Dan Ning / AETAC 33.1 / 66.9 13 Danning / AETAC 33. 1 / 66.9 14 Danning / AETAC 33.1 / 66.9 15 Danning / AETAC 30/70 16 Danning / AETAC 30/70 17 Danning / AETAC 40/60 18 Danning NING / AETAC 50/50 19 DENNING / AETAC 50/50 20 DENNING / AETAC 55/45 21 DENNING / (AETAC / AM) 50 / (40/10) 22 DENNING / AETAC 50/50 23 DENNING / AETAC 50/50 AETAC is dimethylaminoethyl acrylate methyl chloride (please read the precautions on the back before filling in this page) AA is acrylic acid AGE is allyl glycidyl ether AM is acrylic acetamide economy Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the People's Republic of China -15- 83. 3. 10,000 This paper standard is applicable to the Chinese National Standard (CNS) A4 (210X297mm) Printed by the Employee Consumer Cooperative of the Central Standard Bureau of the Ministry of Economics A7 B7 V. Description (13) m__a Physical properties of tannin-containing polymer Ϊ_Μ_ sister compound solid skeleton% Bruikoffi (Γ DS) 2 tannin MAETAC / AA / AGE) 27.3 4.0 1070 3 tannin / (AETAC / AA / AGE) 24.5 3.5 243 4 tannin / (AETAC / AA / AGE) 21.8 3.1 81 5 tannin / (AETAC / AGE) 26.9 4.6 1050 6 tannin / (AETAC / AGE) 24.4 4.4 151 7 tannin / (AETAC / AGE) 21.8 4.0 89 8 Danning / (AETAC / AGE) 35. 5 3.4 583 9 Danning WAETAC / AA) 35.6 3.2 754 10 Danning / AETAC 35.2 4.0 625 11 Danning / AETAC 33.3 4.0 323 12 Danning / AETAC 36.3 3.6 109 13 Danning / AETAC 36.4 3.6 204 14 Danning / AETAC 36.3 3 3.5 238 15 Danning / AETAC 31.2 1.8 173 16 Danning / AETAC 32. 5 2.2 133 17 Danning / AETAC 33.2 2.3 148 18 Danning / AETAC 31.8 2.4 118 19 Danning / AETAC 33.5 2.8 180 20 Danning / AETAC 32.1 2.2 189 21 Danning / (AETAC / AM) 31.2 2.4 459 Gutter (Please read the precautions on the back before filling in this ranunculus) -16- 83. 3. 10,000 The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) Employees of the Central Bureau of the Ministry of Economic Affairs Printed by the consumer cooperative 312685 at B7 V. Description of the invention (14) 22 Danning / AETAC 37.2 2.2 1150 23 Danning / AETAC 38.2 2.5 407 Comparative example: Danning / amine / formaldehyde 40.5 2.4 200 AETAC = dimethylaminoethyl Acrylic acid methyl quaternary salt AA = acrylic acid AGE = allyl glycidyl ether AM = propenylamine comparative example = US Patent 4,558,080, polymer power of Example 1> Tests to show that the present invention contains The effect of Ning Polymer on reducing turbidity and color is to use synthetic river water and water samples from American rivers as test substrates to conduct water purification tests. Synthetic river water substrates include distilled water, reagent grade chemicals (CaC〇3 and MgC03), and naturally occurring clay and humic acid. It is prepared to have the following sister compounds, which are very close to those of typical low-medium turbidity river water. Turbidity = 8-10 ΝΤϋ Total suspended solids = 30 mg / 1 True color = 25 Pt-Co color unit pH = 7.0
Ca= 40 ppra as CaC03 Mg= 20 ppb as CaC03 試驗葙庠 一 17_ 裝 I II I ^ 線 (請先閏讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 83. 3.10,000 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明(15 ) 所用程序為一棟準懸浮物體分離試驗(jar test ),設 計成剌激典型水處理淨化器之操作。關於單一成份之處理 ,試驗程序包含:Μ各種劑呈將聚合物處理加入試驗基材 中,混合處理過之基材並使形成於水中之固體沉降,及最 後测定由各項處理所產生之上浮水之殘餘濁度及顔色。 用Μ評估產物功效之分析程序包括灞度测定及真色度測 定。未處理及已處理遇之水樣品之濁度係使用Hach Model 18900比濁度計所決定。真色濃度係藉测定已藉由 0. 45微過濾器過濾之樣品在455奄微米之吸收率而決定。 吸收率係使用一校準以將吸收率值轉換成標準鉑一鈷顔色 單位(Pt-Co cu)之HachDR 2000光譜光度計所測定。 瞄於雙成份處理,試驗成序包含:將含丹寧聚合物處理 加入試驗基材中,混合2分鐘,將陰離子絮凝劑加入處理 過之基材中,混合2 0分鏟•沉降15分鐘及測定上浮清液之 濁度。 表III及IV顬示在此濁度之聚合物劑量下,各聚合物之 最低測定的猓度值。 表V及VI顯示含丹寧聚合物之殘餘真色度及殘餘濁度之 結果。 商用物質如明礬(硫酸鋁),三聚氰胺甲醛之水溶性樹 脂及丹寧/胺/甲醛亦被試驗供比較。 一 1 8 一 本紙張尺度適用中國國家標準(CNS ) A4g ( 210x297公釐) 83. 3.10,000 11 I I 裝 I I I 訂 I I I 線 I (請先閲讀背面之注意事項再填寫本頁) 五、發明説明(16 ) A7 B7 恙T T T 含丹寧聚合物之濁度試驗 在ppm活性劑量下之最低濁度(NTU) 菝揮Ca = 40 ppra as CaC03 Mg = 20 ppb as CaC03 Test No. 17_ Install I II I ^ line (please read the notes on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 specification ( 210X297 mm) 83. 3.10,000 A7 B7 printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of invention (15) The procedure used is a quasi-suspended object separation test (jar test), designed to stimulate typical water treatment Operation of the purifier. Regarding the treatment of single ingredients, the test procedure includes: M various agents add polymer treatments to the test substrate, mix the treated substrates and allow the solids formed in the water to settle, and finally determine the uplift produced by each treatment The residual turbidity and color of water. Analytical procedures for evaluating the efficacy of products using M include bait determination and true color measurement. The turbidity of untreated and treated water samples is determined using the Hach Model 18900 Turbidimeter. The true color concentration is determined by measuring the absorption rate of the sample that has been filtered through the 0.45 microfilter at 455 μm. The absorbance is determined using a HachDR 2000 spectrophotometer that uses a calibration to convert the absorbance value to a standard platinum-cobalt color unit (Pt-Co cu). Aiming at the two-component treatment, the test sequence includes: adding the polymer containing tannin to the test substrate, mixing for 2 minutes, adding the anionic flocculant to the treated substrate, mixing for 20 minutes, shoveling and settling for 15 minutes and Measure the turbidity of the supernatant. Tables III and IV show the lowest measured enthalpy values for each polymer at this turbidity polymer dose. Tables V and VI show the results of residual true color and residual turbidity of tannin-containing polymers. Commercial substances such as alum (aluminum sulfate), melamine formaldehyde water-soluble resin and tannin / amine / formaldehyde were also tested for comparison. One 1 8 One paper size applies to the Chinese National Standard (CNS) A4g (210x297mm) 83. 3.10,000 11 II Binding III Binding III Line I (Please read the precautions on the back before filling this page) V. Description of invention (16) A7 B7 柙 TTT The minimum turbidity (NTU) of turbidity test containing tannin polymer at ppm active dose
合成水 (8-10 NTU) ppm NTHSynthetic water (8-10 NTU) ppm NTH
德拉威河水 (4-7 NTU) ppm NTHDravidian water (4-7 NTU) ppm NTH
德拉威河水 NT IIDravidian Water NT II
p P 經濟部中央標隼局員工消費合作社印製 實例2 1.0 0,9 2.0 實例 3 1.0 1.5 0.5 實例 4 0.5 2.1 0 實例5 實例6 實例7 實例8 實例9 0.75 0 實例 10 0.75 0 實例 11 1.5 0.3 2.0 2.8 2. 實例 12 1.5 0.6 2.0 2.0 2. 實例13 1 實例1 4 1 MF 6 明礬 15.0 0.2 10 丹寧 /AM/F 7, 0 0.2 4 比較例 6.00 β具有0. 1 ppm陰離子(丙烯醯胺/丙烯酸)(90/10)共 2. (請先閲讀背面之注意事項再填寫本頁) -裝·p P Printed example 2 1.0 0,9 2.0 Example 3 1.0 1.5 0.5 Example 4 0.5 2.1 0 Example 5 Example 6 Example 7 Example 8 Example 9 0.75 0 Example 10 0.75 0 Example 11 1.5 0.3 2.0 2.8 2. Example 12 1.5 0.6 2.0 2.0 2. Example 13 1 Example 1 4 1 MF 6 Alum 15.0 0.2 10 Tannin / AM / F 7, 0 0.2 4 Comparative Example 6.00 β with 0.1 ppm anion (acrylamide) / Acrylic) (90/10) Total 2. (Please read the precautions on the back before filling out this page) -Installed ·
、tT 19 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 83. 3. 10,000 五、發明説明(17 聚物 A7 B7 MF為芾面上可得之三聚氰胺/甲醛樹脂 丹寧/ AM/F為市面上可得之丹寧/胺/甲醛聚合物 比較例為美國專利4, 558,080之實例1 表、 TT 19 This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) 83. 3. 10,000 5. Description of the invention (17 polymer A7 B7 MF is melamine / formaldehyde resin tannin available on the surface AM / F is the commercially available tannin / amine / formaldehyde polymer. The comparative example is US Patent 4,558,080, Example 1 Table
IVIV
含丹寧聚合物之濁度試驗 在ppm活性劑量下之最低濁度(ΝΤϋ) 7 . 2 HTU未處理河水濁度 德拉威河水 NT II 處揮 實例15 實例16 實例17 實例18 實例19 實例20 實例21 MF 明礬 ppm 4 0 2 德拉威河水 ppm N T U ppm/AM/AA 4.0 1.5 0 . 25 : 0.25 0.25' 0.100.25 0.10 0.10 裝 訂 線 (請先閱讀背面之注意事項再填寫本頁) 12 經濟部中央標準局員工消費合作社印製 丹寧/AM/F 6 0 0 8 e ppm 90/10丙烯醯胺/丙烯酸共聚物之共聚物之PPm MF為市面上可得之三聚氰胺/甲醛樹脂 丹寧/ AM/F為市面上可得之丹寧/胺/甲醛聚合物 20 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 83. 3.10,000 A7 B7 五、發明説明(I8 ) m__i 濁度及顔色減少試驗 威斯康辛河水基材 經濟部中央標準局員工消費合作社印製 聚合物劑量 上浮水 品質 (mg活性聚 殘餘濁度 殘餘真色度 莨例 合物/并) (n t. u ) (P t - Π ο r π ) 未處 理 0 10.6 69 實例 14 4 10.7 42 實例 14 8 4.4 27 實例 14 12 2.5 19 實例 14 16 1.7 14 實例 14 20 3.7 10 實例 17 4 11.6 45 實例 17 8 4.2 26 實例 17 12 2.8 19 實例 17 16 2.5 15 實例 17 20 3.0 12 實例 18 4 11.4 60 實例 18 8 8.2 33 實例 18 12 3.4 26 賁例 18 16 3.4 22 實例 18 20 2.7 19 實例20 4 10.8 61 (請先閲讀背面之注意事項再填寫本頁) •裝 -21 - 83. 3.10,000 本紙張尺度適用中國國家標準(CNS ) A4说格(210X297公釐) ^12685 A7 B7 五、發明説明(19) 經濟部中央標準局員工消費合作社印製 實 例 20 8 11 . 0 40 賁 例 20 12 3 . 6 30 實 例 20 16 2 . 9 29 實 例 20 20 2 . 6 26 實 例 21 4 11. 2 56 實 例 21 8 7 . 1 39 實 例 21 12 2 . 8 33 實 例 21 16 2 . 7 30 實 例 21 20 3 . 1 29 丹 寧 /AM/F 12 9 . 4 47 丹 寧 /AM/F 14 6 . 1 40 丹 寧 /AM/F 16 2 . 7 35 丹 寧 /AM/F 20 1 . 41 26 丹 寧 /AM/F 24 1 . 08 22 丹 寧 / AM/F 為市面上可得 之丹寧/胺 /甲 醛聚合物 (請先閲讀背面之注意事項再填寫本頁) -22- 83. 3.10,000 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 五、發明説明(2Q) 顔 色 減少 之 試驗 哈 德 遜河 水 基材 聚合物劑 量 (ns活性 聚 例 合物/羿1 無 處 理 0 賁 例 22 3 實 例 22 6 賁 例 22 9 實 例 22 12 實 例 22 15 實 例 23 3 實 例 23 6 實 例 23 9 實 例 23 12 實 例 23 15 表 III 及 IV之结果顧示 少試驗基材内之濁度。 A7 B7 上浮水品質 餘濁度 (n t. u ) 殘餘真色度 (P t. - Π n r. u ) 16.7 22 9.4 13 3.1 12 1.55 11 0.98 8 1.13 7 10.8 15 3.2 10 1.52 10 1.50 10 0.98 10 ---------裝-- *· (請先閱讀背面之注意事項再填寫本頁) 訂 線 經濟部中央標準局員工消費合作社印製 表V及VI之结果顯示本 少流入水之顔色方面有效 為了顧示丹寧系聚合物 來自不同工業之若干廢水 本發明之聚合物在低劑量下可減 • /r 發明之含丹寧聚合物亦證實在減 0 淨化廢水之功效,在實驗室中對 樣品進行試驗。試驗基材之說明 -23- 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 83. 3. 10,000 A7 B7 五、發明説明(21) 、試驗程序及試驗结果被提供於Μ下實例。 使用來自德州煉製廠之油狀廢水樣品作為試驗基材,進 行懸浮物質分離試驗。廢水之澄清度係藉测定濁度而決定 。未處理之水具有澳度為32 ntu。將未處理之油狀廢水之 樣品放入40 0 mi燒杯中,再用不同劑量之各凝聚劑處理之 。評估之凝聚劑包括硫酸鋁(作為代表習知技術之對照處 理)及丹寧系聚合物之溶液。 下列程序被用來混合各處理遇之油狀廢水樣品: 1 ) 200 ml/試驗;使用1”χ2"槳狀物將樣品混合於 400 ml燒杯中; 2) 加入凝聚劑,同時混合S 100 rpm ; 3) 混合5分鐘0 100 rpm ; ( K IN NaOH將pH調整至 6 . 5-8 . 0 ); 4) 加人聚合物1115L ( AA/AM共聚物),混合30秒S 10 0 r p m ; 5) 混合5分鐘§ 35 rpm; 6) 停止混合,靜止狀況維持5分鐘以分離油; 7) Μ淨化水為揉品,使用Hach Model 18900比率濁度 計分析殘餘獨度。 此等試驗结果被示於下表VII 。 (請先Μ讀背面之注意事項再填寫本萸) -裝 訂 經濟部中央標準局負工消費合作社印装 —2 4 一 83.3.10,000 本紙張又度適用中國國家標準(CNS ) Α4規格(210X297公釐) 五、發明説明(22) A7 B7 經濟部中央標準局員工消费合作社印製 表 V T T 油狀 廢水淨化 西南 煉油廠 A12 (S04)3 劑量(mg 聚合物 殘餘 試驗 -14H20 實例 活性聚合 1115L 濁度 # (m κ / 孙) 號齡 物/孙) (m 2 / 并) (n t υ ) 1 0 — — 1.5 33 2 50 — — 1.5 4.7 3 75 — — 1.5 2.8 . 4 100 — — 1.5 2.9 5 125 --- — 1.5 1.8 6 150 一-- — 1.5 2.3 7 0 20 10 1.5 6 . 2 8 0 20 15 1.5 4.4 9 0 20 20 1.5 7 . δ 10 0 20 25 1.5 5.5 11 0 21 10 1.5 5.2 12 0 21 15 1.5 5.3 13 0 21 20 1.5 6.1 14 0 21 25 1.5 2.2 15 0 18 10 1.5 6.7 16 0 18 15 1 . 5 10.4 17 0 18 20 1.5 6.3 18 0 18 25 1.5 8.7 -25 - 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 83. 3. 10,000 裝 訂 線 (請先閱讀背面之注意事項再填寫本頁) A7Turbidity test of tannin-containing polymer Minimum turbidity (NTT) at ppm active dose 7.2 HTU untreated river turbidity Dravidian water NT II Example 15 Example 16 Example 17 Example 18 Example 19 Example 20 Example 21 MF alum ppm 4 0 2 Dravidian water ppm NTU ppm / AM / AA 4.0 1.5 0. 25: 0.25 0.25 '0.100.25 0.10 0.10 gutter (please read the notes on the back before filling this page) 12 Economy Ministry of Central Standards Bureau employee consumer cooperative printed tannin / AM / F 6 0 0 8 e ppm 90/10 PPm MF copolymer of acrylic amide / acrylic acid copolymer is melamine / formaldehyde resin tannin available on the market / AM / F is the tannin / amine / formaldehyde polymer available on the market. 20 This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) 83. 3.10,000 A7 B7 V. Description of the invention (I8) m__i Turbidity and color reduction test Wisconsin River Water Base Material Ministry of Economy Central Standards Bureau Staff Consumer Cooperative Printed polymer dosage floating water quality (mg active poly residual turbidity residual true color chromophore sample compound / parallel) (n t. U) (P t-Π ο r π) Unprocessed 0 10.6 69 Example 14 4 10.7 42 Example 14 8 4.4 27 Example 14 12 2.5 19 Example 14 16 1.7 14 Example 14 20 3.7 10 Example 17 4 11.6 45 Example 17 8 4.2 26 Example 17 12 2.8 19 Example 17 16 2.5 15 Example 17 20 3.0 12 Example 18 4 11.4 60 Example 18 8 8.2 33 Example 18 12 3.4 26 Example 18 16 3.4 22 Example 18 20 2.7 19 Example 20 4 10.8 61 (Please read the precautions on the back before filling in this page) • Install-21- 83. 3.10,000 This paper scale applies the Chinese National Standard (CNS) A4 specification (210X297mm) ^ 12685 A7 B7 5. Invention description (19) Printed example of the employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 20 8 11. 0 40 Examples 20 12 3. 6 30 Examples 20 16 2. 9 29 Examples 20 20 2. 6 26 Examples 21 4 11. 2 56 Examples 21 8 7. 1 39 Examples 21 12 2. 8 33 Examples 21 16 2. 7 30 Example 21 20 3. 1 29 Denim / AM / F 12 9. 4 47 Denim / AM / F 14 6. 1 40 Denim / AM / F 16 2. 7 35 Denim / AM / F 20 1. 41 26 Tannin / AM / F 24 1. 08 22 Tannin / AM / F is a commercially available tannin / amine / formaldehyde polymer (please Read the precautions on the back before filling this page) -22- 83. 3.10,000 The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) V. Description of the invention (2Q) Hudson test for color reduction River water base polymer dosage (ns active polymer compound / Yi 1 No treatment 0 Example 22 3 Example 22 6 Example 22 9 Example 22 12 Example 22 15 Example 23 3 Example 23 6 Example 23 9 Example 23 12 Example 23 15 The results in Tables III and IV suggest less turbidity in the test substrate. A7 B7 Floating water quality residual turbidity (n t. U) residual true color (P t.-Π n r. U) 16.7 22 9.4 13 3.1 12 1.55 11 0.98 8 1.13 7 10.8 15 3.2 10 1.52 10 1.50 10 0.98 10 --------- installed-* · (please read the notes on the back before filling in this page) The results of the printing of Forms V and VI by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economics shows that this book has little inflow The water color is effective in order to show that the tannin polymer comes from several wastewaters from different industries. The polymer of the present invention can be reduced at a low dose Test the samples in the laboratory. Explanation of the test substrate-23- This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 83. 3. 10,000 A7 B7 5. Description of the invention (21), test procedures and test results are provided under Μ Examples. A sample of oily wastewater from the Texas refinery was used as the test substrate to conduct a suspended material separation test. The clarity of wastewater is determined by measuring turbidity. The untreated water has an Australian degree of 32 ntu. Put the sample of untreated oily wastewater into a 40 mi beaker, and then treat it with different dosage of each coagulant. Coagulants evaluated included aluminum sulfate (as a control treatment representing conventional technology) and solutions of tannin-based polymers. The following procedures were used to mix the oily wastewater samples encountered in each treatment: 1) 200 ml / test; mix the sample in a 400 ml beaker using a 1 ”× 2” paddle; 2) Add coagulant while mixing S 100 rpm 3) Mix for 5 minutes at 0 100 rpm; (K IN NaOH adjusts the pH to 6.5-8. 0); 4) Add human polymer 1115L (AA / AM copolymer) and mix for 30 seconds at S 10 0 rpm; 5) Mix for 5 minutes § 35 rpm; 6) Stop mixing and keep at rest for 5 minutes to separate the oil; 7) M purified water is a kneaded product, and the residual uniqueness is analyzed using a Hach Model 18900 ratio turbidimeter. The results of these tests were Shown in the following table VII. (Please read the precautions on the back before filling in this booklet)-Binding and Printing by the Central Bureau of Standards of the Ministry of Economic Affairs and Consumer Cooperatives-2 4-83.3.10,000 This paper is again applicable to the Chinese National Standard (CNS ) Α4 specification (210X297 mm) V. Description of invention (22) A7 B7 Central Ministry of Economic Affairs Employee Consumer Cooperative Printed List VTT Oily Wastewater Purification Southwest Refinery Plant A12 (S04) 3 Dose (mg Polymer Residual Test -14H20 Example Living Polymerization 1115L Turbidity # (m κ / grandchild) (m 2 / parallel) (nt υ) 1 0 — — 1.5 33 2 50 — — 1.5 4.7 3 75 — — 1.5 2.8. 4 100 — — 1.5 2.9 5 125 --- -1.5 1.8 6 150--1.5 2.3 7 0 20 10 1.5 6. 2 8 0 20 15 1.5 4.4 9 0 20 20 1.5 7. Δ 10 0 20 25 1.5 5.5 11 0 21 10 1.5 5.2 12 0 21 15 1.5 5.3 13 0 21 20 1.5 6.1 14 0 21 25 1.5 2.2 15 0 18 10 1.5 6.7 16 0 18 15 1. 5 10.4 17 0 18 20 1.5 6.3 18 0 18 25 1.5 8.7 -25-This paper size is subject to Chinese national standards ( CNS) A4 specification (210X297mm) 83. 3. 10,000 binding line (please read the precautions on the back before filling this page) A7
五、發明説明(23) 經濟部中央標準局員工消費合作社印裝 由濁度數據可知•所有三倨實驗聚合物在油狀廢水之淨 化方面皆可達到顧著改良。須特別注意的是實例21之聚合 物,在劑量為25 ng/Ι下其可減少濁度至2.2 ntu (試驗 #14 )。此項處理可與在125 mg/1下之硫酸鋁處理比較, 其減少殘餘濁度至1.8 (試驗#5)。一由此等處理所 產生之淤泥固體之理論量之比較示出,125 mg/1硫酸鋁由 於氫氧化鋁沉澱會產生65 mg/ι固體,而S例21之25 mg/1則會產生大約25 ms/Ι固體。此表示廢淤泥中62¾減 少,一項顯著減少,其會専致廢物處理廠淤泥處理成本之 實質節省。 使用來自鋁加工廠之油狀裔水之樣品進行懸浮物分離試 驗。水之澄清度係藉測定灞度及油含量而決定。未處理之 廢水濁度為71.6 ntu而氟氛烷冷劑可萃取的油含量為252 ppm 。 將油狀廢水之樣品故入400 ml堍杯中並用實例23之各種 劑量之硫酸鋁處理之。下列程序,設計Μ棋擬完全規模廢 水處理条统内之混合狀況,被用於懸浮物體分離試驗之評 估° 1) 200 ml/試驗;使用1”Χ2"槳狀物將樣品混合於 400 m丨燒杯中; 2) 加人凝聚劑,同時混合§ 125 rpm ;混合36分鐘g 125 rpm ; (KHaOH 將 pH 調整至 7.0 至 7.5 ); 3) 加入4 mg/1聚合物1125L (AA/AM共聚物)作為凝聚 -26- (請先閲讀背面之注意事項再填寫本頁) -裝 線 本紙張尺度逍用中國國家標準(CNS > A4規格(210X297公釐} 83. 3.10,000 經濟部中央標準局貝工消费合作社印製 ί>Ι2βό5 Α7 _ Β7 _ 五、發明説明(24 ) 肋劑;混合30秒Θ 125 rpm;混合24秒8 74 γρπ; 4) 停止混合,靜止狀況維持5分鐘以分離油; 5) 上浮液作為樣品供殘餘濁度及油分析; 6) 使用Hach Model 18900比率濁度計測定濁度; 7) 使用Hor iba OCMA 200F油含最圼分析器拥定氟氛院 冷劑可萃取的油。 此等試驗之結果被示於下表VIII。V. Description of the invention (23) Printed by the Employees ’Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs From the turbidity data, it can be seen that all Santuo experimental polymers can be improved with regard to the purification of oily wastewater. It is important to note that the polymer of Example 21 can reduce the turbidity to 2.2 ntu at a dose of 25 ng / Ι (Test # 14). This treatment can be compared with aluminum sulfate treatment at 125 mg / 1, which reduces the residual turbidity to 1.8 (Test # 5). A comparison of the theoretical amounts of sludge solids produced by these treatments shows that 125 mg / 1 aluminum sulfate will produce 65 mg / ιη solids due to the precipitation of aluminum hydroxide, while 25 mg / 1 of Example 21 will produce approximately 25 ms / Ι solid. This represents a reduction of 62¾ in waste sludge, a significant reduction that will result in substantial savings in the cost of sludge treatment in waste treatment plants. A sample of oily water from an aluminum processing plant was used for the suspension separation test. The clarity of water is determined by measuring the degree of oil and oil content. The turbidity of untreated wastewater is 71.6 ntu and the extractable oil content of fluorocarbon refrigerant is 252 ppm. Samples of the oily waste water were put into a 400 ml cup and treated with various doses of aluminum sulfate in Example 23. The following procedure is to design the mixing condition within the proposed full scale wastewater treatment system, which is used for the evaluation of the separation test of suspended objects ° 1) 200 ml / test; use a 1 ″ Χ2 " paddle to mix the sample at 400 m 丨In the beaker; 2) Add coagulant and mix § 125 rpm; mix for 36 minutes g 125 rpm; (KHaOH adjust pH to 7.0 to 7.5); 3) Add 4 mg / 1 polymer 1125L (AA / AM copolymer ) As Condensation-26- (Please read the precautions on the back before filling in this page) -The Chinese standard of the binding paper size (CNS & A4 specification (210X297mm) 83. 3.10,000 Central Standard of the Ministry of Economic Affairs Printed by Bureau Cooperative Consumer Co., Ltd. Ι2βό5 Α7 _ Β7 _ V. Description of the invention (24) Rib agent; mixing for 30 seconds Θ 125 rpm; mixing for 24 seconds 8 74 γρπ; 4) Stop mixing and keep at rest for 5 minutes to separate Oil; 5) The floating liquid is used as a sample for residual turbidity and oil analysis; 6) The Hach Model 18900 ratio turbidity meter is used to determine the turbidity; 7) The Hor iba OCMA 200F oil is used to contain the most analyte and the fluorochemical refrigerant is used. Extractable oil. The results of these tests are shown in Table VIII below
羌 V T T T 油狀廢水淨化 製鋁廠 卜择水之品皙 A 12 (S04)3 試驗 -14H20 it ( m κ / 孙) 實例23 f m e / -Jl· ) 聚合物 1115L (B K / 并) 殘餘 濁度 (n t u ) 殘餘油 (D d m ) 1 0 0 4 75.5 60 2 50 0 4 39.2 140 3 75 0 4 21.4 42 4 100 0 4 10.7 24 5 125 0 4 11.6 37 6 150 0 4 10.2 50 7 0 100 4 38.3 36 8 0 200 4 15.2 44 9 0 300 4 12.8 30 -27- 本紙張尺度適用中國國家揉準(CNS ) A4規格(210X297公釐) 83. 3. 10,000 裝 I I I 訂— I I I I 線 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 A7 _B7_五、發明説明(25 ) 由濁度及殘餘油數據可知,實例23之丹寧/ AETAC共聚 物之處理造成在此廢水之涅淸度方面顧著改良。 來自玉米加工廠之混合液體之樣品被用來評估實例23之 脫水性。毛佃管吸力次數(CST)被用來評估性能。未處理 的淤泥包含0.6X固體,具有pH為6.5 。將不同聚合物劑量 加人200 ml淤泥之樣品中,將處理遇淤泥在500 rpii下混 合30秒,然後將7 ml整分部份除去供CST分析。 此等試驗之结果被示於下表IX。 B__IX 玉米加工廠廢水脫水 試驗 窗俐 g 物) r:sT(l» ) 1 0 157.1 2 250 63.8 3 500 46.3 4 750 49.9 数據顯示在劑量為500 ppm下,CTS排水時間被減少 70X ,對實例23之丹寧/ AETAC共聚物之合理脫水能力。 對來自市營廢物處理廠(其接受大部份自坊嫌工廠之廢 水)之醆水樣品進行想浮物體分雕試驗。此廢水包含高濃 度之顔色,由纺嫌工廠廢水中之染料所造成。處理遇及未 處理遇水樣品中污染物之濃度係使用Perkin-Elmer· -28- (請先閲讀背面之注意事項再填寫本頁) -裝. 訂 線 本紙張尺度適用中國國家標準(CNS ) A4規格(210 X 297公釐) 83. 3.10,000 3126S5 A7 B7 五、發明説明() Lambda 4B UV/VIS光諶光度計,依照美國染料製造者協會 (ADMI)所推Μ之顔色滴定之分析程度予K決定。未處理 廢水之ADMI顔色為434 ADMI單元。 此實例所評估之丹寧系產物為實例23。硫酸鋁亦被評估 *作為對照處理,代表習知凝聚_技術。 下列程序被用以評估聚合物與硫酸鋁處理之功效: 1) 20 0 ml未處理之廢水/試驗;使用1”χ2”槳狀物將 樣品混合於400 ·1焼杯中; 2) 加人凝聚劑•同時混合§ 100 rpm ; 3) 混合2分鐘Θ 100 rpm ; 4) 混合10分鐘Θ 35 γρβ ; 5) 停止混合,將靜止的狀況維持15分鐘Μ使固體沉降 ! 6) 上浮液作為樣品並使用ADMI程序分析殘餘顔色。 此等試驗之结果被示於下表X 。m_x. 纺織廠廢水之去除染料 (請先閲讀背面之注意事項再填寫本頁) 、-* 經濟部中央標準局員工消費合作社印製 化璺®理夕添加 m 卜择水 試驗 A12 (S04)3-14H20 實例23 .·ί- 殘餘顔色 (me /fl· ) (m κ / 弁) f ADMTSi ft 屋份) 1 0 0 461 2 10 0 459 3 20 0 456 -29- 83.3. 10,000 B7 五、發明説明(27) 4 50 0 443 5 100 0 446 6 200 0 435 7 500 0 389 8 0 10 371 9 0 20 352 10 0 50 329 11 0 100 326 12 0 200 • 428 13 0 500 682 如殘餘顔色數據所示,丹寧-AETAC共聚物(寳例23)可 自比廢水除去大約25JK顔色。此優於用硫酸鋁所達成之去 除。 對來自市營廢水處理工廠(其接受80-90!ί來自纺嫌板之 廢水)之廢水樣品進行懋浮物體分離試驗。分析與懸浮物 體分離試驗之程序與前試驗所述者相同。未處理之廢水具 有ADMI顔色為768 。此實例所評估之產物包括硫酸鋁及實 例23。試驗结果被示於下表XI。 -30- 裝丨-r----訂------線 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家樣準(CNS ) A4規格(210X297公釐) 83. 3. 10,000 3 五、 發明説明( 28 A7 B7 羌 XT化果廣拥夕添加棚 弑驗 l· & 7k. 殘餘顔色 (At)MT厢 ft Μ 位) A12 (S04)3-14H20 實例 23 _( B g / 并)_ ( 1» g / 并) 1 0 0 754 2 10 0 773 3 20 0 774 4 50 0 752 5 100 0 696 6 200 0 620 7 500 0 698 8 0 10 721 9 0 20 720 10 0 50 565 11 0 100 320 12 0 200 240 13 0 500 179 II 裝 訂 線 (請先閲讀背面之注意事項再填寫本萸) 經濟部中央標準局員工消費合作杜印製 如此實例中殘餘顔色數據所示,丹寧/ AETAC共聚物達 成此廢水顔色之顯著減少,而硫酸鋁僅達成顔色之略為減 少Ο 對來自纺嫌工廠(其處理本身之廢水)之二廢水樣品進 行懸浮物體分離試驗。分析程序與懸浮物强分離試驗程序 仍與前試驗所述者相同。未處理廢水之顔色對樣品Α為 31 本紙張尺度逋用中國國家揉準(CNS ) A4規格(210 X 297公釐) 83. 3.10,000 經濟部中央標準局員工消費合作社印製 A7 B7五、發明説明(29 ) 619而對樣品B則為626 。此實例所評估之產物包括硫酸鋁及丹寧/ AETAC共聚物 ,實例23。 羌 XT T坊嫌工廠廢水染料 去除之樣品A结果: 化果廣理之添加割 h浑水 試驗 A12(S04)3-14H20 實例23 殘餘顔色 (請先閱讀背面之注意事項再填寫本頁) -裝. 林 (ms/升) (mg/并) (ADMT澦色Μ位) 1 0 0 619 2 10 0 607 3 20 0 610 4 50 0 607 5 100 0 588 6 200 0 556 7 500 0 474 8 0 10 579 9 0 20 577 10 0 50 523 11 0 100 489 12 0 200 332 13 0 500 145. -32- 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 83.3.10,000Qiang VTTT Oily Wastewater Purification Aluminium Plant Select Water Product Xi A 12 (S04) 3 Test-14H20 it (m κ / Sun) Example 23 fme / -Jl ·) Polymer 1115L (BK / Parallel) Residual Turbidity (ntu) Residual oil (D dm) 1 0 0 4 75.5 60 2 50 0 4 39.2 140 3 75 0 4 21.4 42 4 100 0 4 10.7 24 5 125 0 4 11.6 37 6 150 0 4 10.2 50 7 0 100 4 38.3 36 8 0 200 4 15.2 44 9 0 300 4 12.8 30 -27- The paper size is suitable for China National Standard (CNS) A4 specification (210X297mm) 83. 3. 10,000 Pack III binding-IIII line (please read the back side first Note: Please fill out this page) A7 _B7_ printed by the employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (25) According to the turbidity and residual oil data, the treatment of the tannin / AETAC copolymer of Example 23 resulted in This wastewater has been improved with regard to its nirvana. Samples of mixed liquids from corn processing plants were used to evaluate the dehydration of Example 23. The capillary suction times (CST) are used to evaluate performance. The untreated sludge contains 0.6X solids and has a pH of 6.5. Add 200 ml of silt to different polymer doses, mix the treated sludge at 500 rpii for 30 seconds, and then remove the 7 ml aliquot for CST analysis. The results of these tests are shown in Table IX below. B__IX Corn processing plant wastewater dehydration test window (lig) r: sT (l ») 1 0 157.1 2 250 63.8 3 500 46.3 4 750 49.9 The data shows that at a dose of 500 ppm, the CTS drainage time is reduced by 70X, for the example 23 Reasonable dehydration capacity of tannin / AETAC copolymer. Carry out the sub-carving test of the floating objects on the samples from the municipal waste treatment plant (which accepts most of the waste water from the suspected factory). This wastewater contains high-concentration colors, which are caused by dyes in the textile factory wastewater. The concentration of the pollutants in the treated and untreated water samples is Perkin-Elmer · -28- (please read the precautions on the back before filling in this page) -installation. The paper size of the binding book is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 83. 3.10,000 3126S5 A7 B7 5. Description of invention () Lambda 4B UV / VIS photometric photometer, according to the analysis of color titration pushed by the American Dyestuff Manufacturers Association (ADMI) The degree is decided by K. The color of ADMI of untreated wastewater is 434 ADMI unit. The tannin product evaluated in this example is Example 23. Aluminum sulfate has also been evaluated * as a control treatment, representing conventional coagulation technology. The following procedures were used to evaluate the efficacy of polymer and aluminum sulfate treatment: 1) 200 ml of untreated wastewater / test; use 1 ”× 2” paddles to mix the sample in a 400 · 1 baking cup; 2) Add people Coagulant • Simultaneous mixing § 100 rpm; 3) Mixing for 2 minutes Θ 100 rpm; 4) Mixing for 10 minutes Θ 35 γρβ; 5) Stop mixing and maintain a static state for 15 minutes Μ to allow solids to settle! 6) Floating liquid as a sample And use the ADMI program to analyze the residual color. The results of these tests are shown in Table X below. m_x. Dye removal of textile mill wastewater (please read the precautions on the back before filling in this page),-* Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, printed by the Chemical Industry Co., Ltd. Li Xi added m water selection test A12 (S04) 3 -14H20 Example 23 ..-Residual color (me / fl ·) (m κ / 弁) f ADMTSi ft share) 1 0 0 461 2 10 0 459 3 20 0 456 -29- 83.3. 10,000 B7 V. Invention Description (27) 4 50 0 443 5 100 0 446 6 200 0 435 7 500 0 389 8 0 10 371 9 0 20 352 10 0 50 329 11 0 100 326 12 0 200 • 428 13 0 500 682 It is shown that the tannin-AETAC copolymer (Bao Example 23) can remove approximately 25JK of color from the wastewater. This is superior to the removal achieved with aluminum sulfate. Separation test of floating objects was carried out on wastewater samples from municipal wastewater treatment plants (which accept 80-90! Ί wastewater from spinning boards). The procedure for analysis and separation of suspended matter is the same as described in the previous test. Untreated wastewater has an ADMI color of 768. The products evaluated in this example include aluminum sulfate and Example 23. The test results are shown in Table XI below. -30- Pack 丨 -r ---- order ------ line (please read the precautions on the back before filling in this page) This paper size is applicable to China National Standards (CNS) A4 specification (210X297mm) 83. 3. 10,000 3 V. Description of the invention (28 A7 B7 Qiang XT Huaguo Guangyongxi added shed test l · & 7k. Residual color (At) MT compartment ft M bit) A12 (S04) 3-14H20 Example 23 _ (B g / parallel) _ (1 »g / parallel) 1 0 0 754 2 10 0 773 3 20 0 774 4 50 0 752 5 100 0 696 6 200 0 620 7 500 0 698 8 0 10 721 9 0 20 720 10 0 50 565 11 0 100 320 12 0 200 240 13 0 500 179 II Gutter (please read the precautions on the back before filling in the booklet) The Ministry of Economic Affairs Central Standards Bureau staff consumption cooperation du printing the residual color in this example The data shows that the tannin / AETAC copolymer achieves a significant reduction in the color of this wastewater, while aluminum sulfate only achieves a slight reduction in color. The second wastewater sample from the textile mill (which treats its own wastewater) was subjected to a suspended object separation test. The analysis procedure and the suspended solids separation test procedure are still the same as those described in the previous test. The color of the untreated wastewater is 31 for the sample A. The paper size is in accordance with the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 83. 3.10,000 Printed by the Ministry of Economic Affairs Central Standards Bureau Staff Consumer Cooperative A7 B7 5. Description of the invention (29) 619 and 626 for sample B. The products evaluated in this example include aluminum sulfate and tannin / AETAC copolymer, Example 23. Qiang XT T Fang factory waste water dye removal sample A results: Huaguo Guangli's addition of cut water muddy water test A12 (S04) 3-14H20 Example 23 Residual color (please read the precautions on the back before filling this page)- Pack. Lin (ms / L) (mg / Band) (ADMT Color M) 1 0 0 619 2 10 0 607 3 20 0 610 4 50 0 607 5 100 0 588 6 200 0 556 7 500 0 474 8 0 10 579 9 0 20 577 10 0 50 523 11 0 100 489 12 0 200 332 13 0 500 145. -32- This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 83.3.10,000
、tT A7 B7 五、發明説明(3Q ) 羌 XT T T坊嫌工廠廢水染料 去除之樣品B结果:化學處理之添加麵 卜浑水 試驗 A12 (S04) 3-14H20 寅例23 殘餘顔色ft (·κ/升) (·κ/升) (ADMT顔色屋符 1 0 0 626 2 10 0 650 3 20 0 674 4 50 0 671 5 100 0 650 6 200 0 617 7 500 0 517 8 0 10 612 9 0 20 597 10 0 50 485 11 0 100 408 12 0 200 331 13 0 500 176 (請先閲讀背面之注意事項再填寫本頁) 裝 線 經濟部中央橾準局負工消費合作社印製 如殘餘顔色數據所示,丹寧-AETAC共聚物對來自此纺嫌 工廠之二廢水樣品均達成顯著顔色之去除。雖然本發明已參照其特定具體例說明之,惟預知本發明 之各種其他形式及改良會對熟悉此技藝者顯而易知。所附 -33- 本紙張尺度適用中國國家揉隼(CNS ) A4規格(210X297公釐) 83. 3.10,000 312635 A7 B7 五、發明説明(31 ) 申請專利範圍及本發明通常應被註釋為涵蓋所有該顯而易 知形式及改良,其在本發明之真正精神及範圍内。 (請先閲讀背面之注意事項再填寫本頁) 裝· 經濟部中央標準局員工消費合作社印製 -34- 83. 3. 10,000 本紙張尺度適用中國國家揉準(CNS ) A4規格(210X297公釐)、 TT A7 B7 V. Description of the invention (3Q) Sample B of Qiang XT TT Square ’s waste water dye removal: Results of chemical treatment with added muddy water test A12 (S04) 3-14H20 Example 23 Residual color ft (· κ / L) (· κ / L) (ADMT color house symbol 1 0 0 626 2 10 0 650 3 20 0 674 4 50 0 671 5 100 0 650 6 200 0 617 7 500 0 517 8 0 10 612 9 0 20 597 10 0 50 485 11 0 100 408 12 0 200 331 13 0 500 176 (Please read the precautions on the back before filling in this page) Printed by the Resident Consumer Cooperative of the Central Bureau of Preparatory Bureau of the Ministry of Economics as shown in the residual color data, The tannin-AETAC copolymer has achieved significant color removal of the two wastewater samples from this spinning plant. Although the present invention has been described with reference to its specific examples, it is predicted that various other forms and improvements of the present invention will be familiar with this technique The attached -33- This paper scale is applicable to the Chinese National Falcon (CNS) A4 specification (210X297mm) 83. 3.10,000 312635 A7 B7 V. Description of invention (31) The scope of patent application and the invention It should normally be annotated to cover all the obvious and easy to understand forms and It is well within the true spirit and scope of the present invention. (Please read the precautions on the back before filling out this page) Outfit · Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs -34- 83. 3. 10,000 This paper size is applicable Chinese National Standardization (CNS) A4 specification (210X297mm)
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TWI426054B (en) * | 2010-04-20 | 2014-02-11 | China Steel Corp | Wastewater treatment methods |
TWI694974B (en) * | 2015-05-19 | 2020-06-01 | 日商栗田工業股份有限公司 | Coagulant and water treatment method |
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TWI426054B (en) * | 2010-04-20 | 2014-02-11 | China Steel Corp | Wastewater treatment methods |
TWI694974B (en) * | 2015-05-19 | 2020-06-01 | 日商栗田工業股份有限公司 | Coagulant and water treatment method |
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