TWI454428B - Copper sulfate recovery method and copper sulfate recovery device - Google Patents
Copper sulfate recovery method and copper sulfate recovery device Download PDFInfo
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本發明係關於使用螯合物樹脂，自含有不純物的硫酸銅廢液回收硫酸銅的硫酸銅回收方法及硫酸銅回收裝置。The present invention relates to a copper sulfate recovery method and a copper sulfate recovery apparatus for recovering copper sulfate from a copper sulfate waste liquid containing an impurity using a chelate resin.
銅係電子組件製造上不可或缺的金屬，由於需求多，近年來價格亦有急劇升高的傾向。因此，已提議各種自電解純化、銅箔製造、銅鍍敷等步驟中排出的硫酸銅廢液回收硫酸銅，而純化再利用的方法。Metals, which are indispensable for the manufacture of copper-based electronic components, have a tendency to rise sharply in recent years due to the high demand. Therefore, various methods for purifying and recycling copper sulfate waste liquid discharged from the steps of electrolytic purification, copper foil production, copper plating, and the like have been proposed.
例如，專利文獻1已揭示將於製造電解銅箔的步驟中排出的硫酸銅廢液以活性碳處理後，加以電解，而製造銅箔的方法。依據專利文獻1之方法，藉由將硫酸銅廢液以活性碳處理而除去有機物，可減少所製造的銅箔中的金屬不純物。For example, Patent Document 1 discloses a method of producing a copper foil by subjecting a copper sulfate waste liquid discharged in the step of producing an electrolytic copper foil to treatment with activated carbon and then electrolyzing. According to the method of Patent Document 1, by removing the organic substance by treating the copper sulfate waste liquid with activated carbon, metal impurities in the produced copper foil can be reduced.
又，例如，就回收鎳含有量少的硫酸銅的方法而言，專利文獻2已揭示將硫酸銅廢液加熱而使硫酸銅分離沉澱的方法。Further, for example, in the method of recovering copper sulfate having a small nickel content, Patent Document 2 discloses a method of heating copper sulfate waste liquid to separate and precipitate copper sulfate.
又，例如，專利文獻3已揭示為了由市售之硫酸銅獲得更高純度的硫酸銅，將硫酸銅溶液以活性碳處理而去除有機物後，進一步使其再結晶的方法。Further, for example, Patent Document 3 discloses a method of obtaining a copper sulfate having a higher purity from commercially available copper sulfate, and treating the copper sulfate solution with activated carbon to remove the organic substance and then recrystallizing it.
又，例如，專利文獻4已揭示以製造於飼料中混入的硫酸銅為目的，自銅電解純化步驟所排出的硫酸銅廢液，除去有毒金屬的方法。Further, for example, Patent Document 4 discloses a method of removing a toxic metal from a copper sulfate waste liquid discharged from a copper electrolysis purification step for the purpose of producing copper sulfate mixed in a feed.
又，專利文獻5已揭示自含硫酸銅的銅蝕刻廢液濃縮回收硫酸及硫酸銅的方法。Further, Patent Document 5 discloses a method of concentrating and recovering sulfuric acid and copper sulfate from a copper etching waste liquid containing copper sulfate.
[專利文獻1] 特開2004-269950號公報[Patent Document 1] JP-A-2004-269950
[專利文獻2] 特開2001-31419號公報[Patent Document 2] JP-A-2001-31419
[專利文獻3] 國際公開第2005/023715號小冊[Patent Document 3] International Publication No. 2005/023715
[專利文獻4] 特開2009-112280號公報[Patent Document 4] JP-A-2009-112280
[專利文獻5] 特開2010-59502號公報[Patent Document 5] JP-A-2010-59502
本發明之目的係提供一種硫酸銅回收方法及硫酸銅回收裝置，該硫酸銅回收方法係自電解純化、銅箔製造、銅鍍敷步驟等所排出的含鐵、鎳等之不純物的硫酸銅廢液，回收所含不純物少的硫酸銅。An object of the present invention is to provide a copper sulfate recovery method and a copper sulfate recovery method, which are copper sulfate wastes containing impurities such as iron and nickel discharged from electrolysis purification, copper foil production, copper plating step, and the like. Liquid, recovering copper sulfate containing less impurities.
本發明之硫酸銅回收方法具備下列步驟：不純物析出步驟，其係於含不純物的硫酸銅廢液中添加pH調整劑，而將前述硫酸銅廢液之pH調整至3.5~5.0之範圍，使前述不純物析出；不純物分離步驟，其係自前述硫酸銅廢液分離前述析出的不純物；銅吸附步驟，其係使經分離前述不純物的硫酸銅廢液流通氫形螯合物樹脂，而使銅吸附；硫酸銅回收步驟，其係於吸附銅的螯合物樹脂使硫酸，而回收硫酸銅溶液。The method for recovering copper sulfate of the present invention comprises the steps of: adding a pH adjusting agent to a copper sulfate waste liquid containing impurities, and adjusting the pH of the copper sulfate waste liquid to a range of 3.5 to 5.0, so that the foregoing The impurity is separated; the impurity separation step is performed by separating the precipitated impurities from the copper sulfate waste liquid; and the copper adsorption step is to pass the hydrogen sulfide chelate resin through the copper sulfate waste liquid separating the impurities to adsorb the copper; A copper sulfate recovery step is carried out by adsorbing a copper chelate resin to sulfuric acid, and recovering a copper sulfate solution.
又，於前述硫酸銅回收方法，前述氫形螯合物樹脂係具有亞胺基二乙酸基、胺基磷酸基、聚胺基、雙吡啶甲基胺(bispicolylamine)基、氧醯胺基(amidoxy)之任一官能基者為較佳。Further, in the copper sulfate recovery method, the hydrogen chelate resin has an iminodiacetic acid group, an aminophosphoric acid group, a polyamine group, a bispicolylamine group, or an amidoxy group (amidoxy). Any of the functional groups is preferred.
又，於前述硫酸銅回收方法，將前述硫酸銅回收步驟所使用的硫酸的濃度作成0.5~20wt%，將硫酸之供給量作成100~300g-H2 SO4 /L-R，而相對於銅濃度，回收硫酸濃度成為0.5~2.0倍的硫酸銅溶液者為較佳。Further, in the copper sulfate recovery method, the concentration of sulfuric acid used in the copper sulfate recovery step is 0.5 to 20% by weight, and the supply amount of sulfuric acid is 100 to 300 g-H 2 SO 4 /LR, and relative to the copper concentration. It is preferred to recover a copper sulfate solution having a sulfuric acid concentration of 0.5 to 2.0 times.
又，本發明之硫酸銅回收裝置係具備：不純物析出手段，其係於含不純物的硫酸銅廢液中添加pH調整劑，將前述硫酸銅廢液之pH調整至3.5~5.0之範圍，而使前述不純物析出；不純物分離手段，其係自前述硫酸銅廢液分離前述析出的不純物；銅吸附手段，其係使經分離前述不純物的硫酸銅廢液流通氫形螯合物樹脂，而使銅吸附；硫酸銅回收手段，其係使硫酸流通吸附銅的螯合物樹脂液，而回收硫酸銅溶液。Moreover, the copper sulfate recovery apparatus of the present invention includes an impurity deposition means for adding a pH adjuster to the copper sulfate waste liquid containing impurities, and adjusting the pH of the copper sulfate waste liquid to a range of 3.5 to 5.0. The impurity is precipitated; the impurity separation means separates the precipitated impurities from the copper sulfate waste liquid; and the copper adsorption means causes the copper sulfate waste liquid to separate the impurities to flow through the hydrogen-shaped chelate resin to adsorb the copper A copper sulfate recovery means for causing a sulfuric acid to flow through a copper chelate resin liquid to recover a copper sulfate solution.
依據本發明，可提供自由電解純化、銅箔製造、銅鍍敷步驟等排出的鐵、鎳等之含有不純物的硫酸銅廢液，回收不純物少的硫酸銅的硫酸銅回收方法及硫酸銅回收裝置。According to the present invention, it is possible to provide a copper sulfate waste liquid containing impurities such as iron or nickel which are discharged by a free electrolytic purification, a copper foil production process, a copper plating process, and the like, and a copper sulfate recovery method for recovering copper sulfate having less impurities and a copper sulfate recovery device. .
[用以實施發明的形態][Formation for carrying out the invention]
以下，說明本發明之實施形態。又，本實施形態係實施本發明的一例，本發明並未限定於本實施形態。Hereinafter, embodiments of the present invention will be described. Further, the present embodiment is an example of the present invention, and the present invention is not limited to the embodiment.
第1圖係顯示與本實施形態有關的硫酸銅回收裝置之一例的概略構成圖。第1圖所示的硫酸銅回收裝置1係具備：逆滲透膜分離裝置(以下，稱為RO膜分離裝置)10、不純物析出反應槽12、固液分離槽14(固液分離手段)、填充螯合物樹脂的筒座16(銅吸附手段)、蒸發濃縮裝置18。Fig. 1 is a schematic block diagram showing an example of a copper sulfate recovery device according to the present embodiment. The copper sulfate recovery apparatus 1 shown in Fig. 1 includes a reverse osmosis membrane separation device (hereinafter referred to as an RO membrane separation device) 10, an impurity precipitation reaction tank 12, a solid-liquid separation tank 14 (solid-liquid separation means), and a filling. A base 16 (copper adsorption means) of a chelate resin, and an evaporation concentration device 18.
RO膜分離裝置10、RO膜分離裝置10與不純物析出反應槽12之間、不純物析出反應槽12與固液分離槽14之間、固液分離槽14與筒座16之間、及筒座16各自連接配管20a~20e。又，不純物析出反應槽12連接pH調整劑添加管線22，筒座16連接硫酸添加管線24。又，於配管20e設置檢測廢液中之銅濃度或銅濃度與硫酸濃度的感應器30。筒座16與蒸發濃縮裝置18之間連接脫附液管線26a。脫附液管線26a連接檢測脫附液中之銅濃度或銅濃度與硫酸濃度的感應器32。脫附液管線26a於感應器32與蒸發濃縮裝置18之間分叉為硫酸銅回收管線26b與廢液管線27。The RO membrane separation device 10, the RO membrane separation device 10 and the impurity precipitation reaction tank 12, the impurity precipitation reaction vessel 12 and the solid-liquid separation tank 14, the solid-liquid separation tank 14 and the cylinder block 16, and the cylinder block 16 The pipes 20a to 20e are connected to each other. Further, the impurity precipitation reaction tank 12 is connected to the pH adjuster addition line 22, and the cartridge holder 16 is connected to the sulfuric acid addition line 24. Further, an inductor 30 for detecting the copper concentration or the copper concentration and the sulfuric acid concentration in the waste liquid is provided in the pipe 20e. A desorption liquid line 26a is connected between the cartridge holder 16 and the evaporation concentration device 18. The detachment liquid line 26a is connected to an inductor 32 for detecting the copper concentration or the copper concentration and the sulfuric acid concentration in the desorption liquid. The detachment liquid line 26a is branched between the inductor 32 and the evaporation concentrating device 18 into a copper sulfate recovery line 26b and a waste liquid line 27.
於本實施形態，不純物析出手段係由不純物析出反應槽12及pH調整劑添加管線22所構成，但調整硫酸銅廢液之pH於3.5~5.0之範圍，只要可使硫酸銅廢液中之不純物析出的構成即可並未限定。又，於本實施形態，硫酸銅回收手段係由筒座16與硫酸添加管線24、脫附液管線26a、硫酸銅回收管線26b及廢液管線27所構成，但只要使硫酸流通吸附銅的螯合物樹脂而可回收硫酸銅的構成即可並未限定。In the present embodiment, the impurity deposition means is composed of the impurity precipitation reaction tank 12 and the pH adjuster addition line 22, but the pH of the copper sulfate waste liquid is adjusted in the range of 3.5 to 5.0 as long as the impurities in the copper sulfate waste liquid can be made. The composition of the precipitation is not limited. Further, in the present embodiment, the copper sulfate recovery means is constituted by the cylinder block 16 and the sulfuric acid addition line 24, the desorption liquid line 26a, the copper sulfate recovery line 26b, and the waste liquid line 27, but the sulfuric acid is circulated to adsorb the copper. The composition of the resin which can recover copper sulfate is not limited.
以下，說明本實施形態之硫酸銅回收裝置1之動作。Hereinafter, the operation of the copper sulfate recovery apparatus 1 of the present embodiment will be described.
自電解純化、銅箔製造、銅鍍敷等之步驟等排出的含不純物的硫酸銅廢液通過配管20a，被輸送液體至RO膜分離裝置10，經RO膜分離裝置10進行濃縮處理。金屬離子經平衡吸附而吸附於螯合物樹脂，故溶液中之金屬離子濃度高者於吸附上為有利。若為相同樹脂量，溶液中之金屬離子濃度高者吸附的金屬離子量會變多。使吸附相同量之金屬的情形，若溶液中之金屬離子濃度低，則較金屬離子濃度高的情形需要較多的樹脂。於本實施形態，設置RO膜分離裝置10雖非必要，但於濃縮硫酸銅、縮短後段之處理時間、提升處理效率，以及可使筒座16內之螯合物樹脂之填充量減低的觀點，則設置RO膜分離裝置10為較佳。The impurity-containing copper sulfate waste liquid discharged from the steps of electrolytic purification, copper foil production, copper plating, etc., is passed through the pipe 20a, and the liquid is transported to the RO membrane separation device 10, and concentrated by the RO membrane separation device 10. The metal ions are adsorbed to the chelate resin by equilibrium adsorption, so that the metal ion concentration in the solution is high in adsorption. If it is the same amount of resin, the amount of metal ions adsorbed in the solution having a high concentration of metal ions will increase. When the same amount of metal is adsorbed, if the concentration of the metal ions in the solution is low, a larger amount of resin is required than when the metal ion concentration is high. In the present embodiment, the RO membrane separator 10 is not required, but the copper sulfate is concentrated, the processing time in the subsequent stage is shortened, the processing efficiency is improved, and the filling amount of the chelate resin in the stem 16 is reduced. It is preferable to provide the RO membrane separation device 10.
進行RO膜處理的硫酸銅廢液係通過配管20b而輸送液體至不純物析出反應槽12。又，由pH調整劑添加管線22將pH調整劑添加至不純物析出反應槽12，而調整槽內之硫酸銅廢液的pH。其中，自電解純化、銅箔製造、銅鍍敷等之步驟等排出的硫酸銅廢液，於大多情形，含有為不純物之鐵離子。鐵離子(以下，有僅記載為鐵的情形)與銅離子(以下，有僅記載為銅的情形)同樣地，因容易吸附於設置在後段的筒座16內的螯合物樹脂，自螯合物樹脂要將硫酸銅廢液中之銅離子與鐵離子分離係有困難的。The copper sulfate waste liquid subjected to the RO membrane treatment is transported to the impurity precipitation reaction tank 12 through the pipe 20b. Moreover, the pH adjuster is added to the impurity precipitation reaction tank 12 by the pH adjuster addition line 22, and the pH of the copper sulfate waste liquid in the tank is adjusted. Among them, the copper sulfate waste liquid discharged from the steps of electrolysis purification, copper foil production, copper plating, etc., in many cases, contains iron ions which are impurities. In the same manner as in the case of copper ions (hereinafter, the case where only copper is described), the iron ions (hereinafter, referred to as only the case of copper) are self-chelating because they are easily adsorbed to the chelate resin provided in the post 16 of the rear stage. It is difficult for the resin to separate the copper ions in the copper sulfate waste liquid from the iron ions.
第2圖係顯示廢液中之pH與銅離子及鐵離子濃度之關係的圖。如第2圖所示，廢液中之pH為3.5以上時，鐵離子無法溶解於廢液中而幾乎被析出。另一方面，廢液中之pH為3.5~5之範圍時，銅離子會溶解於溶液中，幾乎不會被析出。因此，於本實施形態，添加pH調整劑於硫酸銅廢液，藉由將pH調整於3.5~5.0之範圍，較佳為3.5~4.5之範圍，可使大部份廢液中之鐵(其他之重金屬等)析出(不純物析出步驟)。然後，廢液通過配管20c，被輸送液體至固液分離槽14，於固液分離槽14內，自廢液析出的鐵等之不純物被分離(不純物分離步驟)。析出的鐵等之不純物被排出至系統外。Fig. 2 is a graph showing the relationship between the pH in the waste liquid and the concentration of copper ions and iron ions. As shown in Fig. 2, when the pH in the waste liquid is 3.5 or more, iron ions are not dissolved in the waste liquid and are almost precipitated. On the other hand, when the pH in the waste liquid is in the range of 3.5 to 5, copper ions are dissolved in the solution and hardly precipitated. Therefore, in the present embodiment, a pH adjusting agent is added to the copper sulfate waste liquid, and the iron in most of the waste liquid can be obtained by adjusting the pH to a range of 3.5 to 5.0, preferably 3.5 to 4.5. The heavy metal or the like is precipitated (the impurity precipitation step). Then, the waste liquid is sent to the solid-liquid separation tank 14 through the pipe 20c, and the impurities such as iron precipitated from the waste liquid are separated in the solid-liquid separation tank 14 (the impurity separation step). The impurities such as precipitated iron are discharged to the outside of the system.
藉由pH調整劑而調整的硫酸銅廢液中之pH低於3.5時，不但無法使鐵等之不純物析出，而且後段之螯合物樹脂之吸附性能會降低，硫酸銅廢液中之銅離子之吸附量會降低。又，硫酸銅廢液中之pH一旦超過5，因銅會成為氫氧化物而沉澱，變成無法呈硫酸銅回收。如此，於本實施形態，以可分離鐵等之不純物、抑制銅之沉澱、充分確保螯合物之吸附量等之觀點下，調整硫酸銅廢液之pH於3.5~5.0之範圍。When the pH of the copper sulfate waste liquid adjusted by the pH adjuster is less than 3.5, not only the impurities such as iron can be precipitated, but also the adsorption property of the chelate resin in the latter stage is lowered, and the copper ion in the copper sulfate waste liquid is lowered. The amount of adsorption will decrease. Further, when the pH in the copper sulfate waste liquid exceeds 5, copper is precipitated as a hydroxide and cannot be recovered as copper sulfate. As described above, in the present embodiment, the pH of the copper sulfate waste liquid is adjusted in the range of 3.5 to 5.0 in view of the possibility of separating impurities such as iron, suppressing precipitation of copper, and sufficiently ensuring the adsorption amount of the chelate compound.
pH調整劑以於後段設置的筒座16內難以吸附螯合物樹脂者為較佳，例如，可使用氫氧化鈉、氫氧化鉀等之鹼劑。The pH adjuster is preferably one in which it is difficult to adsorb the chelate resin in the post 16 provided in the subsequent stage. For example, an alkali agent such as sodium hydroxide or potassium hydroxide can be used.
藉由固液分離槽14的固液分離方式為自然沉澱、凝集沉澱或過濾法等，並未特別限制，其中以未使用藥品且高速地進行處理的過濾法為較佳。The solid-liquid separation method by the solid-liquid separation tank 14 is not particularly limited as long as natural precipitation, aggregation precipitation, filtration, and the like, and a filtration method in which treatment is carried out at a high speed without using a chemical is preferable.
其次，藉由固液分離槽14去除不純物的硫酸銅廢液係通過配管20d，而被輸送液體至筒座16。而且，硫酸銅廢液中之銅離子被吸附於藉由筒座16所填充的螯合物樹脂(銅吸附步驟)，廢液則通過配管20e被排出至系統外。Next, the copper sulfate waste liquid from which the impurities are removed by the solid-liquid separation tank 14 passes through the pipe 20d, and is transported to the drum seat 16. Further, the copper ions in the copper sulfate waste liquid are adsorbed to the chelate resin filled in the cylinder holder 16 (copper adsorption step), and the waste liquid is discharged to the outside of the system through the pipe 20e.
通常，為了提高金屬離子之吸附效率，螯合物樹脂係將離子交換基之一部份變換為Na形來使用。因此，螯合物樹脂係以Na形被販售。然而，若以回收或再利用為目的而將吸附的金屬脫附，有必要流通強酸，此時螯合物樹脂會變換為H形。因此為了再利用相同螯合物樹脂，則必須再度回到Na形。將螯合物樹脂回到Na形係除了藉由流通氫氧化鈉等變換劑之外，亦必須增加變換劑之洗淨除去等之步驟，步驟變複雜，且使用水量亦變大量。Generally, in order to increase the adsorption efficiency of metal ions, the chelate resin is used by converting a part of the ion exchange group into a Na shape. Therefore, the chelate resin is sold in the form of Na. However, if the adsorbed metal is desorbed for the purpose of recovery or reuse, it is necessary to circulate a strong acid, and at this time, the chelate resin is converted into an H shape. Therefore, in order to reuse the same chelate resin, it is necessary to return to the Na shape again. In order to return the chelate resin to the Na-form, in addition to the conversion agent such as sodium hydroxide, the step of washing and removing the conversion agent must be added, the steps are complicated, and the amount of water used is also large.
然而，為了分離鐵等之不純物，預先添加pH調整劑，經由將pH調整至3.5~5.0之範圍，即使H形之螯合物樹脂，可達到如與Na形同等之吸附效率係由本案發明者檢討而明瞭。因此，於本實施形態，使用H形之螯合物樹脂成為可能。據此，與使用Na形之螯合物樹脂的情形相較，可縮短步驟及減少使用水量以及排水量。又，於本實施形態，亦如上述說明，因流通pH3.5~5.0之硫酸銅廢液，而抑制銅之沉澱的同時，即使以H形之螯合物樹脂亦可充分確保銅之吸附量。However, in order to separate impurities such as iron, a pH adjuster is added in advance, and by adjusting the pH to a range of 3.5 to 5.0, even the H-shaped chelate resin can achieve the same adsorption efficiency as the Na shape. The review is clear. Therefore, in the present embodiment, it is possible to use an H-shaped chelate resin. Accordingly, the number of steps and the amount of water used and the amount of water discharged can be shortened as compared with the case of using a Na-shaped chelate resin. Further, in the present embodiment, as described above, the copper sulfate waste liquid having a pH of 3.5 to 5.0 is passed, and precipitation of copper is suppressed, and the amount of copper adsorbed can be sufficiently ensured even with the H-shaped chelate resin. .
於筒座16填充Na形之螯合物樹脂的情形，如上述調整pH，即使直接流通除去沉澱的廢液，銅之吸附亦無問題，但於脫附回收的硫酸銅溶液中會有混入鈉的情形。為了避免鈉之混入，Na形之螯合物樹脂於使用之前，有必要將酸流通使變換為H形螯合物樹脂。In the case where the base 16 is filled with a Na-shaped chelate resin, the pH is adjusted as described above, and even if the precipitated waste liquid is directly circulated, the adsorption of copper is not problematic, but sodium is mixed in the copper sulfate solution recovered by desorption. The situation. In order to avoid the incorporation of sodium, it is necessary to convert the acid into a H-shaped chelate resin before the use of the Na-shaped chelate resin.
本實施形態之H形螯合物樹脂係只要可吸附銅離子即可，並未特別限制，但於對銅離子具有高選擇性的觀點，以H形螯合物樹脂係以具有亞胺基二乙酸基、胺基磷酸基、聚胺基、雙吡啶甲基胺基、氧醯胺基肟基任一種之官能基者為較佳。The H-chelate resin of the present embodiment is not particularly limited as long as it can adsorb copper ions. However, in view of high selectivity to copper ions, the H-chelate resin has an imine group. A functional group of any one of an acetate group, an aminophosphoric acid group, a polyamino group, a bispyridylmethylamino group or a oxonium fluorenyl group is preferred.
於填充螯合物樹脂的筒座16流通硫酸銅廢液之際之SV為1~20L/L-R‧h之範圍(本說明書中之R為樹脂之縮寫)者較佳，2~10L/L-R‧h之範圍更佳。SV較1L/L-R‧h低的情形，若為了獲得一定的處理量，樹脂管柱要大以確保流通量，自然而然地，因有必要使螯合物樹脂量變多，經濟性會變低。較20L/L-R‧h高的情形，有無法充分發揮螯合物樹脂之吸附性能的情形。It is preferable that the SV at the time of flowing the copper sulfate waste liquid in the tubular seat 16 filled with the chelate resin is in the range of 1 to 20 L/LR‧h (in the present specification, R is an abbreviation of resin), 2 to 10 L/LR‧ The range of h is better. When the SV is lower than 1L/L-R‧h, in order to obtain a certain amount of processing, the resin column is large to ensure the amount of flow, and naturally, it is necessary to increase the amount of the chelate resin, and the economy is lowered. In the case where the temperature is higher than 20 L/L-R‧h, the adsorption performance of the chelate resin may not be sufficiently exhibited.
第3圖係顯示流通螯合物樹脂的銅負荷量與銅之吸附率之關係的圖。此圖顯示IRC748(Rohm and Haas公司)之吸附曲線，但其他螯合物樹脂亦有相同的傾向。又，本文所謂的吸附率係藉由下式定義。Fig. 3 is a graph showing the relationship between the copper loading amount of the flow-through chelate resin and the adsorption ratio of copper. This figure shows the adsorption curve of IRC748 (Rohm and Haas), but other chelate resins have the same tendency. Further, the so-called adsorption rate is defined by the following formula.
吸附率(%)=[(Qin-Qout)/Qin]×100(%)Adsorption rate (%) = [(Qin-Qout) / Qin] × 100 (%)
Qin：螯合物樹脂每1L流通的銅負荷量(g-Cu/L-R)Qin: Copper loading per liter of chelate resin (g-Cu/L-R)
Qout：螯合物樹脂每1L之銅漏出量(g-Cu/L-R)Qout: copper leakage per 1L of chelate resin (g-Cu/L-R)
如第3圖所示，流通螯合物樹脂的銅負荷量於10~60g-Cu/L-R(樹脂每1L的銅負荷量)之範圍較佳，10~40g-Cu/L-R之範圍更佳。銅負荷量低於10g-Cu/L-R的情形，樹脂中之吸附部位成為未吸附的狀態而過剩地殘存，經濟性會降低，較60g-Cu/L-R高的情形，因增加吸附銅的吸附部位之比率，銅離子被平衡吸附的量會減少，而被排出至系統外的銅離子量會增加，最終硫酸銅之回收率會降低。As shown in Fig. 3, the copper loading amount of the flow-through chelate resin is preferably in the range of 10 to 60 g-Cu/L-R (the amount of copper per 1 L of the resin), and the range of 10 to 40 g-Cu/L-R is more preferable. When the copper load is less than 10 g-Cu/LR, the adsorption site in the resin is in an unadsorbed state and remains excessively, and the economy is lowered. When the amount is higher than 60 g-Cu/LR, the adsorption site of the adsorbed copper is increased. The ratio of copper ions to equilibrium adsorption will decrease, and the amount of copper ions that are discharged outside the system will increase, and eventually the recovery rate of copper sulfate will decrease.
吸附時之溫度並非特別被管理的項目，但設定為70℃以下者較佳。又，於流入筒座16的廢液中之銅濃度會變動的情形，藉由設置於配管20e的感應器30，測量自筒座16排出的廢液中之銅離子濃度，其值達到指定值時，結束銅吸附步驟。藉此，實施安定的銅吸附步驟成為可能。又，檢測銅離子濃度的感應器30可使用吸光光度計等，但特別適合使用硫酸銅鍍敷液用分析計。The temperature at the time of adsorption is not particularly managed, but it is preferably set to 70 ° C or less. Further, in the case where the concentration of copper in the waste liquid flowing into the cartridge holder 16 fluctuates, the concentration of copper ions in the waste liquid discharged from the cartridge holder 16 is measured by the inductor 30 provided in the pipe 20e, and the value reaches a specified value. At the end, the copper adsorption step is ended. Thereby, it is possible to carry out a stable copper adsorption step. Further, as the sensor 30 for detecting the copper ion concentration, a spectrophotometer or the like can be used, but an analyzer for a copper sulfate plating solution is particularly suitable.
其次，結束吸附步驟後(即，停止硫酸銅廢液之輸送液體後)，自硫酸添加管線24添加硫酸於筒座16內。據此，銅離子會自螯合物樹脂脫附，而呈硫酸銅溶液自脫附液管線26a被排出(硫酸銅回收步驟)。排出的硫酸銅溶液因應必要通過硫酸銅回收管線26b而被送至蒸發濃縮裝置18，濃縮或固形化之後，被排出。經回收的硫酸銅溶液於可減少保管空間的觀點，藉由蒸發濃縮裝置18而被濃縮或固形化者為較佳。Next, after the adsorption step is finished (that is, after the transport liquid of the copper sulfate waste liquid is stopped), sulfuric acid is added to the base 16 from the sulfuric acid addition line 24. According to this, the copper ions are desorbed from the chelate resin, and the copper sulfate solution is discharged from the desorption liquid line 26a (copper sulfate recovery step). The discharged copper sulfate solution is sent to the evaporation concentration device 18 through the copper sulfate recovery line 26b as necessary, and is discharged after being concentrated or solidified. The recovered copper sulfate solution is preferably concentrated or solidified by the evaporation concentration device 18 from the viewpoint of reducing the storage space.
於填充螯合物樹脂的筒座16流通硫酸之際之SV於0.5~10L/L-R‧h之範圍為較佳，1~4L/L-R‧h之範圍為更佳。SV低於0.5L/L-R‧h的情形，因銅離子之脫附時間變長故效率變差，SV高於10L/L-R‧h的情形，回收的銅濃度有降低的情形。脫附時之溫度並非特別被管理的項目，但設定為70℃以下較佳。The SV at the time of flowing sulfuric acid in the cylinder 16 filled with the chelate resin is preferably in the range of 0.5 to 10 L/L-R‧h, and more preferably in the range of 1 to 4 L/L-R‧h. When the SV is lower than 0.5 L/L-R‧h, the efficiency of the copper ion desorption time becomes long, and the efficiency is deteriorated. When the SV is higher than 10 L/L-R‧h, the recovered copper concentration is lowered. The temperature at the time of desorption is not particularly managed, but it is preferably set to 70 ° C or less.
流通硫酸後，亦可回收筒座16內之銅全量，但硫酸流通初期僅可回收低濃度之硫酸銅。又，硫酸銅廢液中所含的不純物係藉由上述pH調整而存有難以析出的鎳離子等之不純物的情形，於筒座16內之螯合物樹脂中，恐有鎳離子(以下，有時簡單記載為鎳)與銅離子一起被吸附之虞。而且，如此鎳離子藉由流通硫酸，因自螯合物樹脂被脫附，一旦回收筒座16內之銅全量時，有混入作為不純物之鎳離子的情形。因此，為了有效率地回收純度高的硫酸銅，於本實施形態中採用以下條件者為較佳。After the sulfuric acid is circulated, the total amount of copper in the base 16 can be recovered, but only a low concentration of copper sulfate can be recovered at the initial stage of the sulfuric acid flow. In addition, in the case where the impurities contained in the copper sulfate waste liquid contain impurities such as nickel ions which are hard to be precipitated by the pH adjustment, nickel ions are likely to be present in the chelate resin in the holder 16 (hereinafter, Sometimes it is simply described as nickel) which is adsorbed together with copper ions. Further, in the case where the nickel ions are condensed by the sulfuric acid, the self-chelating resin is desorbed, and when the total amount of copper in the ferrule 16 is recovered, nickel ions which are impurities are mixed. Therefore, in order to efficiently recover copper sulfate having high purity, it is preferable to use the following conditions in the present embodiment.
首先，流通的硫酸濃度為0.5~20wt%之範圍者較佳，1~10wt%之範圍更佳。硫酸濃度低於0.5wt%的情形，銅之脫附效率會降低，高於20wt%的情形，分離回收作為不純物吸附的鎳與銅有困難，同時硫酸對回收的銅的比率會變高，於再利用之際之便利性有降低之虞。又，後段中設置蒸發濃縮的情形，硫酸比率高時沸點上升變顯著，硫酸銅呈固形物回收變困難。First, the concentration of sulfuric acid to be circulated is preferably in the range of 0.5 to 20% by weight, and more preferably in the range of 1 to 10% by weight. When the concentration of sulfuric acid is less than 0.5% by weight, the desorption efficiency of copper is lowered. When the concentration is higher than 20% by weight, it is difficult to separate and recover nickel and copper adsorbed as impurities, and the ratio of sulfuric acid to recovered copper becomes high. The convenience at the time of reuse is reduced. Further, in the case where the evaporation concentration is set in the latter stage, the boiling point rises significantly when the sulfuric acid ratio is high, and the recovery of the solid sulfate by the copper sulfate becomes difficult.
其次，供給筒座16的硫酸的供給量係100~300g-H2 SO4 /L-R(樹脂每1L供給的硫酸量(g))之範圍為較佳，100~200g-H2 SO4 /L-R之範圍更佳。硫酸之供給量低於100g-H2 SO4 /L-R時，銅之回收率會降低，高於300g-H2 SO4 /L-R時，變成過度使用硫酸，有經濟性降低之虞。Next, the supply amount of sulfuric acid supplied to the base 16 is preferably in the range of 100 to 300 g-H 2 SO 4 /LR (the amount of sulfuric acid (g) supplied per 1 L of the resin), preferably 100 to 200 g-H 2 SO 4 /LR. The range is better. When the supply amount of sulfuric acid is less than 100 g-H 2 SO 4 /LR, the recovery of copper is lowered, and when it is higher than 300 g-H 2 SO 4 /LR, sulfuric acid is excessively used, which is economically disadvantageous.
一般而言，硫酸流通初期(硫酸供給量低的區域)中銅濃度低，為不純物的鎳濃度變高，硫酸流通後期(硫酸供給量高的領域)中銅濃度降低且硫酸濃度變高，故回收的硫酸銅中的硫酸比率會變高。因此，於本實施形態，自硫酸供給量到達50g-H2 SO4 /L的時點開始硫酸銅之回收，較佳為到達250g-H2 SO4 /L-R的時點，更佳若於到達180g-H2 SO4 /L-R的時點停止回收，可抑制鎳離子等之不純物之混入，又，可提高硫酸銅溶液之銅之純度及濃度，同時硫酸與銅之莫耳比可接近為硫酸銅的比率之1附近。又，硫酸供給量低於50g-H2 SO4 /L時，及超過250g-H2 SO4 /L-R時，此時之廢液會自配管20e排出系統外，自脫附液管線26a通過廢液管線27而排出系統外者為較佳。In general, in the initial stage of sulfuric acid flow (the region where the sulfuric acid supply amount is low), the copper concentration is low, the nickel concentration of the impurity is high, and the copper concentration is lowered and the sulfuric acid concentration is high in the later stage of sulfuric acid flow (the field in which the sulfuric acid supply amount is high). The ratio of sulfuric acid in the recovered copper sulfate becomes high. Therefore, in the present embodiment, recovery of copper sulfate is started from the time when the sulfuric acid supply amount reaches 50 g-H 2 SO 4 /L, preferably at a time point of reaching 250 g-H 2 SO 4 /LR, more preferably at 180 g- When H 2 SO 4 /LR is stopped, it can suppress the incorporation of impurities such as nickel ions, and can increase the purity and concentration of copper in the copper sulfate solution, and the molar ratio of sulfuric acid to copper can be close to the ratio of copper sulfate. Near 1. Further, when the sulfuric acid supply amount is less than 50 g-H 2 SO 4 /L, and when it exceeds 250 g-H 2 SO 4 /LR, the waste liquid at this time is discharged from the piping 20e to the outside of the system, and the waste liquid is discharged from the desorption liquid line 26a. It is preferred that the liquid line 27 is discharged outside the system.
如上述，可依流通回收的硫酸銅溶液的硫酸量來決定，但藉由設置於管線20e的感應器30或設置於脫附液管線26a的感應器32，分析硫酸銅溶液之硫酸濃度及銅濃度，使硫酸濃度與銅濃度之比於指定範圍內回收硫酸銅溶液的方法為宜。具體而言，相對於硫酸濃度之銅濃度之莫耳比設定為0.5倍~2倍之指定範圍者較佳。硫酸濃度為已知的情形，僅測定銅濃度，可於銅濃度指定範圍內回收硫酸銅溶液。將硫酸濃度與銅濃度之比於指定範圍之硫酸銅溶液通過硫酸銅回收管線26b而於蒸發濃縮裝置18回收，指定範圍外之溶液可自廢液管線27排出。分析銅濃度的感應器係以吸光光度計等為較適當，分析硫酸濃度的感應器係以導電率計或密度計等為較適當，但特別適合使用硫酸銅鍍敷液用分析計。As described above, it can be determined according to the amount of sulfuric acid of the copper sulfate solution recovered in circulation, but the sulfuric acid concentration and copper of the copper sulfate solution are analyzed by the inductor 30 provided in the line 20e or the inductor 32 provided in the desorption liquid line 26a. The concentration is such that the ratio of the sulfuric acid concentration to the copper concentration is preferably within a specified range to recover the copper sulfate solution. Specifically, it is preferable to set the molar ratio of the copper concentration to the sulfuric acid concentration to 0.5 to 2 times the specified range. In the case where the sulfuric acid concentration is known, only the copper concentration is measured, and the copper sulfate solution can be recovered within the specified range of the copper concentration. The copper sulfate solution having a ratio of the sulfuric acid concentration to the copper concentration in the specified range is recovered in the evaporation concentration device 18 through the copper sulfate recovery line 26b, and the solution outside the specified range can be discharged from the waste liquid line 27. The sensor for analyzing the copper concentration is preferably an absorbance photometer or the like, and the sensor for analyzing the sulfuric acid concentration is preferably a conductivity meter or a densitometer, etc., but is particularly suitable for an analyzer for using a copper sulfate plating solution.
藉由流通硫酸銅廢液而銅離子對螯合物樹脂之吸附、及藉由流通硫酸之硫酸銅溶液之回收可重複實施複數次。又，銅離子之吸附後，於筒座16內流通洗淨液而導入洗淨筒座16內之螯合物樹脂的洗淨步驟以使回收的硫酸銅溶液中不會混入不純物者為較佳。此洗淨步驟中使用的洗淨液可使用工業用水、市面水、純水之外，亦可使用自後段設置的蒸發濃縮裝置18排出的凝縮水等。若使用凝縮水，於可減少水之使用量的觀點，使用凝縮水為較佳。流通洗淨液之際之SV於0.5~10L/L-R‧h之範圍為較佳，1~5L/L-R‧h之範圍更佳。又，處理倍量為1~20L/L-R之範圍者較佳，2~5L/L-R之範圍更佳。The adsorption of copper ions to the chelate resin by the flow of the copper sulfate waste liquid and the recovery of the copper sulfate solution by the flow of sulfuric acid can be repeated a plurality of times. Further, after the adsorption of the copper ions, the cleaning liquid is passed through the cylinder 16 and introduced into the cleaning step of the chelate resin in the cleaning cylinder holder 16 so that the recovered copper sulfate solution does not contain impurities. . The washing liquid used in the washing step may be industrial water, commercial water, or pure water, or condensed water discharged from the evaporation concentrating device 18 provided in the subsequent stage. When condensed water is used, it is preferred to use condensed water from the viewpoint of reducing the amount of water used. The SV at the time of circulating the cleaning liquid is preferably in the range of 0.5 to 10 L/L-R‧h, and the range of 1 to 5 L/L-R‧h is more preferable. Further, the treatment amount is preferably in the range of 1 to 20 L/L-R, and the range of 2 to 5 L/L-R is more preferable.
又，於硫酸銅回收後再使用螯合物樹脂的情形，亦藉由硫酸流通來降低pH，導入洗淨步驟而不抑制之後的銅離子吸附者為較佳。就洗淨液而言，以上述例示的洗淨液為較佳。流通洗淨液之際之SV於0.5~10L/L-R‧h之範圍為較佳，1~5L/L-R‧h之範圍更佳。又，處理倍量於1~20L/L-R之範圍較佳，2~5L/L-R之範圍更佳。Further, in the case where the chelate resin is used after the recovery of the copper sulfate, the pH is lowered by the flow of sulfuric acid, and it is preferred to introduce the washing step without suppressing the subsequent adsorption of copper ions. In the case of the washing liquid, the above-exemplified washing liquid is preferred. The SV at the time of circulating the cleaning liquid is preferably in the range of 0.5 to 10 L/L-R‧h, and the range of 1 to 5 L/L-R‧h is more preferable. Further, the treatment amount is preferably in the range of 1 to 20 L/L-R, and the range of 2 to 5 L/L-R is more preferable.
[實施例][Examples]
以下，舉例實施例，更具體詳細地說明本發明，但本發明並未受限於以下之實施例。Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited by the examples.
(實施例1-1)(Example 1-1)
於硫酸銅為主成分的廢液中添加氫氧化鈉(濃度25%)，而將pH作成4。之後，將此廢液流通過濾器(JAPAN FILTER TECHNOLOGY,LTD.)而將固形物分離。硫酸銅廢液之組成、pH調整及過濾的硫酸銅廢液之組成整理於表1。Sodium hydroxide (concentration: 25%) was added to the waste liquid containing copper sulfate as a main component, and the pH was changed to 4. Thereafter, the waste liquid was passed through a filter (JAPAN FILTER TECHNOLOGY, LTD.) to separate the solid matter. The composition of the copper sulfate waste liquid, the pH adjustment, and the composition of the filtered copper sulfate waste liquid are summarized in Table 1.
由表1可判別，適切地添加pH調整劑下，不會使銅減少，且可充分減少容易與不純物同時吸附於後段之螯合物樹脂的鐵。It can be judged from Table 1 that the appropriate addition of the pH adjuster does not reduce the copper, and the iron which is easily adsorbed to the chelate resin in the subsequent stage at the same time as the impurities can be sufficiently reduced.
(實施例1-2)(Example 1-2)
將實施例1-1所獲得的廢液流通螯合物樹脂，進行銅離子之吸附處理。螯合物樹脂係使用Rohm and Haas公司製之IRC748(0.3L：Na形)。此螯合物樹脂藉由硫酸變換為H形，以純水洗淨後來使用。將流通時之SV作成5L/L-R‧h(Na形樹脂之基準SV)，處理倍量作為10.5L/L-R，進行吸附處理(流通量為3.15L)。此螯合物樹脂具有亞胺基二乙酸基作為官能基，pH為4.5時，銅吸附量之目錄值為≧0.5mol(32g)/L-R(Na形)。The waste liquid obtained in Example 1-1 was passed through a chelate resin to carry out adsorption treatment of copper ions. As the chelate resin, IRC748 (0.3 L: Na form) manufactured by Rohm and Haas Co., Ltd. was used. This chelate resin was converted into an H shape by sulfuric acid, washed with pure water and then used. The SV at the time of circulation was set to 5 L/L-R‧h (the reference SV of the Na-shaped resin), and the treatment amount was 10.5 L/L-R, and the adsorption treatment was carried out (the flow amount was 3.15 L). This chelate resin has an iminodiacetic acid group as a functional group, and when the pH is 4.5, the catalogue value of the amount of copper adsorption is ≧0.5 mol (32 g) / L-R (Na form).
將前述廢液流通螯合物樹脂，於樹脂出口採取自流通2.85L的時點至流通3.15L的時點(處理倍量9.5L/L-R至10.5L/L-R)之0.3L。調查經採取樣品之金屬離子之濃度，結果整理於表2。銅及鎳濃度藉由ICP發光法測量，鈉濃度藉由原子吸光法測量。如表2可判明，螯合物樹脂入口所含的銅，於流通螯合物樹脂後大幅地被減低，可知被吸附於螯合物樹脂。另一方面，可知主要的不純物鎳與鈉難以吸附於螯合物樹脂。The waste liquid was passed through the chelate resin, and the resin outlet was taken from 0.3 L of the flow point to 0.3 L of the flow point of 3.15 L (treatment amount of 9.5 L/L-R to 10.5 L/L-R). The concentration of the metal ions of the sample taken was investigated, and the results are summarized in Table 2. The copper and nickel concentrations were measured by ICP luminescence and the sodium concentration was measured by atomic absorption. As can be seen from Table 2, the copper contained in the chelate resin inlet was greatly reduced after the flow of the chelate resin, and it was found that it was adsorbed to the chelate resin. On the other hand, it is understood that the main impurities, nickel and sodium, are difficult to adsorb to the chelate resin.
其次，以純水洗淨螯合物樹脂層內。洗淨時之SV成為4L/L-R‧h，處理倍量成為2L/L-R。之後，將5wt%硫酸流通螯合物樹脂，將吸附的銅脫附。硫酸流通之SV作成2L/L-R‧h。採取硫酸供給量0g、36g、45g、54g、62g、71g、89g、107g、116g、125g、134g、142g、161g之間的劃分(處理倍量各自為0、0.67、0.83、1.0、1.17、1.3、1.67、2.0、2.2、2.3、2.5、2.67、3.0L/L-R)，調查銅、鎳、硫酸之濃度。銅及鎳濃度藉由ICP發光法，硫酸濃度藉由毛細管電泳法各別測量。結果示於第4圖。如第4圖可知，硫酸流通初期，鎳成為一個高峰而脫附，其次開始銅之脫附。經過硫酸流通之中期，銅有效率地被脫附，劃分中的銅濃度被保持於高濃度。其次，硫酸流通之後期，吸附的銅之大部分會脫附，故劃分中的銅濃度會降低。Next, the inside of the chelate resin layer was washed with pure water. The SV at the time of washing was 4 L/L-R‧h, and the treatment amount was 2 L/L-R. Thereafter, 5 wt% of sulfuric acid was passed through the chelate resin to desorb the adsorbed copper. The SV of sulfuric acid circulation was made into 2L/L-R‧h. The division between the sulfuric acid supply amounts of 0 g, 36 g, 45 g, 54 g, 62 g, 71 g, 89 g, 107 g, 116 g, 125 g, 134 g, 142 g, and 161 g was used (the treatment amounts were 0, 0.67, 0.83, 1.0, 1.17, 1.3, respectively). , 1.67, 2.0, 2.2, 2.3, 2.5, 2.67, 3.0L/LR), investigate the concentration of copper, nickel and sulfuric acid. The copper and nickel concentrations were measured by ICP luminescence, and the sulfuric acid concentration was measured by capillary electrophoresis. The results are shown in Figure 4. As can be seen from Fig. 4, in the initial stage of sulfuric acid circulation, nickel became a peak and desorbed, and secondly, copper desorption was started. During the middle period of the sulfuric acid circulation, copper is efficiently desorbed, and the copper concentration in the division is maintained at a high concentration. Secondly, in the later stage of sulfuric acid circulation, most of the adsorbed copper will desorb, so the concentration of copper in the division will decrease.
硫酸之供給量為0~62g/L-R之範圍作為硫酸流通初期，硫酸之供給量為62~125g/L-R之範圍作為硫酸流通中期，硫酸供給量為125~161g/L-R之範圍作為硫酸流通後期而回收該當的劃分。硫酸流通初期之處理倍量為1.17L/L-R(回收容積0.35L)、硫酸流通中期之處理倍量為1.17L/L-R(回收容積0.35L)、硫酸流通後期之處理倍量為0.5L/L-R(回收容積0.15L)。初期、中期、後期之各劃分之組成整理於表3。The range of supply of sulfuric acid is 0 to 62 g/LR as the initial stage of sulfuric acid circulation, and the supply amount of sulfuric acid is 62 to 125 g/LR as the middle stage of sulfuric acid circulation, and the supply amount of sulfuric acid is 125 to 161 g/LR as the later stage of sulfuric acid circulation. Recycle the division. The treatment amount at the initial stage of sulfuric acid circulation is 1.17 L/LR (recovery volume 0.35 L), the treatment volume in the middle stage of sulfuric acid circulation is 1.17 L/LR (recovery volume 0.35 L), and the treatment amount in the later stage of sulfuric acid circulation is 0.5 L/LR. (Recovery volume 0.15L). The composition of each division in the initial, middle, and late stages is summarized in Table 3.
可於硫酸流通後回收經回收的硫酸銅溶液之全量，但如表3可判別，藉由僅於硫酸流通中期回收，與於初期、中期、後期回收的銅之合計比較時，雖然減少銅之回收量，但可抑制鎳等之不純物之混入。又，硫酸流通中期，銅與硫酸之莫耳比接近1。如此硫酸銅溶液係適合於後段中蒸發濃縮。The total amount of the recovered copper sulfate solution can be recovered after the sulfuric acid is circulated, but as shown in Table 3, it can be determined by reducing only the total amount of copper recovered in the initial, intermediate, and late stages when compared with the total amount of copper recovered in the initial, intermediate, and late stages. The amount of recovery is reduced, but the incorporation of impurities such as nickel can be suppressed. In addition, in the middle stage of sulfuric acid circulation, the molar ratio of copper to sulfuric acid is close to 1. Such a copper sulfate solution is suitable for evaporation concentration in the latter stage.
(實施例2)(Example 2)
將銅濃度相異的2種類硫酸銅廢液流通螯合物樹脂。本實施例中使吸附於螯合物樹脂的硫酸銅廢液基本上與實施例1-1所獲得者相同，但於實施例2-1，廢液中之銅濃度為2500ppm，實施例2-2之廢液中的銅濃度為4000ppm。螯合物樹脂之前處理、硫酸銅廢液之SV係與實施例1-2相同，處理倍量為10L/L-R。Two types of copper sulfate waste liquids having different copper concentrations are passed through the chelate resin. In the present embodiment, the copper sulfate waste liquid adsorbed to the chelate resin was substantially the same as that obtained in Example 1-1, but in Example 2-1, the copper concentration in the waste liquid was 2,500 ppm, and Example 2 The copper concentration in the waste liquid of 2 was 4000 ppm. The SV system of the chelate resin before treatment and the copper sulfate waste liquid was the same as that of Example 1-2, and the treatment amount was 10 L/L-R.
於螯合物樹脂之出口設置直列(inline)型之吸光光度計(笠原理化工業股份有限公司製之CU-502)。開始硫酸銅廢液之流通的同時，以吸光光度計測量樹脂出口之銅濃度。於表4整理於實施例2-1及2-2之流通處理倍量10L/L-R時點的螯合物樹脂出口之銅濃度及流通該處理倍量時之銅離子之吸附率。吸附率如以下方式算出。首先，將以吸光光度計CU-502測量的螯合物樹脂出口之銅濃度，自流通開始時至10L/L-R處理的時點作積分，算出流通時漏出的銅量。其次，於螯合物樹脂以SV4L/L-R‧h流通2L/L-R之純水而洗淨，積分洗淨液中之銅濃度，算出經洗淨而漏出的銅量。將流通時及洗淨時漏出的銅量作為漏出的銅之總量。自負荷的銅之總量減去漏出的銅之總量，將其除以負荷的銅之總量，而求得吸附率(100分率)。An inline type spectrophotometer (CU-502, manufactured by Seiki Kagaku Kogyo Co., Ltd.) was installed at the outlet of the chelate resin. At the same time as the flow of the copper sulfate waste liquid was started, the copper concentration of the resin outlet was measured by an absorbance photometer. Table 4 shows the copper concentration of the chelate resin outlet at the time of the flow-through treatment of 10 L/L-R of Examples 2-1 and 2-2, and the adsorption ratio of copper ions when the treatment amount was passed. The adsorption rate was calculated as follows. First, the copper concentration of the chelate resin outlet measured by the absorptiometer CU-502 was integrated from the start of the flow to the time of the treatment of 10 L/L-R, and the amount of copper leaked during the flow was calculated. Next, the chelate resin was washed with 2 L/L-R of pure water in SV4L/L-R‧h, and the copper concentration in the cleaning liquid was integrated to calculate the amount of copper which was washed and leaked. The amount of copper leaked during circulation and during washing is taken as the total amount of copper leaked out. The total amount of copper that is self-loaded is subtracted from the total amount of copper that is leaked, and is divided by the total amount of copper in the load to obtain an adsorption rate (100 fractions).
如表4可判別，螯合物樹脂入口之銅濃度高的情形，於流通前述處理倍量10L/L-R的時點，螯合物樹脂出口之銅濃度會大幅地增加。即，如第3圖所預測，螯合物樹脂入口之銅濃度高的情形，即使少的液量，由於螯合物樹脂中之吸附部位已吸附許多銅，難以再吸附更多銅，於流通處理倍量10的時點，因未被吸附而漏出的銅量增加，結果銅的吸附率會降低。另一方面，銅濃度低的情形，即使流通相同處理倍量10的時點，螯合物樹脂之吸附部位上有剩餘，而被維持於高的吸附率。由此結果，未監視螯合物樹脂出口之銅濃度而流通時，依處理的廢液中之銅濃度，漏出的銅量會變多，可預測銅之回收率會降低。As can be seen from Table 4, when the copper concentration at the entrance of the chelate resin was high, the copper concentration at the chelate resin outlet was greatly increased at the time of the above-mentioned treatment magnification of 10 L/L-R. That is, as predicted from Fig. 3, in the case where the copper concentration at the chelate resin inlet is high, even if the amount of liquid is small, since a large amount of copper has been adsorbed at the adsorption site in the chelate resin, it is difficult to adsorb more copper and circulate. At the time of the treatment of the amount of 10, the amount of copper leaked due to no adsorption increases, and as a result, the adsorption rate of copper decreases. On the other hand, in the case where the copper concentration is low, even when the same treatment amount 10 is distributed, the adsorption site of the chelate resin remains, and is maintained at a high adsorption rate. As a result, when the copper concentration of the chelate resin outlet is not monitored and is distributed, the amount of copper leaked depending on the concentration of copper in the treated waste liquid increases, and it is predicted that the copper recovery rate is lowered.
(實施例3)(Example 3)
將銅濃度相異的2種類之硫酸銅廢液流通螯合物樹脂。於本實施例使螯合物樹脂吸附的硫酸銅廢液，基本上與實施例1-1所獲者相同，但於實施例3-1，螯合物樹脂入口之廢液中之銅濃度為2500ppm，實施例3-2中螯合物樹脂入口之廢液中之銅濃度為4000ppm。螯合物樹脂之前處理、硫酸銅廢液之SV及處理倍量與實施例2相同。而且，於螯合物樹脂出口設置直列型之吸光光度計(笠原理化工業股份有限公司製之CU-502)而監視銅濃度，螯合物樹脂出口之銅濃度到達50mg/L的時點時，停止廢液之流通。於表5整理實施例3-1及3-2之螯合物樹脂之銅離子吸附率。積分自開始硫酸銅廢液之流通的時點至停止流通的時點之銅的漏出量及洗淨時漏出的銅，與實施例2同樣地算出吸附率。Two types of copper sulfate waste liquids having different copper concentrations are passed through the chelate resin. The copper sulfate waste liquid which adsorbed the chelate resin in the present embodiment was substantially the same as that obtained in Example 1-1, but in Example 3-1, the copper concentration in the waste liquid of the chelate resin inlet was 2500 ppm, the copper concentration in the waste liquid of the chelate resin inlet in Example 3-2 was 4000 ppm. The SV of the chelate resin before treatment, the copper sulfate waste liquid, and the treatment amount were the same as in Example 2. In addition, an in-line type spectrophotometer (CU-502, manufactured by Kasei Kogyo Co., Ltd.) is installed at the chelate resin outlet to monitor the copper concentration, and when the copper concentration at the chelate resin outlet reaches 50 mg/L, it stops. The circulation of waste liquid. The copper ion adsorption rates of the chelate resins of Examples 3-1 and 3-2 were summarized in Table 5. The adsorption rate was calculated in the same manner as in Example 2, from the time when the flow of the copper sulfate waste liquid was started to the time when the copper leakage at the time of stopping the flow and the copper leaked during the washing.
如表5可判別，於螯合物樹脂之出口監視銅濃度，出口之濃度成為適當的時點時，經由停止流通，不會依存於螯合物樹脂入口之銅濃度，螯合物樹脂維持著高的吸附率。如此，螯合物樹脂入口之銅濃度變動的情形，分析螯合物樹脂出口之銅濃度，可知可保持高的吸附率。As can be seen from Table 5, when the copper concentration is monitored at the outlet of the chelate resin, and the concentration of the outlet becomes an appropriate time, the chelate resin is maintained high by not stopping the flow depending on the copper concentration at the chelate resin inlet. Adsorption rate. As described above, when the copper concentration at the inlet of the chelate resin was changed, the copper concentration at the outlet of the chelate resin was analyzed, and it was found that a high adsorption ratio can be maintained.
(實施例4)(Example 4)
螯合物樹脂吸附的銅量不同的情形，調查脫附的銅之濃度與回收率產生如何的差異。本實施例中螯合物樹脂吸附的硫酸銅廢液基本上與實施例1-1所獲得者相同，但於實施例4-1，廢液中銅濃度為2500ppm，於實施例4-2，廢液中銅濃度為4000ppm。流通相同處理倍量之硫酸銅廢液的情形，通常，銅濃度高的廢液者，螯合物樹脂會吸附許多銅。螯合物樹脂之前處理、硫酸銅廢液之SV及處理倍量、吸附後之洗淨處理與實施例2相同。吸附銅後，於純水洗淨的螯合物樹脂流通5wt%硫酸，進行硫酸銅之回收處理。硫酸流通之SV設為2L/L-R‧h。於樹脂出口設置吸光光度計(笠原理化工業股份有限公司製之CU-502)，測量銅濃度。藉由硫酸流通，回收硫酸銅溶液的時期，作為硫酸流通中期，將硫酸之供給量為60g/L-R之時作為開始點，供給量為120g/L-R之時作為結束點。將硫酸供給量由60g/L至120g/L之間脫附的銅量，積分藉由吸光光度計的測定值，作為銅之回收量。又，硫酸流通開始後，積分出口之銅濃度成為1mg/L以下為止之銅濃度，作為對螯合物樹脂吸附的銅之總吸附量。將銅之回收量除以銅之總吸附量，求得回收率。於表6，整理實施例4-1及4-2之硫酸流通中期之開始時點及結束時點中的硫酸銅溶液的銅濃度及銅之回收率。When the amount of copper adsorbed by the chelate resin is different, it is investigated how the concentration of the desorbed copper differs from the recovery rate. The copper sulfate waste liquid adsorbed by the chelate resin in the present embodiment is basically the same as that obtained in Example 1-1, but in Example 4-1, the copper concentration in the waste liquid is 2500 ppm, in Example 4-2, The copper concentration in the waste liquid was 4000 ppm. In the case of circulating the same amount of copper sulfate waste liquid, usually, in the case of a waste liquid having a high copper concentration, the chelate resin adsorbs a large amount of copper. The pretreatment of the chelate resin, the SV of the copper sulfate waste liquid, the treatment amount, and the washing treatment after the adsorption were the same as in the second embodiment. After the copper is adsorbed, the chelate resin washed in pure water is passed through 5 wt% of sulfuric acid to carry out recovery treatment of copper sulfate. The SV of sulfuric acid circulation was set to 2 L/L-R‧h. An absorbance photometer (CU-502, manufactured by Kasei Kogyo Co., Ltd.) was placed at the resin outlet to measure the copper concentration. The period in which the copper sulfate solution was recovered by the flow of sulfuric acid was used as the starting point when the supply amount of sulfuric acid was 60 g/L-R in the middle of the sulfuric acid circulation, and the end point was when the supply amount was 120 g/L-R. The amount of copper desorbed from the amount of sulfuric acid supplied from 60 g/L to 120 g/L was integrated as the amount of copper recovered by the measured value of the spectrophotometer. Further, after the start of the sulfuric acid flow, the copper concentration of the integrated outlet becomes a copper concentration of 1 mg/L or less, which is the total adsorption amount of copper adsorbed to the chelate resin. The recovery amount was obtained by dividing the amount of copper recovered by the total amount of copper adsorbed. In Table 6, the copper concentrations and copper recovery rates of the copper sulfate solutions in the beginning and end of the middle of the sulfuric acid flow in Examples 4-1 and 4-2 were adjusted.
如表6可知，於吸附多量之銅的螯合物樹脂與吸附較少銅的螯合物樹脂流通硫酸而脫附時，硫酸之供給量於相同時點，當然，自吸附多量銅的螯合物樹脂脫附的銅之量較由吸附少量銅的樹脂脫附的銅之量更多。此處一律地於相同時點結束回收時，於自吸附多量銅的樹脂的回收，會錯過回收銅濃度高的脫附液，而回收率下降。As can be seen from Table 6, when the chelate resin adsorbing a large amount of copper and the chelate resin adsorbing less copper are condensed by sulfuric acid and desorbed, the supply amount of sulfuric acid is at the same time, and of course, the chelate compound adsorbs a large amount of copper. The amount of copper desorbed by the resin is greater than the amount of copper desorbed by the resin adsorbing a small amount of copper. When the recovery is completed at the same time, the recovery of the resin from which a large amount of copper is adsorbed is missed, and the desorption liquid having a high copper concentration is lost, and the recovery rate is lowered.
(實施例5)(Example 5)
將銅濃度相異的硫酸銅廢液流通螯合物樹脂。本實施例中螯合物樹脂吸附的硫酸銅廢液基本上與實施例1-1所獲得者相同，但實施例5-1中，廢液中之銅濃度為2500ppm，實施例5-2中，廢液中之銅濃度為4000ppm。螯合物樹脂之前處理、硫酸銅廢液之SV及處理倍量、吸附後之洗淨處理與實施例2相同。與實施例4同樣地，藉由此操作，獲得銅吸附量相異的2個螯合物樹脂。其次，將5wt%硫酸流通螯合物樹脂。硫酸流通之SV作為2L/L-R‧h。於樹脂出口設置吸光光度計(笠原理化工業股份有限公司製之CU-502)，監視銅濃度。自吸光光度計之測定值，如以下方式回收脫附液。經脫附而銅濃度上升到達50mg/L的時點後開始回收，銅濃度繼續上升到達穩定狀態，於脫附結束而銅濃度下降至400mg/L的時點結束回收。於表7整理實施例5-1及5-2之回收率。藉由樹脂出口之吸光光度計所測量的銅濃度測定值，積分硫酸流通開始時點至脫附結束之銅濃度下降至1mg/L的時點，算出吸附螯合物樹脂的銅之總量。其次，於回收硫酸銅的範圍，即於樹脂出口之銅濃度到達50mg/L的時點至下降至400ppm的時點，將銅濃度積分，自各別樹脂算出回收的銅量。回收率係將回收的銅量除以吸附樹脂的銅之總量而算出。The copper sulfate waste liquid having a different copper concentration is circulated through the chelate resin. The copper sulfate waste liquid adsorbed by the chelate resin in the present embodiment is basically the same as that obtained in Example 1-1, but in Example 5-1, the copper concentration in the waste liquid is 2500 ppm, in Example 5-2. The concentration of copper in the waste liquid is 4000 ppm. The pretreatment of the chelate resin, the SV of the copper sulfate waste liquid, the treatment amount, and the washing treatment after the adsorption were the same as in the second embodiment. In the same manner as in Example 4, two chelate resins having different amounts of copper adsorption were obtained by this operation. Next, 5 wt% of sulfuric acid was passed through the chelate resin. The SV of sulfuric acid circulation is 2L/L-R‧h. An absorbance photometer (CU-502, manufactured by Kasei Kogyo Co., Ltd.) was installed at the resin outlet to monitor the copper concentration. The measured value of the self-absorption photometer was recovered as follows in the following manner. When the copper concentration was desorbed and the copper concentration rose to 50 mg/L, the recovery was started, and the copper concentration continued to rise to a stable state, and the recovery was completed when the desorption was completed and the copper concentration was lowered to 400 mg/L. The recovery rates of Examples 5-1 and 5-2 were summarized in Table 7. The total amount of copper adsorbed to the chelate resin was calculated from the point of measurement of the copper concentration measured by the absorbance photometer of the resin outlet, from the point of the start of the sulfuric acid flow to the point at which the copper concentration at the end of the desorption was lowered to 1 mg/L. Next, in the range in which copper sulfate was recovered, that is, when the copper concentration at the resin outlet reached 50 mg/L and dropped to 400 ppm, the copper concentration was integrated, and the amount of copper recovered was calculated from the respective resins. The recovery rate was calculated by dividing the amount of copper recovered by the total amount of copper of the adsorbed resin.
如表7可判別，於螯合物樹脂出口監視銅濃度，藉由於適切的濃度範圍回收硫酸銅，可未依存於螯合物樹脂吸附的銅量，而維持高的硫酸銅回收率。於螯合物樹脂入口之銅濃度會變動，而正確地把握螯合物樹脂吸附的銅量為困難的情形，回收銅之際，僅依賴硫酸之供給量而回收時，會錯過回收銅濃度高的脫附液，而回收銅濃度低的脫附液，擔心回收率會下降。可知於螯合物樹脂之出口分析回收的硫酸銅溶液之銅濃度，可回收適當濃度的脫附液，並可確保高回收率。As can be seen from Table 7, the copper concentration was monitored at the chelate resin outlet, and copper sulfate was recovered in a suitable concentration range, and the copper sulfate adsorption rate was maintained without depending on the amount of copper adsorbed by the chelate resin. The concentration of copper at the inlet of the chelate resin varies, and it is difficult to accurately grasp the amount of copper adsorbed by the chelate resin. When copper is recovered, it is missed when the recovery is only dependent on the supply amount of sulfuric acid. The desorption solution is recovered, and the desorption liquid having a low copper concentration is recovered, and the recovery rate is lowered. It is known that the copper concentration of the copper sulfate solution recovered at the outlet of the chelate resin can recover a proper concentration of the desorption liquid and ensure high recovery.
1．．．硫酸銅回收裝置1. . . Copper sulfate recovery unit
10．．．RO膜分離裝置10. . . RO membrane separation device
12．．．不純物析出反應槽12. . . Impurity precipitation reaction tank
14．．．固液分離槽14. . . Solid-liquid separation tank
16．．．填充螯合物樹脂的筒座16. . . a base for filling a chelate resin
18．．．蒸發濃縮裝置18. . . Evaporation concentrator
20a~20e．．．配管20a~20e. . . Piping
22．．．pH調整劑添加管線twenty two. . . pH adjuster addition line
24．．．硫酸添加管線twenty four. . . Sulfuric acid addition pipeline
26a．．．脫附液管線26a. . . Desorption line
26b．．．硫酸銅回收管線26b. . . Copper sulfate recovery pipeline
27．．．廢液管線27. . . Waste pipeline
30、32．．．感應器30, 32. . . sensor
第1圖顯示與本實施形態有關的硫酸銅回收裝置之一例的概略構成圖。Fig. 1 is a schematic block diagram showing an example of a copper sulfate recovery apparatus according to the present embodiment.
第2圖顯示廢液中之pH與銅離子及鐵離子濃度之關係的圖。Fig. 2 is a graph showing the relationship between the pH in the waste liquid and the concentration of copper ions and iron ions.
第3圖顯示流通螯合物樹脂的銅之負荷量與銅之吸附率之關係的圖。Fig. 3 is a graph showing the relationship between the amount of copper loaded in the flow-through chelate resin and the adsorption ratio of copper.
第4圖顯示流通筒座的硫酸供給量與筒座出口之劃份之硫酸離子以及脫附的銅離子及鎳離子濃度之關係的圖。Fig. 4 is a graph showing the relationship between the amount of sulfuric acid supplied from the flow-through holder and the fraction of sulfate ions and desorbed copper ions and nickel ions at the outlet of the holder.
1．．．硫酸銅回收裝置1. . . Copper sulfate recovery unit
10．．．RO膜分離裝置10. . . RO membrane separation device
12．．．不純物析出反應槽12. . . Impurity precipitation reaction tank
14．．．固液分離槽14. . . Solid-liquid separation tank
16．．．填充螯合物樹脂的筒座16. . . a base for filling a chelate resin
18．．．蒸發濃縮裝置18. . . Evaporation concentrator
20a~20e．．．配管20a~20e. . . Piping
22．．．pH調整劑添加管線twenty two. . . pH adjuster addition line
24．．．硫酸添加管線twenty four. . . Sulfuric acid addition pipeline
26a．．．脫附液管線26a. . . Desorption line
26b．．．硫酸銅回收管線26b. . . Copper sulfate recovery pipeline
27．．．廢液管線27. . . Waste pipeline
30、32．．．感應器30, 32. . . sensor
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| CN102786076B (en) * | 2012-08-30 | 2014-05-28 | 廖勇志 | Method for preparing high-purity copper sulfate by means of waste liquid of copper-contained circuit boards |
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| TWI636018B (en) * | 2015-12-18 | 2018-09-21 | 水生活資源(海洋)私人有限公司 | Method to recycle copper sulfate in waste from wafer fab or pcb manufacturing and system of wafer or pcb manufacturing having copper sulfate recycling unit |
| CN106380015B (en) * | 2016-08-31 | 2019-04-09 | 无锡中天固废处置有限公司 | A method of copper ion in bluestone waste of the removal containing nitric acid |
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| CN109621488A (en) * | 2019-02-01 | 2019-04-16 | 阳谷祥光铜业有限公司 | A method of using ion chelating resin purification copper electrolyte |
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| CN115044769B (en) * | 2021-05-31 | 2023-10-27 | 阮氏化工（常熟）有限公司 | Combined production line and production method of stripping solution and copper nitrate, copper sulfate and tin crystal |
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