經濟部中央樣準局貝工消費合作社印製 f! τη fi：説明書條正苜 _ i、發明説明（1 ) r 在目前生活環境中，有一重要課題是如何把製造業排 ' 放的廢水加以處理，使之成爲符合環保要求標準的排放水 5 ，製造業排放的廢水中，包含許多可能危害生態環境的有 機或無機有毒物質，在無機物方面，主要有對動植物影響 ( 極大的重金屬，如汞，鎘，鉛，銅及鉻等，故環保法規上 有嚴苛之管制排放檫準，以避免此類重金屬廢水經排放後 造成環境嚴重污染。 處理重金屬廢水方法有離子浮選法，電解浮上法，逆 滲透壓法，離子交換樹脂法，但以上這些方法處理成本高 ，處理效率低，除少數特殊情形外，對日排放置大的產業 廢水可能不適用，另一最常被採用的處理方法爲化學沉澱 法，此法常用藥劑爲氫氧化鈉或氫氧化鈣等強鹼性物質， 其主要是形成水不溶性之重金層氫氧化物，使用此種強鹼 性薬劑，處理成本雖低*但有其處理極限，且形成氫氧化 物沉澱最佳之P Η值範圓窄，在連績式的廢水處理流程中 難以做穩定控制，使得處理效果差異很大，再者如以氫氧 化鈉處理形成的重金屬氫氧化物膠羽顆粒極細，沉降速度 很慢及脫水性差，更且處理後的重金屬污泥渣在自然的廢 棄或掩埋過程中會再度溶解釋出重金靥離子，而衍生出二 次公害的問題，故運用上經常需搭配使用金屬螯合劑（ Metal Chelating Agent)以提高處理的整體效果，金屬整 合劑的種類依螯合基化學組成可分爲胺乙酸鹽（ Aminoacetate) ’ 硫代（Thio),硫腺（Thiourea)及二硫代胺 基甲酸鹽（Dithiocarbamate)等數型’以上數型重金層蝥 本纸張尺度遥用中國國家梂準（C’NS ) A4规格（210X297公釐） ---------1^------1T------ i f t請先閲讀背面之注意事項再填寫本頁)Printed by the Beige Consumer Cooperative of the Central Bureau of Samples of the Ministry of Economic Affairs f! Τη fi: the instruction sheet is alfalfa _ i. Description of the invention (1) r In the current living environment, there is an important issue of how to drain the waste water from the manufacturing industry Treat it as a discharge water that meets the requirements of environmental protection standards5. The wastewater discharged from the manufacturing industry contains many organic or inorganic toxic substances that may harm the ecological environment. In terms of inorganic substances, it mainly affects animals and plants (great heavy metals, such as Mercury, cadmium, lead, copper and chromium, etc., so there are strict emission control standards in environmental regulations to avoid serious pollution of the environment after such heavy metal wastewater is discharged. Methods for treating heavy metal wastewater include ion flotation and electrolytic floatation Method, reverse osmotic pressure method, ion exchange resin method, but these methods have high treatment cost and low treatment efficiency. Except for a few special cases, it may not be suitable for industrial wastewater with large daily discharge. Another most commonly used treatment The method is chemical precipitation. The commonly used agent in this method is strong alkaline substances such as sodium hydroxide or calcium hydroxide, which mainly form water-insoluble Heavy gold layer hydroxide, using this strong alkaline solution, the treatment cost is low * but it has its treatment limit, and the formation of hydroxide precipitation is the best P Η value range is narrow, in the continuous performance of wastewater treatment process It is difficult to perform stable control in the process, which makes the treatment effect vary greatly. Furthermore, if the heavy metal hydroxide gel feather particles formed by sodium hydroxide treatment are very fine, the settling speed is very slow and the dehydration is poor, and the heavy metal sludge after treatment is in During the natural discarding or burial process, heavy gold ions will be dissolved again to explain the problem of secondary pollution. Therefore, it is often necessary to use a metal chelating agent to improve the overall effect of the treatment. The type of chelating group can be divided into amine acetate (Aminoacetate) 'thio (Thio), thio gland (Thiourea) and dithiocarbamate (Dithiocarbamate) and other types' above the number of heavy gold layers The size of the paper can be used remotely. China National Standard (C'NS) A4 specification (210X297mm) --------- 1 ^ ------ 1T ------ ift please first (Read the notes on the back and fill in this page)
A7 B7 五、發明説明（2 ) 合劑中二硫代胺基甲酸鹽是一種螯合重金屬離子能力極強 的重金屬處理薬劑。 二硫代胺基甲酸鹽（Dithiocarbamate)型重··金龎蜜合 劑，最早被使用的是低碳數烷基之二烷基二硫代胺基甲酸 鹽（Dialkyldithiocarbamate)，如二甲基二硫代胺基甲 酸鹽（Dimethyldithiocarbamate)和二乙基二硫代胺基甲 酸鹽（D i e t h y 1 d i t h i 〇 c a r b a m a t e )，此類低碳數焼基之二 烷基二硫代胺基甲酸鹽，蝥合重金屬的能力雖強，但因分 子童太低，只能形成細小的沉澱物顆粒，無法做快速沉降 及過濾處理，經常需配合使用凝結劑（Coagulant)或凝集 劑（Flocculant),爲增進此類螯合劑的使用效果，在 Europea Patent Application 009055A1,US Patent No.4,670,160,US Patent No. 5,164,095, US Patent No.4, 731, 187,日本公開特許公報昭5 7 - 2 0 7 5 9 1 平3 -2 3 1 9 2 1等篇專利，均提及可使用聚次乙亞胺 ((Polyethyleneimine)和二硫化碳（Carbon disulfide) 反應製成二硫代胺基甲酸納鹽（Dithiocarbamate sodium salt)，但以上專利所提之二硫代胺基甲酸鈉鹽，均有若 干缺點，如螯合重金層離子能力較弱，或形成之膠羽（ floe)較細小，或此蝥合劑無法完全溶解於水中，故在實 際使用上對處理效率不能作滿意的提昇。 因此，本發明的目的之一在於提供一種製造含有二硫 代胺基甲酸鈉鹽變性基之聚次乙亞胺衍生物之水溶性高分 子的方法； 本紙張尺度逋用中國國家橾準（CNS ) Α4· ( 210X297公釐) " _ I^、1ΤI I ^ ί f t請先閲讀背面之注意事項再填寫本頁) 經濟部中央標率局貝工消费合作杜印製 經濟部中央#準局員工消費合作社印策 A7 B7 五、發明説明（3 ) 本發明之另一目的在於提供一種使用上述方法製成的 高分子作爲重金屬蝥合劑之用途， 本發明之又一目的在於提供一種利用上述高分子以處 理廢水之用途。 本發明所提之重金屬蝥合劑爲聚次乙亞胺（ Polyethyleneimine)之二硫代胺基甲酸鈉鹽衍生物，在製 造上是以環氧丙醚化合物（Glycidyl ether)來改變以聚次 乙亞胺（Polyethyleneimine)爲主镰之化學結構，然後再 用二硫化碳加以變性，製成含二硫代胺基甲酸鈉鹽（ Dithicoarbamate sodium salt)水溶性高分子。 本發明所提之聚次乙亞胺（Polyethyleneimine)分子 量適宜範圍爲一萬至十萬，使用低於此分子量範圍聚次乙 亞胺之製得成品效果不彰，高於此分子置範圍聚次乙亞胺 之製得成品水溶性不佳，環氧丙醚化合物（Glycidyl ether)可爲烷基醇，芳香族醇，花楸醉（Sorbitol)或丙二 醇（Glycerol)等類之環氧丙醚化合物，此化合物上環氧基 數目最好爲兩個或兩個以上，如丙三醇雙環氧丙醚（ Glycerol diglycidyl ether)，丙三醇三環氧丙魅（ Glycerol trig lycidyl ether)，間苯二紛雙環氧丙魅（ Resorcinol diglycidyl ether)，新戊燒基二元醇雙環氧 丙魅（Neopentyl Glycol dig lycidy ether)，聚乙二醇雙 環氧丙魅（Polyethylene Glycol diglycidyl ether)等， 環氧丙醚相對於聚次乙亞胺重量比適宜量可爲〇. 1 — 1 0 %，最適宜量需視聚次乙亞胺分子置而定，適宜反應 本紙浪尺度適用中國國家標隼（CNS ) A4说格（210X297公釐） --------- 衣------1T------聲 (請先閲讀背面之注意事項再填寫本頁) A 7 B7 經濟部中央橾率局負工消費合作杜印製 五、發明説明（4 ) 溫度爲3 0 — 8 0 °C，二硫化碳相對於聚次乙亞胺重量比 適宜量爲1 G 0 — 3 0 0%，二硫化碳加料溫度最好是在 —5至5°C，後績反應溫度適宜在2 0 — 5 0°C下進行。 爲進一步說明本發明之技術內容與增進之功效，謹提 供下列實驗例與試驗數據，唯提供實驗例之目的僅供說明 之用而非用以限制本發明之範園。 〔實驗例一〕 一升反應器中準備64. 5克溴度50%之聚次乙亞 胺（分子量70000)，加水411. 9克充份攪拌均 勻溶解後升溫至5 0°C，加入0· 2 9 4克（百分比 0. 9 1%)新戊烷基二元醇雙環氧丙醚（Neopentyl Glycol diglycidyl ether)，於此溫度攪拌一小時，以冰 浴將內溫降至〇°C，激烈搅拌下同時加入二硫化碳 55. 8克（重量百分比173· 02%)及50%氫氧 化鈉水溶液60. 6克，待這兩料加完後繼績攪拌15分 鐘，再升溫至3 Ot：攢拌兩小時，灌入氮氣除去未反應之 二硫化碳，最終產物爲澳度2 〇 %之褐紅色黏稠液體。 〔實驗例二〕 一升反應器中準備71. 6克濃度30%之聚次乙亞 胺（分子量5 0 0 〇〇)加水3 16. 2克後攪拌溶解均 匀後，加入〇· 82克（重置百分比3. 83%)聚乙二 酵雙環氧丙醚（P 〇 丨 y e t h y 1 e n e G 1 y c 〇 1 d i g 1 y c i d y 1 e t h e r ---------1------IT------線’ * (請先閱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说格（210X297公釐） 經濟部中央橾牟局員工消費合作杜印製 A7 _____B7_ 五、發明説明（5 ) )反溫至5 0°C反應一小時後，將內溫降至0°C，激烈攪 拌下同時加入二硫化碳4 9. 7克（重量百分比 232. 35%)及50%氫氧化鈉水溶液57. 5克， 待加完後繼績攪1 5分鐘，再升溫至3 0°C撹拌兩小時， 灌入氮氣除去未反應之二硫化碳，再補加入至澳度爲2 0 〔實驗例三〕 同〔實驗例二〕之反應，丙三酵雙環氧丙醚（ glycerol diglycidyl ether)用置改爲 0 . 3 6 克（重量 百分比1, 6 8%)，最終產物澳度加水調整爲20%。 〔實驗例四〕 同〔實驗例二〕之反應，聚次乙亞分子量改爲 10000，絕乾用置爲21. 4克，聚乙二醇雙環氧丙 醚用；1:改爲1. 62克（重:：百分比7. 75%)，最終 產物澳度加水調整至2 0%。 〔比較例一〕 反應條件及各項原料同US Patent No.4.670,160。 同〔實例例一〕之反應設備，置入11. 2克之50 %聚次乙亞胺（分子量7 0 0 0 0 )，加1. 1%氫氧化 鈉水溶液4 6 6 . 6克，於5 0 °C —小時連績滴入二硫化 碳9. 9克，搅拌二小時後，三小時連績滴入表氯醇（ ---------1¾衣------ΪΤ------^ (請先閱讀背面之注意事項再填寫本頁) 本紙张尺度適用中國國家標隼（CNS ) A4规格（210X297公釐） -8 - 經濟部中央標牟局員工消費合作社印製 A7 B7 五、發明説明（6 )A7 B7 V. Description of the invention (2) Dithiocarbamate in the mixture is a heavy metal treatment agent with extremely strong ability to chelate heavy metal ions. Dithiocarbamate (Dithiocarbamate) type heavy · · Jin Ping honey mixture, the earliest used is low-carbon alkyl dialkyldithiocarbamate (Dialkyldithiocarbamate), such as dimethyl Dithiodicarbamate (Dimethyldithiocarbamate) and diethyldithiocarbamate (D iethy 1 dithi 〇carbamate), such low-carbon-number dialkyl dithiocarbamate Although the ability of salt and assembling heavy metals is strong, because the molecular weight is too low, it can only form fine precipitate particles, which cannot be quickly settled and filtered. It is often necessary to use a coagulant or a flocculant. In order to improve the use effect of such chelating agents, in Europea Patent Application 009055A1, US Patent No. 4,670,160, US Patent No. 5,164,095, US Patent No. 4, 731, 187, Japanese Laid-Open Patent Publication 5-7-2 0 7 5 9 1 Ping 3 -2 3 1 9 2 1 and other patents all mentioned that dithiocarbamate sodium salt (Dithiocarbamate sodium salt) can be made by the reaction of (Polyethyleneimine) and Carbon disulfide (Carbon disulfide) ), But with The dithiocarbamate sodium salt mentioned in the patent has several shortcomings, such as weak chelating ability of heavy gold layer ions, or the formation of small floe, or the candidate mixture cannot be completely dissolved in water, so In practical use, the treatment efficiency cannot be improved satisfactorily. Therefore, one of the objects of the present invention is to provide a method for producing a water-soluble polymer containing a polyethylenimine derivative modified with a sodium dithiocarbamate salt group; This paper uses the Chinese National Standard (CNS) Α4 · (210X297mm) " _ I ^, 1ΤI I ^ ί ft, please read the notes on the back before filling out this page) Consumer Cooperation Du Printing Ministry of Economic Affairs Central #Public Bureau Employee Consumer Cooperative Institution A7 B7 V. Description of the invention (3) Another object of the present invention is to provide a use of the polymer made by the above method as a heavy metal gadolinium compound, this Another object of the invention is to provide a use of the above polymer to treat wastewater. The heavy metal cane admixture mentioned in the present invention is a dithiocarbamate sodium salt derivative of Polyethyleneimine, which is modified by a Glycidyl ether compound in the manufacture of polyethyleneimine (Polyethyleneimine) The chemical structure of the main sickle, and then denatured with carbon disulfide to make a water-soluble polymer containing dithicoarbamate sodium salt. The suitable molecular weight range of the polyethyleneimine (Polyethyleneimine) mentioned in the present invention is 10,000 to 100,000, and the use of polyethyleneimine lower than this molecular weight range to produce a finished product is not effective, and the molecular weight is higher than the molecular weight range. The finished product of ethyleneimine has poor water solubility. Glycidyl ether can be alkyl alcohol, aromatic alcohol, Sorbitol or Glycerol, etc. The number of epoxy groups on this compound is preferably two or more, such as Glycerol diglycidyl ether, Glycerol trig lycidyl ether, m-benzene Resorcinol diglycidyl ether, Neopentyl Glycol dig lycidy ether, Polyethylene Glycol diglycidyl ether, etc., The appropriate amount of glycidyl ether relative to the weight ratio of polyethyleneimine can be 0.1-10%. The most suitable amount depends on the molecular position of the polyethyleneimine. It is suitable to reflect the size of the paper wave. The national standard falcon is applicable. (CNS) A4 said grid (210X 297mm) --------- clothing ------ 1T ------ sound (please read the notes on the back before filling out this page) A 7 B7 Central Bureau of the Ministry of Economic Affairs Du Printing by Negative Work Consumer Cooperation V. Description of the invention (4) The temperature is 3 0-80 ° C, the weight ratio of carbon disulfide to polyethyleneimine is 1 G 0-3 0 0%, and the temperature of carbon disulfide feeding is the most Fortunately, the temperature is -5 to 5 ° C, and the reaction temperature is suitable to be carried out at 20-50 ° C. In order to further illustrate the technical content and improved efficacy of the present invention, the following experimental examples and experimental data are provided. The purpose of providing experimental examples is for illustrative purposes only and not to limit the scope of the present invention. [Experimental Example 1] Prepare 64.5 g of polyethylenimine (molecular weight 70,000) with a bromine content of 50% in a one-liter reactor, add water to 411.9 g and stir to dissolve it, and then warm to 50 ° C, add 0 · 2 9 4 grams (percentage 0.9 1%) of neopentyl glycol diglycidyl ether (Neopentyl Glycol diglycidyl ether), stirring at this temperature for one hour, the internal temperature was reduced to 0 ° C with an ice bath At the same time, add 55.8 grams of carbon disulfide (173.02% by weight) and 60. 6 grams of 50% sodium hydroxide aqueous solution under vigorous stirring. After the addition of these two materials is completed, continue to stir for 15 minutes, and then heat up to 3 Ot: save After stirring for two hours, nitrogen was poured in to remove unreacted carbon disulfide. The final product was a brownish red viscous liquid with a degree of 20%. [Experimental Example 2] In a one-liter reactor, 71.6 g of polyethylenimine (molecular weight 50000) with a concentration of 30% was added with water 3 16. 2 g, stirred and dissolved uniformly, and 0.82 g ( (Reset percentage 3.83%) Polyethylene glycol diglycidyl ether (P 〇 丨 yethy 1 ene G 1 yc 〇1 dig 1 ycidy 1 ether --------- 1 ------ IT ------ LINE '* (Please read the precautions on the back before filling in this page) This paper standard is applicable to the Chinese National Standard (CNS) A4 grid (210X297mm) Employee consumption cooperation of the Central Bureau of Economic Affairs of the Ministry of Economic Affairs Du Printed A7 _____B7_ V. Description of the invention (5)) After inversion to 50 ° C for one hour, the internal temperature was reduced to 0 ° C, and carbon disulfide was added at 4.9.7 g (232. 35%) and 50% sodium hydroxide aqueous solution 57.5 g, after the addition is completed, stir for 15 minutes, then warm to 30 ° C and stir for two hours, pour nitrogen to remove unreacted carbon disulfide, and then add to Australia The degree is 2 0 [Experiment Example 3] The reaction with [Experiment Example 2], the glycerol diglycidyl ether is changed to 0.36 g (weight Percentage 1, 6 8%), the final product is adjusted to 20% by adding water. [Experiment Example 4] With the reaction of [Experiment Example 2], the molecular weight of polyethylene glycol was changed to 10,000, the dry-use was set to 21.4 g, and polyethylene glycol diglycidyl ether; 1: changed to 1. 62g (weight :: 7.75%), the final product is adjusted to 20% by adding water. [Comparative Example 1] The reaction conditions and raw materials are the same as US Patent No. 4.670,160. With the reaction equipment of [Example Example 1], 11.2 g of 50% polyethyleneimine (molecular weight 7000 0 0 0) was added, and 1.1% sodium hydroxide aqueous solution 4 6 6 6 g was added to 5 0 ° C-9.9 g of carbon disulfide was dripped continuously for one hour, after stirring for two hours, epichlorohydrin was dripped for three hours continuously (--------- 1¾ clothing ------ ΪΤ-- ---- ^ (Please read the precautions on the back before filling out this page) This paper size is applicable to China National Standard Falcon (CNS) A4 specification (210X297mm) -8-Printed by the Employee Consumer Cooperative of the Central Standard Mou Bureau of the Ministry of Economic Affairs A7 B7 5. Description of the invention (6)
Epichlorohydrin)0 · 2 5 克，再升溫至 8 0°C 反應二小 時，成品爲澳度5 %之白濁液髏。 〔比較例二〕 同〔實驗例一〕之反應設備，置入32. 3克之5〇 %聚次乙亞胺（同實驗例一），和水2 0 6克，均句携伴 後加入表氯醇0. 0628克（重量百分比0.389% )，升溫至5 0°C反應一小時，再降溫至0°C，滴入二硫 化碳27. 9克（重量百分比172 . 76%),携持__ 小時後加5 0%氫氧化鈉水溶液3 0 . 3克，升溫至3 〇 °C攪拌二小時，灌入氮氣，成品爲濃度2 0 %黏稠液邇[。 〔重金屬離子螯合試驗方法〕 試驗前重金屬螯合劑先以純水稀釋成1 %，再以此稀 釋液添加於試驗水樣中。 試驗水樣是以硫酸銅粉末加純水溶解，再以濾紙濾去 不溶物，銅離子含置以原子吸收光譜儀檢測。 重金屬螯合劑及氫氧化鈉添加置皆相對於試驗水樣中 銅離子澳度。Epichlorohydrin) 0 · 25 grams, then heated to 80 ° C for two hours, the finished product is a white turbid liquid with a degree of 5%. [Comparative Example 2] With the reaction equipment of [Experiment Example 1], put 32.3 g of 50% polyethylenimine (same as Experimental Example 1), and 206 g of water. Chlorohydrin 0.0628g (0.389% by weight), heated to 50 ° C for one hour, and then cooled to 0 ° C, 27.9g of carbon disulfide was dropped (172.76% by weight), holding __ After 30 hours, add 30% sodium hydroxide aqueous solution 30. 3 grams, warm to 30 ° C and stir for 2 hours, pour nitrogen, the finished product is a 20% viscous liquid. [Heavy metal ion chelation test method] Before the test, the heavy metal chelator is first diluted with pure water to 1%, and then this diluted solution is added to the test water sample. The test water sample was dissolved with copper sulfate powder plus pure water, and then the insoluble matter was filtered off with filter paper, and the copper ion was detected by atomic absorption spectrometer. The addition of heavy metal chelating agent and sodium hydroxide are relative to the degree of copper ion in the test water sample.
攪拌設備爲杯皿試驗機（Jar tester)，過濾用濾紙爲 0 . 4 5 // m(MILLIP0RE HV)，原子吸收光譜儀爲 PERKIN -ELMER 3 0 0 0型，燈管爲銅標準燈管。 試驗步騄：試驗水樣每杯取5 0 Omi，先加重金靥 蝥合劑再加氫氧化鈉，加槊攪拌速度爲 水紙張尺度適用中國國家梂率（CNS ) Α4洗格（2丨0Χ297公釐） --------1 |扣衣------ΐτ------m I (請先閱讀背面之注意事β再填寫本頁) A7 B7 丨 i'發明説明（7 ) 1 0 Orpm，績攪1 0分鏟，降爲2 Ο r pm再搅5分鐘後，以濾紙過濾，濾液 加硝酸使pH降至2. 0，再以原子吸收 光譜儀檢測銅含量。 處理率計算式：1 0 0% —(殘餘銅量/試驗水樑中 銅置）* 1 〇 0 % 〔轼驗一〕 重金屬蝥合劑爲〔實驗例一〕及〔實驗例二〕成品 氫氧化鈉添加量爲8 0 p pm，試驗水樣中銅含量爲 97. 3 9 p p m ° 重金靥蝥合劑添加置及試驗結果見下表： 重金饜蝥合劑 金饜螯合劑 殘餘飼量 處理率 種類 添加量ppm ppm % 10 66.12 27.65 20 54.23 40.66 [實驗例一] 40 42.71 53.27 80 19.13 79.07 120 1.29 98.58 20 53.62 41.33 [實驗例二] 40 49.22 46.Η 80 3.92 95.71 120 2.07 97.74 〔試驗二〕 重金羼蝥合劑爲〔實驗三〕成品 試驗水樣中銅含置爲7 4. 3 1 ppm。 氫氧化鈉添加置，重金屬蝥合劑添加量及試驗結果見下表 本紙張尺度逋用中國國家揉窣（CNS ) A4規格（210X297公釐） --------——装—I - (請先閱讀背面之注意事項再填寫本萸) 訂 經濟部中央揉準局員工消费合作社印製 A7 B7 五、發明説明（8 重金屬蝥合劑 氫氧化納 殘餘铜量 處理率 添加量ppn 浓加鱼ppm ppm % 0 74.31 0.00 20 65.12 12.37 — 80 46.72 37.13 100 3.07 95.87 200 3.65 95.09 0 62.99 15.23 20 45.60 38.51 60 80 1.99 97.32 100 1.32 98.21 200 0.91 98.78 L, —裝-- (請先閲讀背面之注意事項再填寫本頁) 經濟部中央揉準局負工消費合作社印製 trThe stirring equipment is a jar tester (Jar tester), the filter paper for filtration is 0.4 5 // m (MILLIP0RE HV), the atomic absorption spectrometer is a PERKIN-ELMER 3 0 0 0 type, and the lamp tube is a copper standard lamp tube. Test step: Take 50 Omi per cup of the test water sample, firstly add the gold-admixture mixture and then add sodium hydroxide, and add the stirring speed to the water paper scale. Applicable to China National Frame Rate (CNS) Α4 wash grid (2 丨 0Χ297 public %) -------- 1 | Clothing ------ lτ ------ m I (please read the notes on the back first and then fill in this page) A7 B7 丨 i'instructions (7) 100 Orpm, shovel for 10 minutes, reduce to 2 Ο r pm and then stir for 5 minutes, filter with filter paper, add nitric acid to the filtrate to reduce the pH to 2.0, and then measure the copper content by atomic absorption spectrometer. Calculation formula of treatment rate: 1 0 0% — (Residual copper content / copper set in the test water beam) * 1 〇0% [轼 测 一] The mixture of heavy metal assemblages is [Experiment Example 1] and [Experiment Example 2] The addition amount of sodium is 80 p pm, the copper content in the test water sample is 97. 3 9 ppm ° The addition and test results of the heavy gold taurantium mixture and the test results are shown in the following table: Amount ppm ppm% 10 66.12 27.65 20 54.23 40.66 [Experiment Example 1] 40 42.71 53.27 80 19.13 79.07 120 1.29 98.58 20 53.62 41.33 [Experiment Example 2] 40 49.22 46.Η 80 3.92 95.71 120 2.07 97.74 [Experiment 2] Heavy Jin Yuga The mixture is [Experiment 3] The copper content in the finished test water sample is 7 4. 3 1 ppm. The sodium hydroxide is added, the amount of heavy metal assemblage added and the test results are shown in the table below. The paper size is based on China National Rolling Mill (CNS) A4 specification (210X297mm) ------------ installed -I- (Please read the precautions on the back before filling in the cornel) Order A7 B7 printed by the Employee Consumer Cooperative of the Central Bureau of Economic Development of the Ministry of Economy V. Description of the invention (8 Heavy Metal Candidate Mixture Sodium Hydroxide Residual Copper Amount Processing Rate Added Amount PPN Concentrated Fish ppm ppm% 0 74.31 0.00 20 65.12 12.37 — 80 46.72 37.13 100 3.07 95.87 200 3.65 95.09 0 62.99 15.23 20 45.60 38.51 60 80 1.99 97.32 100 1.32 98.21 200 0.91 98.78 L,-install-(please read the precautions on the back first (Fill in this page) Printed tr by the Ministry of Economic Affairs Central Bureau of Accreditation Consumer Cooperative
〔試驗三〕 I[Experiment 3] I
I 重金屬蝥合劑爲〔實驗例一〕 丨 氫氧化鈉添加量200ppm，重金屬蝥合劑添加量 | 1 2 Ο ρ p m ° ^ 試驗水樣銅離子含：t210_77ppm。 | 再溶出率計算式：（殘餘銅量/試驗水樣中銅量）· 丨 ! 10 0% i 網再溶出試驗，試驗結果見下表： 本紙浪尺度適用中國國家揉準（CNS ) A4規格（210X297公釐） -11 - 五、發明説明（9 ) A7 B7 處理第劑 種類 \疏酸 添加量ppm 漶液 Pirn 殘餘鋦悬 ppm 再溶出率 % 0 10.5 2.09 9.61 氫氧化納 100 8.4 40.90 19.40 230 5.0 203.19 96.31 重金属蝥合劑 0 10.5 0.851 0.40 118 8.4 0.881 0.42 氫氧化納 234 5.0 29.17 13.84 〔試驗四〕 氫氧化鈉添加置3 0 0 p pm，試驗水樣銅離子含量 16 7. 2 p p m ° 試驗比較結果如下表： 重金靥蝥合劑 金靥蝥合劑 殘餘飼量 處理率 種類 添加董ppm ppm % 40 0.979 99.41 [實驗例一] 60 0.869 99.48 80 0.622 99.63 40 21.47 87.14 [比較例一] 60 12.16 92.72 80 6.53 96.09 40 18.94 88.66 [比較例二] 60 9.38 94,38 80 3.42 97.95 --------.—裝------訂------線 * (請先閱讀背面之注意事項再填寫本頁) 經濟部中央橾準局負工消费合作杜印製 由以上試驗結果可知，透過本發明方法所製成的高分 子可有效處理水中的銅離子，而其處理率也比使用先前技 術之金靥蝥合劑爲優。上述幾種製備本發明高分子以及整 合銅離子之實驗例係僅供說明之用而非用以限制本發明， 在不脫離本發明之技術思想與範圍之下可做各種不同的變 本紙浪尺度適用中國國家揉準（CNS ) A4規格（210X297公釐） -12 - A7 B7 五、發明説明（10 ) 更與修飾，由於產製本發明高分子之方法確屬新穎而且使 的’ 目件 之要。 水利11 廢專爲 屬定利 金法專 重之准 理性賜 處步日 到進早 達與懊 屬性情 金穎之 重新慎 合法明 蝥利正 效專公 有合持 可符秉 子已局 分應贵 髙此 該因請 用，懇 ------„----/-¾衣------1T------^ (請先閱讀背面之注意事項再填寫本頁) 經濟部中央樣隼局員工消費合作杜印製 本紙張尺度逋用中國國家標準（CNS ) A4规格（210X297公董）I. Heavy metal assemblage is [Experiment example 1] 丨 The amount of sodium hydroxide added is 200ppm, and the amount of assemblage of heavy metal assemblage | 1 2 Ο ρ p m ° ^ The test water sample contains copper ions: t210_77ppm. | Calculation formula of re-dissolution rate: (residual copper amount / copper amount in test water sample) · 丨! 10 0% i Net re-dissolution test, the test results are shown in the table below: This paper wave scale is applicable to China National Standard (CNS) A4 (210X297mm) -11-V. Description of the invention (9) A7 B7 Treatment agent type \ Sulphuric acid addition amount ppm Washing liquid Pirn Residual hang suspension ppm Re-dissolution rate% 0 10.5 2.09 9.61 Sodium hydroxide 100 8.4 40.90 19.40 230 5.0 203.19 96.31 Mixture of heavy metal assemblage 0 10.5 0.851 0.40 118 8.4 0.881 0.42 sodium hydroxide 234 5.0 29.17 13.84 [test 4] sodium hydroxide added 3 0 0 p pm, test water sample copper ion content 16 7. 2 ppm ° test comparison The results are shown in the following table: The treatment rate of the residual feed rate of the heavy gold-hematocrit mixture is added by ppm ppm% 40 0.979 99.41 [Experiment example 1] 60 0.869 99.48 80 0.622 99.63 40 21.47 87.14 [comparative example one] 60 12.16 92.72 80 6.53 96.09 40 18.94 88.66 [Comparative Example 2] 60 9.38 94,38 80 3.42 97.95 --------.— installed ------ ordered ------ line * (please read the note on the back first Please fill in this page again) According to the above test results, the polymer produced by the method of the present invention can effectively treat copper ions in water, and its processing rate is also better than that of the prior art gold-admixture mixture. . The above experimental examples for preparing the polymer of the present invention and integrating copper ions are for illustrative purposes only and are not intended to limit the present invention. Various variations of the paper wave scale can be made without departing from the technical idea and scope of the present invention Applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) -12-A7 B7 5. Description of the invention (10) More and modified, because the method of producing the polymer of the present invention is indeed new and important . The water conservancy 11 is a quasi-rational gift that belongs to the special deposit gold law. The advancement is early and the sorrowfulness of Jin Ying ’s renewed prudence and lawfulness. For this reason, please use, sincerely ------ „---- /-¾ clothing ------ 1T -------- ^ (please read the precautions on the back before filling this page) Economy The Ministry of Central Sample Falcon Bureau ’s consumer cooperation to print this paper uses the Chinese National Standard (CNS) A4 specification (210X297 company director)