TW510891B - Method for treating used electroplating solution - Google Patents

Abstract

A method for treating a used electroplating solution is disclosed. By using an ozone/ultraviolet (UV)/additive system to treat the organic substances in the used electroplating solution, the organic substances can be decomposed and thus removed by the oxidation of ozone, which is a strong oxidant. The ozone may be combined with UV and additive so as to catalytically oxidize the organic substances. The additive may also absorb the residual organic substances. The used additive, which absorbs the residual organic substances, may be further removed by filtration. The removal efficiency of organic substances by the combined ozone, UV and additive can exceed 90%. The used electroplating solution, after being treated by this method and adjusted by the addition of some fresh organic substances to fit the recipe, can then be reutilized again. By doing this, one can achieve the goal for the removal of the organic wastes as well as the recovery and reutilization of the resources.

Description

510891510891

，，係有關一種廢液之處理方法，特別是關於一種利 用臭氧高氧化力配合紫外光和添加物吸附催化而去除電鍍 程序廢液中有機物的方法。 發明背景 印刷電路板（Printed wiring board，pwB 或printed, It is related to a method for treating waste liquid, especially a method for removing organic matter in electroplating process waste liquid by using high oxidation power of ozone in combination with ultraviolet light and additive adsorption catalysis. BACKGROUND OF THE INVENTION Printed wiring board (pwB or printed)

ClrCUlt、b〇ard，PCB)工業在近年來成長快速，其廢水的 處理已成為一項重要的課題。 電鍍液中的主要成份為無機物，（如：金屬離子 '強 酸等），為了增進電鍍品質，尚需加入—些有機助劑， (如:光澤劑、載流劑、安定劑、分散劑等）。對於無機物 的部分’有人曾提出以硫化亞鐵還原電鍍液中的六價鉻的 方法（US patent,專利號碼4705639 )。對於有機物的處 理，則尚無有效方法。根據經濟部工業局（1 996 )的資 印刷電路板廢水處理的方式仍舊以傳統式的化學混凝 主，生物處理為輔。所產生的污泥則委託清除處理業者負 責清除處S。^吏含有機物之電鍍程序廢液亦委託廢水處 理廠處理而未回收利用，成為印刷電路板廢 問題。 ^ 上述之化學混凝法及生物處理，仍存在許多問題而 使處理效果不彰。例 化學混凝法所加入之物質㈣ 電鑛廢液的性質而使回收廢液變為不可行。而因為合= 污泥’則其後續處理將更加麻煩。此夕卜，電鍍廢液：^ 性質將使微生物無法生存。因此，在生物處理程，酸 510891 __案號88110499 年：Γ月#日 修正_ 五、發明說明（2) / 勢必要將電鍍廢液稀釋以降低其酸度，如此不單增加成 本，也降低了處理的效率。且由於生物處理僅為化學處理 的輔助程序，所以處理後之廢水仍屬不可回收。 臭氧應用於高級氧化處理程序（advance oxidation process，AOPs)已廣泛的使用於水及廢水處理。比如以臭 氧控制飲用水中之三自.甲烷（Rice，r. G. "The Use ofClrCUlt, PCB, PCB) industry has grown rapidly in recent years, and its wastewater treatment has become an important subject. The main components in the plating solution are inorganic substances (such as: metal ions' strong acids, etc.). In order to improve the quality of electroplating, some organic auxiliaries need to be added (such as: gloss agents, current carriers, stabilizers, dispersants, etc.) . For the part of inorganic substances, a method of reducing hexavalent chromium in a plating solution with ferrous sulfide has been proposed (US patent, patent number 4705639). There is no effective method for organic matter treatment. According to the Industrial Bureau of the Ministry of Economic Affairs (1 996), the printed circuit board wastewater treatment method is still mainly traditional chemical coagulation, supplemented by biological treatment. The generated sludge is entrusted to the removal and treatment operator S to be responsible for removal. ^ The waste liquid of electroplating process containing organic materials is also entrusted to a waste water treatment plant for treatment without recycling, which has become a waste of printed circuit boards. ^ The above-mentioned chemical coagulation method and biological treatment still have many problems and make the treatment effect inadequate. Example: The nature of the material added by the chemical coagulation method: The nature of the waste liquid from the power plant makes it impossible to recover the waste liquid. And because the combined = sludge ', its subsequent processing will be more troublesome. Moreover, electroplating waste liquid: ^ nature will make microorganisms unable to survive. Therefore, in the biological treatment process, acid 510891 __ Case No. 88110499: Γ 月 # 日 改 _ V. Description of the invention (2) / It is necessary to dilute the electroplating waste solution to reduce its acidity, which not only increases costs but also reduces Processing efficiency. And because biological treatment is only an auxiliary procedure for chemical treatment, the treated wastewater is still not recyclable. The application of ozone in advanced oxidation processes (AOPs) has been widely used in water and wastewater treatment. For example, the use of ozone to control three-methane in drinking water (Rice, r. G. " The Use of

Ozone to Control Trihalomethanes in Drinking Water Treatment, ,f Ozone Sci. Eng., Vol. 2, pp. 75-99, 1 9 8 0 ) ’或處理農藥（林鴻祥，顧洋，"以臭氧及紫外線/ 臭氧程序處理福瑞松農藥水溶液反應行為之研究，"第二 =一屆廢水處理技術研討會論文集，ρρ· 155_162，1997) 等等。已申請專利者則有如以臭氧/紫外光去除廢水中之 酮類，醛類，酯類及有機酸（us patent，專利編號 I!7231) ’甚至將臭氧/紫外光程序用於土壤污染物之復 利編號5259962)。然而將其應用於電鑛 紅序廢液所3有機物的處理則尚未見諸文獻。 發明說明 法 本發明之目的係提供一種 本案之另-目的則為提供=液中有機物的去除方 廢液處理法。本案以臭氧、臭"w以回收電鍍液的電鍍 /添加物程序處理電鍵程序廢=右:&臭氧/紫外光 含之總有機碳。以供回收再利有機添加劑，去除其所 則可於補充新料調配後再刹 所回收之處理後廢液， 」用為新電鍍液。Ozone to Control Trihalomethanes in Drinking Water Treatment,, f Ozone Sci. Eng., Vol. 2, pp. 75-99, 1 9 8 0) 'Or treat pesticides (Lin Hongxiang, Gu Yang, " Ozone and UV / Ozone Study on the reaction behaviors of program treatment of furosemide pesticide aqueous solution, " Second = Proceedings of the Second Symposium on Wastewater Treatment Technology, ρ · 155_162, 1997) and so on. Patent applicants have used ozone / ultraviolet light to remove ketones, aldehydes, esters, and organic acids (us patent (patent number I! 7231)) from wastewater. Even ozone / ultraviolet light programs are used for soil pollutants. Compound interest number 5299962). However, its application to the treatment of organic matter in the red-sequence waste liquid of power ore has not been found in the literature. DESCRIPTION OF THE INVENTION Method The object of the present invention is to provide a waste liquid treatment method which provides another aspect of the present case to remove organic matters in the liquid. This case uses ozone, odor " w to recover the electroplating solution by electroplating / additive program to treat the key program waste = right: & ozone / ultraviolet light Total organic carbon contained. Recycling organic additives can be recycled, and the waste liquid can be removed after being replenished with new materials and mixed, and used as a new plating solution.

第8頁 510891Page 510891

--_t#. «R110AQQ 五、發明說明（3) 本案提供了一種處理一含有機助劑之電鍍程序廢液 方法’其步驟包括收集電鍍程序廢液，及通入一 #、片 電鍍程序廢液，並以一紫外光照射該電鍍程序賡^乳二^ 除該有機助劑。 & 去 ，了達到更好的效果，更可以加入一添加物於該電贫 私序廢液中以吸附該有機助劑。其中，該添加物可 $ 鐵、氧化銅等金屬氧化物，或其他任何可以達到吸附 或催化效果的物質。--_ t #. «R110AQQ V. Description of the invention (3) This case provides a method for treating a plating solution waste liquid containing organic additives. The steps include collecting the plating solution waste liquid, and passing in a #, sheet plating program waste Liquid, and irradiate the plating process with a UV light to remove the organic auxiliary. & Go, to achieve better results, you can also add an additive to the electrolyzed private sequence waste liquid to adsorb the organic auxiliary. Among them, the additive can be a metal oxide such as iron, copper oxide, or any other substance that can achieve adsorption or catalytic effects.

於該添加物吸附該有機助劑後，更可以過濾法移除該 添加物以回收該電鍍程序廢液。其中，該添加^更可以^ 有催化臭氧/紫外光氧化反應之能力，以達更佳效果。^ 其中，臭氧、添加物與電鍍程序廢液係可利用一氣/液/ 接觸裝置進行直接接觸。 因應電鍍程序廢液性質，可適當調整添加物的種類及 /或添加量。 ^ 忒有機助劑可為光澤劑、分散劑、載流劑或安定劑 等等任何有機添加物，而會在電鍍過程中參與反應或隨之 改變性質者。 在該電鍍程序廢液中之該有機助劑去除後，可以重新After the additive adsorbs the organic assistant, the additive can be removed by filtration to recover the electroplating process waste liquid. Among them, the addition can have the ability to catalyze the ozone / ultraviolet oxidation reaction to achieve better results. ^ Among them, ozone, additives and waste liquid of the plating process can be directly contacted by a gas / liquid / contact device. Depending on the nature of the waste liquid of the plating process, the type and / or amount of additives can be adjusted appropriately. ^ 忒 Organic additives can be any organic additives such as gloss agents, dispersants, current carriers or stabilizers, and will participate in the reaction or change properties in the plating process. After the organic auxiliary agent is removed from the electroplating process waste liquid, it can be restarted.

加入未使用過之有機助劑以回收再利用該電鍵程序廢 液。 該紫外光可為直接或間接照射或直接/間接兩者組合 照射該電鍍程序廢液。 因應各種不同的電鍍程序廢液的性質，可適當調整該Add unused organic auxiliaries to recover and reuse this key program waste. The ultraviolet light may be directly or indirectly irradiated or a combination of both directly / indirectly irradiated the plating solution waste liquid. Due to the nature of various different plating process waste liquids, this can be adjusted appropriately

修正一 案號 88110499 五、發明說明（4) ^氧濃度以及該紫外光強度的步驟。臭氧/紫外光/添加物 吸附中之一種或數種程序亦可視情況單獨使用或互相搭 配。 遠庐^氧與電鍍程序廢液接觸的方式可為批式、半批式或 、、、 六氧與電錢程序廢液可於一單样式、多槽式、串 =或並聯式反應裝置中進行氧化反應：：動之方向可為 同向、逆向或複合流向。 案知藉由下列圖示及詳細說明，俾得一更深入之了解： 圖:為本案之一反應裝置系統實施例示意圖； 圖=為圖一之詳細反應裝置示意圖； 圖二為本案方法實施流程之示意圖； _ @ ΐ四3為只以臭氧程序處理之有機物去除率與臭氧化反 應時間關係圖； &圖五為臭氧程序配合紫外光處理之有機物去除率與 乳化反應時間關係圖；以及 、 為臭氧/紫外光/添加物程序處理之有機物去 與臭氧化反應時間關係圖。 千 圖示中各主要元件之簡單說明如下： 反應槽外層 攪拌裝置 氧或空氣供應裝置 12 16 20 1 〇:反應裝置 1 4 : 反應槽内層 1 8 :攪拌翼裝置Amendment Case No. 88110499 V. Description of the Invention (4) ^ The step of oxygen concentration and the intensity of the ultraviolet light. One or more procedures of ozone / ultraviolet light / additive adsorption can also be used individually or in combination with each other. The method of contacting Yuanluo oxygen with the waste liquid of the electroplating process can be batch, semi-batch type, or ,,,, and hexaoxygen. The waste liquid can be used in a single-type, multi-tank, string =, or parallel reaction device. Perform oxidation reaction: the direction of movement can be co-directional, reverse or composite flow direction. The case knows a more in-depth understanding through the following diagrams and detailed descriptions: Figure: a schematic diagram of an embodiment of a reaction device system of the case; Figure = is a schematic diagram of a detailed reaction device of Figure 1; Figure 2 is the implementation process of the method of the case Schematic diagram; _ @ ΐ 四 3 is the relationship between organic matter removal rate and ozonation reaction time treated with ozone program only; & Figure 5 is the relationship between organic matter removal rate and emulsification reaction time with ozone program and ultraviolet light treatment; and, Relation diagram of organic matter removal and ozonation reaction time for ozone / ultraviolet light / additive program. Thousands of the main components in the picture are briefly explained as follows: Outside layer of reaction tank Stirring device Oxygen or air supply device 12 16 20 1 〇: Reaction device 14 4: Inside layer of reaction tank 1 8: Stirring wing device

第10頁 510891 _ 案號88110499 年Γ月 五、發明說明（5) 22 臭 氧 產 生 裝 置 24 26 氣 相 臭 氣 濃度 量 測 裝 置 28 30 液 相 臭 氣 濃 度 量 測 裝 置 32 34 液 體 取 樣 幫 浦 36 38 擋 板 裝 置 40 42 氣 體 取 樣 或 排 氣 裝 置 44 46 液 體 取 樣 裝 置 47 48 進 氣 51 52 添 加 物 53 54 紫 外 光 55 56 臭 氧/紫外光/ 添 加 物 反應57 58 過 濾 添 加 物 59 60 添 加 物 及 被 吸 附 之 有 機物61 62 添 加 混 合 63 流量量測裝置 臭氧進氣管 十互溫裝置 臭氣散氣裝置 紫外光裝置 酸驗值量測裝置 排氣罩 電鑛廢液 臭氧 混合吸附 進—步混合吸附 回收之電鍍液 新的有機助劑 回收再利用 本發明所使用之裝置可如圖一及圖二所示之一具備恆 溫流體夾層的攪拌反應裝置10，内層14由破璃製造， 12是壓克力，夾層之間有由恆溫裝置32所提供t之恆 體持續通過。攪拌裝置16為機械式攪拌，附攪拌翼18夂〜詈 (如：六葉平輪），並附有轉速及扭力計數裝置。攪^ 16與反應裝置10頂蓋間以軸封裝置（如： 十装^ 示)連結。反應裝置頂蓋上並有數個直徑不蓋未 用以裝置紫外光裝置4〇，酸鹼值計44，液體取樣裝置 46(取樣口及取樣管），曝氣管28及曝氣頭36。氧氣或空氣 “由氧或空氣供應裝置2〇通入臭氧產生裝置22 故Page 10 510891 _ Case No. 88110499 Γ May 5. Description of the invention (5) 22 Ozone generating device 24 26 Gas phase odor concentration measuring device 28 30 Liquid phase odor concentration measuring device 32 34 Liquid sampling pump 36 38 Baffle device 40 42 Gas sampling or exhaust device 44 46 Liquid sampling device 47 48 Intake 51 52 Additives 53 54 Ultraviolet light 55 56 Ozone / ultraviolet light / additive reaction 57 58 Filtering additives 59 60 Additives and adsorption Organic matter 61 62 Adding and mixing 63 Flow measuring device Ozone inlet pipe Ten mutual temperature device Odor dispersing device Ultraviolet light device Acid value measuring device Exhaust hood Electric mine waste liquid Ozone mixed adsorption-step mixed adsorption recovery New organic additives for electroplating bath recovery and reuse. The device used in the present invention can be a stirred reaction device 10 with a constant temperature fluid interlayer as shown in one of Figs. 1 and 2. The inner layer 14 is made of broken glass. 12 is acrylic. There is a constant t between the interlayers provided by the thermostatic device 32 By continuing. The stirring device 16 is a mechanical stirring device, with stirring wings 18 夂 ~ 詈 (such as a six-blade flat wheel), and a rotating speed and torque counting device. The shaft 16 and the top cover of the reaction device 10 are connected by a shaft sealing device (such as: ten devices). The top cover of the reaction device is provided with several diameter unused UV devices 40, pH meter 44, liquid sampling device 46 (sampling port and sampling tube), aeration tube 28 and aeration head 36. Oxygen or air "O2 from the oxygen or air supply device to the ozone generator 22

510891 修正 #號 8811(Uqq 五、發明說明（β) ^ f机里S測裝置24 (如··浮子流量計）調整並記錄其流 置、’ f由臭氧氣相分析儀26監測其濃度值，至濃度穩定後 =進行正式操作。所產生之濃度穩定的臭氧由曝氣管28内 : '通往槽底由曝氣頭36分散進入液相。氣體由裝於槽 二的”=樣或排氣裝置42通至氣相臭氧分析儀26，連續 ^測臭氧濃度，偵測後之臭氧則送至排氣罩47排出。操作 #槽内液體由液體取樣裝置46(取樣管）抽出，經液體取樣 幫浦3 4抽至液相臭氧分析儀3 〇，進行液相臭氧濃度的監 測，亚有取樣閥可在不同時間取樣進行總有機碳 organic carbon，TOC)的分析。 紫外光裝置40包括一個或數個石英套管内放置不同瓦 特，之紫外光（ultravi〇let，uv)燈管，並由光強度計事先 測量其在波長254 run (臭氧的吸收波長）的表面光強度， 热習本項技藝者雖可逕以任意可行之氣/液/固接觸裝置及 光反應裝置（如：中華民國專利號碼299770號，19 月8號申請之”注入式紫外光/臭氧氧化裝置，，，等等）取代此 處理裝置，然皆不脫本專利所欲保護之處理方法。 添加物可為如氧化鐵、氧化銅等金屬氧化物，更可為 任何其他吸附劑及/或氧化性觸媒（如鉑或過渡金屬觸媒 等），以利用其吸附及或對臭氧/紫外光氧化反應的催化效 果，來進一步移除電鍍程序廢液中的有機物質。當然，添 加物的選用仍以能在儘量不影響電鍍程序廢液中的其他有 用物質（如其他無機物）的組成為原則對有機物進行吸附/ 催化作用’以利回收使用。即使無機物亦被吸附或催化，510891 Amendment No. 8811 (Uqq V. Description of the invention (β) ^ f S-measurement device 24 in the machine (such as a float flowmeter) adjusts and records its flow position, 'f is monitored by the ozone gas phase analyzer 26 concentration value After the concentration is stable = the formal operation is performed. The ozone with a stable concentration is generated from the aeration tube 28: 'to the bottom of the tank is dispersed into the liquid phase by the aeration head 36. The gas is installed in the second tank "= sample or The exhaust device 42 is connected to the gas phase ozone analyzer 26, and the ozone concentration is continuously measured, and the detected ozone is sent to the exhaust hood 47 for discharge. Operation #The liquid in the tank is extracted by the liquid sampling device 46 (sampling tube), The liquid sampling pump 34 is pumped to the liquid ozone analyzer 30 to monitor the liquid ozone concentration, and the sub-sampling valve can sample at different times for total organic carbon (TOC) analysis. The ultraviolet light device 40 includes One or several quartz tubes are placed with different watts of ultraviolet light (ultraviolet, uv) lamps, and the surface light intensity at a wavelength of 254 run (the absorption wavelength of ozone) is measured by a light intensity meter in advance. Artists can use any viable manner / / Solid contact device and photoreaction device (such as: "Injection UV / Ozone Oxidation Device," etc., applied for the Republic of China Patent No. 299770, applied on September 8th, etc.) instead of this processing device, but do not depart from this patent The treatment method you want to protect. Additives can be metal oxides such as iron oxide, copper oxide, etc., and can also be any other adsorbent and / or oxidizing catalyst (such as platinum or transition metal catalyst, etc.) to use its adsorption and / or ozone / ultraviolet The catalytic effect of the photo-oxidation reaction to further remove organic substances from the plating solution waste liquid. Of course, the selection of additives is still based on the principle that the composition of other useful substances (such as other inorganic substances) in the electroplating process waste liquid is not affected as much as possible to facilitate the adsorption / catalysis of organic substances' to facilitate recycling. Even inorganic substances are adsorbed or catalyzed,

第12頁 510891 ^^ 88110499 修正 年厂月 五、發明說明（7) 只要其不留下難以過濾或移除之殘留物’，仍可對處理後之 程序廢液進行適當之補料後予以回收使用。 處理流程 處理流程大致如圖三，將電鍍程序廢水51加入添加物 52(如：氧化鐵），經混合吸附程序55後並通入臭氧53/紫 外光54，進行反應程序56，期間可視情況再加又添加物52 進行混合吸附程序57，最後以過濾程序58去除添加物沈 澱，即可將電鍍廢液及吸附有機物之添加物6〇分開，而得 已去除有機物之電鍍廢液59，並可進一步加入新的有機助 劑61與電鍍廢液59進行添加混合之程序62，以進行回收再 利用之步驟63。其中，各步驟及其順序均可視實際需要而 作調整。一般而言，添加物的混合吸附僅需在臭氧/紫外 光程序之前或之後擇一為之即可。然而，視實際情況兩 要，亦可在臭氧/紫外光程序進行時加入添加物。若添加 物加入時機為臭氧/紫外光程序進行之前或進行時，在某 些情況下添加物除了吸附的功能外，尚可作為臭氧及/ 紫外光氧化反應之催化劑。 < 1圓 紫外光可為直接或間接照射或直接/間接兩者袓合照 射該電鍍程序廢液。因應各種不同的電電鍍程序廢液口的性 質，可適當調整該臭氧濃度以及該紫外光強度的步驟。臭 軋與電鍍程序廢液接觸的方式可為批式、半批式或連續 式。臭氧與電鍍程序廢液可於一單槽式、多槽式、串^式 或並聯式反應裝置中進行氧化反應。流動之方向可為同 向、逆向或複合流向。臭氧、添加物與電鍍程序廢液係可Page 12 510891 ^^ 88110499 Revised Year 5. Description of the invention (7) As long as it does not leave residues that are difficult to filter or remove, it is still possible to recycle the treated process waste liquid after appropriate supplementation. use. Treatment process The treatment process is roughly shown in Figure 3. The electroplating process wastewater 51 is added to the additive 52 (such as iron oxide). After the mixed adsorption process 55 and ozone 53 / ultraviolet light 54 is passed, the reaction process 56 is performed. Add and add the additive 52 to perform the mixing adsorption procedure 57 and finally remove the additive precipitation by the filtering procedure 58 to separate the electroplating waste liquid and the organic adsorption additive 60, and obtain the electroplating waste liquid 59 from which organic matter has been removed, and Further, a new organic assistant 61 and a plating waste liquid 59 are added and mixed in a procedure 62 to perform a recycling step 63. Among them, each step and its order can be adjusted according to actual needs. In general, the mixed adsorption of the additives need only be selected before or after the ozone / UV program. However, depending on the actual situation, it is also possible to add additives during the ozone / UV process. If the timing of the addition of the additive is before or during the ozone / ultraviolet program, in some cases the additive can be used as a catalyst for ozone and / or ultraviolet photooxidation in addition to its adsorption function. < 1 circle UV light can be direct or indirect irradiation or a combination of both direct / indirect irradiation of the plating process waste liquid. The steps of adjusting the ozone concentration and the intensity of the ultraviolet light can be adjusted according to the properties of the waste liquid port of various electroplating procedures. The method of contacting the odor rolling with the waste liquid of the plating process can be batch, semi-batch or continuous. The ozone and electroplating process waste liquid can be oxidized in a single-tank, multi-tank, series or parallel reactor. The direction of flow can be co-directional, reverse or composite. Ozone, additives and waste liquids from plating processes

第13頁Page 13

處理效果 效果兹鑛廢液中有機物去除之處理 TOC)去除率代表）為6〇 %左 J carbon， 五） 則有78%的去除率.如果/；^搭配上紫外光（圖 六） 則去除桌可、去Γ ί，果軋化鐵吸附前處理（圖 麥定詹採、ρ達九成。實務上可依所需有機物去除率來 量-3U 配。圖四至圖六實例之實驗條件為廢液 里-3.705 L，氣體流量=1.78 SLpM，氣體臭氧 液 mg/L，紫外光表面光強度=44 w/m2，氧化鐵添加=ι〇〇 g，廢液T0C濃度=16 mg/L ,酸鹼值（pH)在〇17-〇 44之 間，CuS04 · 5H20 濃度= 2 0 0 g/L，離子強度=5 M。 電鍍程序廢液通常為酸鹼值在丨或丨以下之強酸廢液，而對 熟習此技藝之人士而言，傳統臭氧程序必需在鹼性環境中 方能發揮最大效果，故一般均不會以之處理強酸廢液。麸 而’本案首先提出利用臭氧/紫外光或臭氧/紫外光/添加… 物之程序來處理電鍍程序廢液，而且已驗證具有良好之效 果。本案之程序不但較傳統化學混凝/生物處理法之程序 較為簡便，更不需要額外的稀釋等繁雜之步驟，是故無論 在處理效率及費用上都較傳統方法為之經濟。更重要的 是’以本案之方法處理後的電鍍程序廢液可有效去除電鍵 510891 _案號88110499_夕d年厂月^/日____ 修+ 五、發明說明（9) 液中已失效之有機物添加物，而且不會殘留任何難以移除 之處理程序廢物於電鍍液中。因而，經本案方法處理後之 電鍍程序廢液可在添加新的有機助劑後重新回收使用。此 一回收功能乃傳統電鍍程序廢液的回收方法中所不可 :程；；液本=之方法不僅可有效並價廉的處理電 電錢業者長期=程；廢液的回收方法，解決了 業價值之作。 序廢液處理之困擾，實乃一極具產 本案所舉，熟習本工 飾，然皆不脫如附申1，藝者雖可任施匠思而為諸般修 τ明專利範圍所欲保護者。The effect of the treatment effect The removal of organic matter in the waste liquid of the mine is TOC) The removal rate represents 60% of the left J carbon, and 5) it has a removal rate of 78%. If /; ^ is matched with ultraviolet light (Figure 6), it is removed The table can be removed, and the pre-adsorption treatment of fruit rolling iron (Tumedin Zhancai, ρ is 90%. In practice, the amount can be -3U according to the required organic removal rate. The experimental conditions of the examples in Figures 4 to 6 are: Waste liquid-3.705 L, gas flow rate = 1.78 SLpM, gas ozone liquid mg / L, ultraviolet light surface light intensity = 44 w / m2, iron oxide addition = ι〇〇g, waste liquid T0C concentration = 16 mg / L, acid Alkaline value (pH) is between 〇17-〇44, CuS04 · 5H20 concentration = 200 g / L, ionic strength = 5 M. Electroplating process waste liquid is usually a strong acid waste liquid with pH value 丨 or below For those who are familiar with this technique, the traditional ozone process must be effective in an alkaline environment, so generally it will not be used to treat strong acid waste liquid. Bran 'The case first proposed the use of ozone / ultraviolet light or ozone / UV light / addition ... process to treat the plating process waste liquid, and has been proven to have a good effect The procedure in this case is not only simpler than the traditional chemical coagulation / biological treatment procedure, but also does not require complicated steps such as additional dilution. Therefore, it is more economical than the traditional method in terms of processing efficiency and cost. It is more important The answer is' the electroplating process waste liquid treated by the method in this case can effectively remove the electric key 510891 _ case number 88110499 _ year d year factory month ^ / day ____ repair + V. description of the invention (9) the addition of invalid organic matter And does not leave any difficult-to-remove process waste in the plating solution. Therefore, the plating process waste liquid treated by the method in this case can be reused after adding new organic additives. This recycling function is traditional The method of recovering the waste liquid of the electroplating process is impossible: Cheng; The liquid method = not only can effectively and inexpensively deal with electricity and electricity suppliers for a long time = Cheng; The method of recovering the waste liquid solves the industrial value. Dealing with the problems is really a very productive case. Familiar with the decoration, but it is not as good as attached application 1. Although the artist can be used as a craftsman, he can repair all kinds of patents that he wants to protect.

510891 88110499510891 88110499

圖式簡單說明 圖一為士安* + 窗- Γ本木反應裝置系統實施例示意圖； 二=圖一之詳細反應裝置示意圖； 圖：c施流程之示意圖； 應時間關係圖、；"乳程序處理之有機物去除率與臭氧化反 圖五為臭氣程序人 氧化反應時間關係圖；二及&理之有機物去除率與臭 圖六為臭氧/紫外光/添加物 與臭氧化反應時間關係圖。序處理之有機物去除率Brief description of the drawing Figure 1 is a schematic diagram of Shi'an * + window-Γ Benmu reaction device system embodiment; 2 = detailed reaction device schematic diagram of Figure 1; Figure: schematic diagram of c application process; time-response diagram; " milk Programmed organic removal rate and ozonation. Figure 5 shows the relationship between the oxidation reaction time of the odor program. Second and & management of organic removal rate and the smell. Figure 6 shows the relationship between ozone / UV light / additives and ozonation reaction time. Illustration. Organic matter removal rate

第16胃16th stomach

Claims (1)

—種j處理一含一有機助劑之電鍍程序廢液的方法，其 、 〇 ^ ^ 肖·』<_ ^ m ^ ΛΓ m w^j 力 係不添加pH調整劑而直接進行氧化處理，該方法包括下列 步驟： 510891 收集該電鍍程序廢液； 通入一臭氧於該電鍍程序廢液，同時以一紫外光照射該電 錢程序廢液，以進行該有機助劑之氧化反應，使該有機助 劑轉化為利於去除之形式；以及 於該氧化反應之前及/或之後加入一可吸附該有機助劑或 ' 催化臭氧/紫外光氧化反應能力之添加物，以利於該有機 助劑之去除。 2 ·如申請專利範圍第1項所述方法，其中該添加物為金屬 4 氧化物。 3·如申請專利範圍第2項所述方法，其中該金屬氧化物為 氧化鐵。 ” 4 ·如申請專利範圍第1項所述之方法，更包括下列步驟： 於該添加物吸附該有機助劑後以過濾法移除該添加物以回 收該電鍍程序廢液。 5 ·如申請專利範圍第1項所述之方法，其中該臭氧、該添 加物與該電鍍程序廢液係利用一氣/液/固接觸裝置進行直 接接觸。 6 ·如申請專利範圍第1項所述之方法，其中該有機助劑係 可為光澤劑、分散劑、載流劑或安定劑。 7.如申請專利範圍第1項所述之方法，更包括下列步驟： 、 於該電鍵程序廢液中之該有機助劑去除後重新加入一未使—A method for treating a waste liquid of an electroplating process containing an organic auxiliary agent. The method is as follows: _ ^ m ^ ^ Λ Γ mw ^ j is a direct oxidation treatment without adding a pH adjuster, which The method includes the following steps: 510891 collecting the electroplating process waste liquid; introducing ozone into the electroplating process waste liquid, and simultaneously irradiating the electric power process waste liquid with an ultraviolet light to perform an oxidation reaction of the organic auxiliary agent to make the organic The auxiliary is converted into a form that is convenient for removal; and before and / or after the oxidation reaction, an additive capable of adsorbing the organic auxiliary or the ability to catalyze the ozone / UV oxidation reaction is added to facilitate the removal of the organic auxiliary. 2. The method according to item 1 of the scope of patent application, wherein the additive is a metal 4 oxide. 3. The method according to item 2 of the scope of patent application, wherein the metal oxide is iron oxide. 4) The method as described in item 1 of the scope of patent application, further comprising the following steps: After the additive adsorbs the organic auxiliary agent, the additive is removed by filtration to recover the electroplating process waste liquid. 5 · If applied The method described in item 1 of the patent scope, wherein the ozone, the additive and the waste liquid of the electroplating process are directly contacted by a gas / liquid / solid contact device. 6 · The method described in item 1 of the patent scope, The organic auxiliary agent can be a glossing agent, a dispersing agent, a carrier agent, or a stabilizer. 7. The method described in item 1 of the scope of patent application, further comprising the following steps: After removing the organic additives, re-add 510891 案號 88110499 修正 六、申請專利範圍 用過之有機助劑以回收再利用該電鍍程序廢液。 8. 如申請專利範圍第1項所述之方法，其中該紫外光與該 電鍍程序廢液為直接或間接照射或直接/間接兩者組合 式。 9. 如申請專利範圍第1項所述之方法，更包括一因應該電 鍍程序廢液性質，調整該臭氧濃度的步驟。 10. 如申請專利範圍第1項所述之方法，更包括一因應該 - 電鍍程序廢液性質，調整該紫外光強度的步驟。 . 11. 如申請專利範圍第1項所述之方法，其中該臭氧與該 電鍍程序廢液接觸的方式可為批式、半批式或連續式。 12. 如申請專利範圍第1項所述之方法，其中該臭氧與該 f 電鍍程序廢液可於一單槽式、多槽式、串聯式或並聯式反 應裝置中進行氧化反應。 13. 如申請專利範圍第1項所述之方法，其中該臭氧與該 廢液流動之方向可為同向、逆向或複合流向。510891 Case No. 88110499 Amendment 6. Scope of Patent Application Used organic additives to recover and reuse the waste liquid of the electroplating process. 8. The method according to item 1 of the scope of patent application, wherein the ultraviolet light and the plating process waste liquid are directly or indirectly irradiated or directly / indirectly combined. 9. The method according to item 1 of the scope of patent application, further comprising a step of adjusting the ozone concentration according to the nature of the waste liquid of the electroplating process. 10. The method described in item 1 of the patent application scope further includes a step of adjusting the intensity of the ultraviolet light in response to-the nature of the waste liquid of the plating process. 11. The method as described in item 1 of the scope of patent application, wherein the way in which the ozone is contacted with the waste liquid of the plating process can be batch, semi-batch or continuous. 12. The method according to item 1 of the scope of the patent application, wherein the ozone and the f plating process waste liquid can be oxidized in a single-tank, multi-tank, serial or parallel reactor. 13. The method according to item 1 of the scope of the patent application, wherein the direction of the ozone and the waste liquid flowing can be the same direction, the reverse direction or the composite flow direction. 第18頁 510891Page 510891 第（f頁P. F