TW576753B

TW576753B - Method of collection Cr(VI) from anion exchange resin column and collecting apparatus

Info

Publication number: TW576753B
Application number: TW090121806A
Authority: TW
Inventors: Tatsuya Hosoi; Fumikazu Ito; Hideyuki Imazu
Original assignee: Nippon Denko
Priority date: 2000-09-05
Filing date: 2001-09-04
Publication date: 2004-02-21
Also published as: JP3993370B2; KR20020019396A; KR100432132B1; JP2002079115A

Abstract

The method of collecting Cr(VI) from an anion exchange resin column, characterized by comprising the steps of: passing a Cr(VI) high-concentration liquid through the ion exchange column filled with an anion exchange resin which has adsorbed ions consisting of Cr(VI) ions and other ions including SO42- and Cl- ions to saturation, so as to force out said other ions, and performing, then, a counter-flow multi-step renewal method so as to collect only Cr(VI) at a high concentration.

Description

576753 五、發明說明（1) 發明之背景發明之範缚本發明係關於一種吸附四價鉻（Cr ( v丨））、負二價四氧化硫（S0/0、負一價氯（ci)等而自吸附飽和之離子交換樹脂將四價鉻（cr (VI))以高濃度及高效率回收之方法及回收之裝置者。相關技術之描述在鉻酸鹽或鍍鉻工廠中，作為利用所產生之含有六價鉻之水洗水之可搬式離子交換塔的處理法，有利用充填有陰離子交換樹脂之離子交換塔僅吸附除去有害的四價鉻 Cr ( V I ))之方法，或者以陽離子交換樹脂與陰離子交換樹脂將陽離子、陰離子（亦包含四價鉻（Cr (νι))以外之陰離ί 部吸附除去而處理水則作&純水在系統内再利用係被二送2 吸附飽和之離子交㈣以;生之方法通常係將口 r二換塔並列排列於再生站，而代用之再生完畢之離子交;:：而；續：用需求者處係設置取之製(有 =7 想之方法。惟，習環保之意義上其亦為最理 576753 五、發明說明（2) 係由需求者對使用完畢之吸附飽和之陰離子交換樹脂除四，鉻（Cr (VI))以外亦吸附負二價四氧化硫（s〇42)及負一價氯（C1)專。因此’此等離子亦混入回收四價絡（以（yi)) 液中’故有必須實施更多之精製處理之嬪要。傘發明之開示本發明係有鑑於上述課題所完成者，其課題為提供一種可容易地減低回收之四價鉻（Cr (VI))液中之不純物且可作為鉻鹽類之製造原料使用之方法及裝置者。為解決前述課題，本發明係一種四價鉻（Cr (vi))之高濃度回收方法，其係自充填有飽和吸附四價鉻（Cr (v I))、負二價四氧化硫（SO?)、負一價氯（c J)離子等之陰離子交換樹脂之陰離子交換樹脂塔（以下稱為「離子交換塔」）以高濃度回收四價鉻（Cr (VI ))之方法，其特徵在於具有：對前述離子交換塔導通以四價鉻（Cr (VI))高濃度、液’而將負二價四氧化硫（SO，）及負一價氯（C1)離子等之四價鉻（Cr (VI))以外之離子推出之工程，與實行逆流級再生法之工程。又’本發明為四價鉻（Cr (VI))之高濃度回收方法，其特徵在於其導通之四價鉻（Cr (VI))高濃度液係將利用逆流多級再生法所取得之液體再利用者。又’本發明為四價鉻（Cr (VI))之高濃度回收方法，其特徵在於：再生係排列多數個離子交換塔而同時再生者0576753 V. Description of the invention (1) Background of the invention The scope of the invention The invention relates to an adsorption tetravalent chromium (Cr (v 丨)), negative divalent sulfur tetraoxide (S0 / 0, negative monovalent chlorine (ci) Self-adsorption saturated ion exchange resins and methods for recovering tetravalent chromium (cr (VI)) at high concentrations and high efficiency, as well as recovery devices. Descriptions of related technologies are used in chromate or chromium plating plants as utilization sites. The treatment method of the transportable ion exchange column containing washing water containing hexavalent chromium is a method in which only the harmful tetravalent chromium Cr (VI) is adsorbed and removed by using an ion exchange column filled with an anion exchange resin, or by cation exchange Resin and anion exchange resin adsorb and remove cations and anions (including tetravalent chromium (Cr (νι))). The treated water is used as & pure water for reuse in the system. The method of ion exchange is usually arranged in parallel at the regeneration station, and replaced with the ion exchange after regeneration. :::; Continued: The system is set by the demander (with = 7 Ways of Thinking. However, Xihuan It is also the most reasonable in the sense of guaranteeing 576753. V. Description of the invention (2) The anion exchange resin which is saturated by the demander after the use is absorbed. In addition to chromium (Cr (VI)), it also adsorbs negative divalent sulfur tetraoxide. (S〇42) and negative monovalent chlorine (C1). Therefore, 'the plasma is also mixed into the recovered tetravalent network (with (yi))', so it is necessary to implement more refined treatment. Umbrella invention The present invention has been developed in view of the above-mentioned problems, and its problem is to provide a method and a device which can easily reduce the impurities in the recovered tetravalent chromium (Cr (VI)) liquid and can be used as a raw material for manufacturing chromium salts. In order to solve the aforementioned problem, the present invention is a high-concentration recovery method of tetravalent chromium (Cr (vi)), which is self-filled with saturated adsorption tetravalent chromium (Cr (v I)), negative divalent sulfur tetraoxide (SO?), Negative monovalent chloride (cJ) ions and other anion exchange resin anion exchange resin tower (hereinafter referred to as "ion exchange tower") method to recover tetravalent chromium (Cr (VI)) at a high concentration, It is characterized in that the ion exchange tower is electrically connected with tetravalent chromium (Cr (VI)). Concentration, liquid 'and the introduction of ions other than tetravalent chromium (Cr (VI)) such as negative divalent sulfur tetraoxide (SO,) and negative monovalent chlorine (C1) ions, as well as the implementation of countercurrent regeneration method The invention also relates to a method for recovering a high concentration of tetravalent chromium (Cr (VI)), which is characterized in that the conductive high concentration of tetravalent chromium (Cr (VI)) liquid system will be obtained by a countercurrent multi-stage regeneration method. Also, the present invention is a high-concentration recovery method of tetravalent chromium (Cr (VI)), which is characterized in that the regeneration system arranges a plurality of ion exchange towers and simultaneously regenerates them.

第5頁 576753Page 5 576753

收梦i 提供一種四價鉻(Cr (VI))之高濃度回收雇置，/、八備有：一離子交換塔，係充填有吸附飽價：(cr (vi))」負二價四氧化硫(sv)及負一價氣(⑴離子4之陰離子交換樹脂者；多數之再生液桶，係充填生前述離子交換塔内之陰離子交換樹脂用之再生液之實打逆流多級再生法用者；一四價鉻（Cr (VI))高濃声桶與回收液桶，係收容自第一再生液桶經由對離子交"換通液所得之液體者。 ^狹〜發明之詳細說明以下詳細說明本發明。依本發明之方法，於實行逆流多級再生前，係由需求者對吸附飽和之陰離子交換樹脂塔流通以不純物較少之四價鉻（Cr (VI))高濃度液，於實行吸附的負二價四氧化硫 (S(V)、負一價氣（ci)離子等之推出後接著實行逆流多= 再生。然後，使用之四價鉻（Cr (VI))高濃度液藉由再使用^一度實行逆流多級再生所的之四價鉻（Cr (VI))液則不_要購入新的無水鉻酸等。又，逆流多級再生者藉由並排多數離子交換塔而實行同時再生則可提高濃縮效率並可縮短作業時間。通液之四價鉻（Cr (VI))之高濃度液並不須對所有的使用元畢的陰離子交換樹脂塔作同量通液，因各個通液量不同之故須要作各個監視。其理由，依需求者實行通液之液種及通液條件等將使對因離子交換樹脂之對四價鉻（CrShuimeng i provides a high-concentration recovery and employment of tetravalent chromium (Cr (VI)). It is equipped with: an ion exchange tower, which is filled with adsorption saturation value: (cr (vi)) "minus two valence four Sulfur oxide (sv) and negative monovalent gas (anion exchange resin of tritium ion 4; most of the regeneration liquid barrels are filled with a regeneration counter-current multistage regeneration method for anion exchange resin in the aforementioned ion exchange tower) User: A tetravalent chromium (Cr (VI)) high-concentration acoustic barrel and a recovery liquid barrel are those liquids received from the first regeneration liquid barrel through ion exchange " exchange of liquid. ^ Narrow ~ details of the invention The following describes the present invention in detail. According to the method of the present invention, before the countercurrent multi-stage regeneration is carried out, the demander circulates the saturated anion exchange resin column with a high concentration of tetravalent chromium (Cr (VI)) with less impurities. Liquid, after the introduction of negative divalent sulfur tetraoxide (S (V), negative monovalent gas (ci) ions, etc.) after the introduction of countercurrent multi = regeneration. Then, the use of tetravalent chromium (Cr (VI)) High-concentration liquids do not use tetravalent chromium (Cr (VI)) liquids, which are used to carry out countercurrent multi-stage regeneration once. Purchase new anhydrous chromic acid, etc. In addition, countercurrent multi-stage regenerators can perform simultaneous regeneration by arranging a large number of ion exchange towers side by side to increase the concentration efficiency and shorten the operation time. Liquid-filled tetravalent chromium (Cr (VI)) The high-concentration liquid does not need to pass the same amount of liquid to all the anion exchange resin towers that use Yuanbi, and each monitoring must be monitored because of the different liquid volume. The reason is to implement the liquid type and The conditions of liquid passing will make the

第6頁 576753 五、發明說明^^" — ---- (VI))之吸附程度為不同之故。因四價鉻（Cr (VI))離子、丁 ’ 一旦吸附後，離子交換樹脂之顏色將變成黃色 f橘^ ’故多數吸附四價鉻（Cr (VI))離子而飽和之離子 $換丨合者通液之四價鉻（Cr (VI))高濃度液之量可為較少二相反地，吸附較少四價鉻（Cr ( v丨））離子之場合，通液S則須要較多。因此，為容易以目視確認樹脂之著色狀況、’ !!離子交換塔之侧面最低限度須於上方及下方設置兩個視窗則較佳。又亦可自動檢測須要通液量而根據檢知訊號停止通液。四價鉻（Cr ( V I ))濃度越濃則推出負二價四氧化硫 (SOJ)、負一價氯（C1)離子等之不純物陰離子之效果越佳。至於四價鉻（Cr (VI))之濃度儘可能為l〇g/L以上，越濃越佳，過濃時則離子交換樹脂將劣化。又，離子交換樹脂因係有機物故考慮其安全性上限為丨〇〇g/L以下較佳。又，為吸附四價鉻（Cr (VI ))而流通之四價鉻（cr (V I ))之高濃度液之pH必須預先調整於酸性側。惟，將所得到的回收液作為鉻酸類之原料使用之場合，因極力減少回收液中之負一價氯（C1)、負二價四氧化硫（s〇42 )濃度，故四價鉻（Cr (VI))高濃度液之pH為6· 7〜7· 0左右較佳。# 為pH調整用之酸使用硫酸或鹽酸較佳。其他，流通之四價鉻（Cr (VI))高濃度液之四價鉻（Cr (VI))濃度為較低時$ 可採用使用濃縮器作濃縮而使用之方法。又，流通之四價鉻（Cr (VI))高濃度液中含有懸濁〉夜之場合，則必須預先以過濾壓機等之過濾機予以除去。Page 6 576753 V. Description of the invention ^^ " — (VI)) The degree of adsorption is different. Due to the adsorption of tetravalent chromium (Cr (VI)) ions, D ', once adsorbed, the color of the ion exchange resin will turn yellow f orange ^' so most of the ions saturated with tetravalent chromium (Cr (VI)) ions are exchanged $ 丨In the combined solution, the amount of tetravalent chromium (Cr (VI)) high-concentration liquid can be less. Conversely, when less tetravalent chromium (Cr (v 丨)) ions are adsorbed, the solution S needs to be more than many. Therefore, in order to make it easy to visually confirm the resin's coloring condition, it is better to have at least two windows above and below the side of the '!! ion exchange tower. It can also automatically detect the amount of fluid required and stop fluid flow based on the detection signal. The stronger the concentration of tetravalent chromium (Cr (V I)), the better the effect of introducing anions of impurities such as negative divalent sulfur tetraoxide (SOJ) and negative monovalent chlorine (C1) ions. Regarding the concentration of tetravalent chromium (Cr (VI)) as much as 10 g / L or more, the more concentrated the better, and the excessively the ion exchange resin will deteriorate. In addition, since the ion exchange resin is an organic substance, its safety upper limit is preferably not more than 1000 g / L. In addition, the pH of a high-concentration solution of tetravalent chromium (cr (V I)) circulating for adsorption of tetravalent chromium (Cr (VI)) must be adjusted in advance on the acid side. However, when the obtained recovered liquid is used as a raw material of chromic acid, the concentration of negative monovalent chlorine (C1) and negative divalent sulfur tetraoxide (s042) in the recovered liquid is minimized, so tetravalent chromium ( The pH of the Cr (VI)) high-concentration liquid is preferably about 6.7 to 7.0. # Sulfuric acid or hydrochloric acid is preferably used as the acid for pH adjustment. In addition, when the tetravalent chromium (Cr (VI)) concentration of the circulating high-valent chromium (Cr (VI)) high-concentration liquid is low, a method using a concentrator for concentration can be used. In the case where the circulating tetravalent chromium (Cr (VI)) high-concentration liquid contains suspension> night, it must be removed in advance by a filter such as a filter press.

576753 五、發明說明（5) 【實施例】兹根據第一圖所示之實施例說明本發明 συ)之^濃度液。又，第一圖為逆流三段法之場合陰離子父換樹脂塔中充填有弱鹽基性陰離子交換樹脂。 (推出工程）首先，需求者將吸附飽和之陰離子交換樹脂塔5搬入集中再生場，實施水洗淨以除去附著於樹脂上之夾雜物後 (惟，第一圖中未記載）配置接續於再生站〗7。於再生站j 7 同樣地於一定之位置配置接續其他之需求者所使用完畢之離子交換塔6-8。於四價絡（Cr (VI))高濃度槽4中置入經硫酸溶液15調整成ρΗ6·5之四價鉻（Cr (VI))高濃度液，將此液體介以閱門 4a、幫浦14 復經由閥門 5a、5b、6a、6b、7a、7b、8a、 8b同時通流至設置於一定位置之4塔之陰離子交換樹脂塔 5〜8，處理水係通過閥門5c、5d、6c、6d、7c、7d、8c、 8 d，復經由閥門1 6 a流動至排水處1 6 (以下稱為鉻再吸附工程。又，關於閥門之開閉只要無特別指定其離子交換塔上部及下部接續用閥門5a〜5d、6a〜6d、7a〜7d、8a〜8d係設為常時開狀態，而以外者僅於有記述之部份呈現打開狀態）。通流終了之標準係以目視確認於各個離子交換塔之處理水顯現四價鉻（Cr (VI))高濃度液之同樣顏色之時刻，為各個離子交換塔入口之閥門關閉而全部之通流終了之時刻。到此，鉻再吸附工程告一段落’移行至次一逆流多級576753 V. Description of the invention (5) [Example] The concentration solution of συ) of the present invention will be described based on the example shown in the first figure. The first figure shows the case of the countercurrent three-stage method. The anion parent resin column is filled with a weakly basic anion exchange resin. (Launch process) First, the demander will move the adsorption-saturated anion exchange resin tower 5 into a centralized regeneration site, and then perform water washing to remove inclusions attached to the resin (however, not shown in the first picture). Station〗 7. At the regeneration station j 7, the ion exchange towers 6-8 which have been used by other demanders are arranged at a certain position. A tetravalent chromium (Cr (VI)) high-concentration solution adjusted to pH 6.5 with sulfuric acid solution 15 was placed in a tetravalent network (Cr (VI)) high-concentration tank 4, and this liquid was passed through the door 4a, The pump 14 flows through the valves 5a, 5b, 6a, 6b, 7a, 7b, 8a, and 8b to the anion exchange resin towers 5 to 8 provided in a certain position at the same time, and the treated water system passes the valves 5c, 5d, and 6c. , 6d, 7c, 7d, 8c, 8 d, and then flows to the drainage 16 through valve 16 a (hereinafter referred to as the chromium resorption process. In addition, the opening and closing of the valve as long as the upper and lower parts of the ion exchange tower are not specifically designated The connection valves 5a to 5d, 6a to 6d, 7a to 7d, and 8a to 8d are always open, and the others are opened only in the part described). The end-of-flow standard is the moment when the treated water of each ion exchange tower shows the same color of high-valent tetravalent chromium (Cr (VI)) liquid, and the entire flow is closed when the valves at the inlet of each ion exchange tower are closed. The end time. At this point, the chromium readsorption project came to an end ’and moved to the next countercurrent multi-stage

第8頁 576753 五、發明說明（6) 再生工程。在此，為實行鉻再吸附工程所設置之陰離子交換塔若吸附多量之四價鉻（Cr (VI))液，則自四價鉻（Cr (VI))濃度液槽4之通流量則可為較少，四價鉻（Cr (VI))濃厚槽4 之液量不太會減少。相反地，設置之陰離子交換塔之樹脂若幾乎不吸附四價鉻（Cr (VI ))，則在鉻再吸附工程須要四價鉻（Cr (VI))濃厚槽4通流多量之液體。 (逆流多級再生工程）將第一再生液槽1之液體之一定里71以閥門1 a幫浦1 3與閥門1 3 a復經由間門5 a、5 b、6 a、 6b、7a、7b、8a、8b同時通流至設置於一定位置之四塔之陰離子交換樹脂塔5 - 8後，處理水通過閥門5 c、5 d、6 c、 6d、7c、7d、8c、8d復通過閥門4b而進入四價鉻（cr (VI))高濃度液槽4。此場合，於四價鉻（cr (vi))高濃度液槽4中於鉻再吸附工程所減少之液量之份量被置入，以Page 8 576753 V. Description of the invention (6) Regeneration engineering. Here, if the anion exchange tower set up for the chromium readsorption project adsorbs a large amount of tetravalent chromium (Cr (VI)) liquid, the flow rate from the tetravalent chromium (Cr (VI)) concentration liquid tank 4 can be For less, the amount of liquid in the tetravalent chromium (Cr (VI)) thick tank 4 is unlikely to decrease. On the contrary, if the resin of the anion exchange tower is hardly adsorbed to the tetravalent chromium (Cr (VI)), a large amount of liquid needs to flow through the Cr (VI) thick tank 4 in the chromium re-adsorption process. (Counter-current multi-stage regeneration project) A certain amount of 71 of the liquid in the first regeneration liquid tank 1 is recirculated through the doors 5 a, 5 b, 6 a, 6 b, 7 a, 1 a, 13 a, and 13 a. After 7b, 8a, 8b flow to the anion exchange resin towers 5-8 of the four towers set in a certain position at the same time, the treated water passes through the valves 5c, 5d, 6c, 6d, 7c, 7d, 8c, 8d and then passes through The valve 4b enters the tetravalent chromium (cr (VI)) high-concentration liquid tank 4. In this case, in the tetravalent chromium (cr (vi)) high-concentration liquid tank 4, the amount of liquid reduced by the chromium readsorption process is put in

作補充，故於對為實行鉻再吸附工程所設置之陰離子交換塔吸附多量四價鉻（Cr (VI))之場合，及與僅吸附少量之、場合，其來自第一再生液槽丨之液補充量將不同。又，第再生液槽1之液體中作為四價鉻（Cr (vi))高濃度液槽4 中之未作為補充液使用之殘留液係介以、As a supplement, when the anion exchange tower installed for the implementation of chromium re-adsorption project adsorbs a large amount of tetravalent chromium (Cr (VI)), and where only a small amount is adsorbed, it comes from the first regeneration liquid tank 丨Fluid replenishment will vary. In addition, the liquid remaining in the liquid in the first regeneration liquid tank 1 as a tetravalent chromium (Cr (vi)) high-concentration liquid tank 4 and not used as a replenishing liquid is via,

至设置於一定位置之四塔之陰離子交還樹脂塔5_8後，通過閥 H5c、5d、6c、6d、7c、7d、8e、8“ 而被納入於回收液槽12中（此為作為鉻鹽用利用）。又，第一再生液槽丨實質上為空物。卄After the anion return resin towers 5_8 of the four towers set in a certain position, they are incorporated into the recovery liquid tank 12 through the valves H5c, 5d, 6c, 6d, 7c, 7d, 8e, and 8 "(this is used as a chromium salt) Utilization). Also, the first regeneration liquid tank is substantially empty.

第9頁 576753 五、發明說明（7) 接著第二再生液槽2之液體係介以閥門2a、幫浦丨3、閥門 13a並經由閥門5a、5b、6a、6b、7a、7b、8a、8b 而流通過四塔之陰離子交換塔5 —8後，處理水係通過閥門 5c、5d、6c、6d、7c、7d、8c、8d 復經由閥 nib 而進入空的第一再生液槽1。此時第二再生液槽2實質上為空物。同樣地’第三再生液槽3之液體係介以閥門3a、幫浦 13、閥門13a 並經由閥門5a、5b、6a、6b、7a、7b、8a、 8 b通流至四塔之陰離子交換樹脂塔5 — 8後，處理水通過閥門5c、5d、6c、6d、7c、7d、8c、8d復介以閥門2b進入空Page 576753 V. Description of the invention (7) Then the liquid system of the second regeneration liquid tank 2 is connected to the valve 2a, the pump 3, the valve 13a, and the valves 5a, 5b, 6a, 6b, 7a, 7b, 8a, 8b After flowing through the anion exchange towers 5-8 of the four towers, the treated water system passes through the valves 5c, 5d, 6c, 6d, 7c, 7d, 8c, and 8d to enter the empty first regeneration liquid tank 1 through the valve nib. At this time, the second regeneration liquid tank 2 is substantially empty. Similarly, the liquid system of the third regeneration liquid tank 3 passes through the valves 3a, pump 13, valve 13a, and passes through the valves 5a, 5b, 6a, 6b, 7a, 7b, 8a, 8b to the four column anion exchange. After resin columns 5-8, the treated water passes through valves 5c, 5d, 6c, 6d, 7c, 7d, 8c, and 8d and is reintroduced into valve 2b to enter the empty space.

的第二再生液槽2。在此，第三再生液槽3實質上為空物。之後’打開空氣10之閥門1〇a，經過閥門5a、5b、 6a、6b、7a、7b、8a、8b，四塔之陰離子交換樹脂塔5一8 内之四價鉻（Cr (VI))含有殘液係通過閥門5c、5d、6c、 6d、7c、7d、8c、8d更經過閥門31)而進入空的第三再生液接著打開水11之閥門，經由閥門5a、5b、6a、 7a、7b、8a、8b而將附著於四塔之陰離子交換樹脂 5-8内之陰離子交換樹脂之表面上的四價鉻（Cf (νι))液 =笛、5d、6c、6d、7c、7d、8c、8d 復介以閥門3bThe second regeneration liquid tank 2. Here, the third regeneration liquid tank 3 is substantially an empty object. After that, the valve 10a of the air 10 is opened and passes through the valves 5a, 5b, 6a, 6b, 7a, 7b, 8a, 8b. The tetravalent chromium (Cr (VI)) in the anion exchange resin tower 5-8 of the four towers Residual liquid is passed through valves 5c, 5d, 6c, 6d, 7c, 7d, 8c, and 8d to enter the empty third regeneration liquid, and then the valve of water 11 is opened, and valves 5a, 5b, 6a, and 7a are opened. , 7b, 8a, 8b, and tetravalent chromium (Cf (νι)) liquid on the surface of the anion exchange resin 5-8 which will adhere to the four tower anion exchange resin = flute, 5d, 6c, 6d, 7c, 7d , 8c, 8d refer to valve 3b

—^再士液槽3。其後對第三再生液槽3介以閥門9a添係2里之可性蘇打溶液9以調整濃度。到目前為止之作， ::工逆流多，再生工程’以後例如於該位置實行水洗 7°h 脫離子父換塔上部及下部之閥門5b、5c、6b、6c 、7c、8b、8c而再別處實行水洗。— ^ 再士液槽 3. Thereafter, the third regenerating liquid tank 3 is added with the soluble soda solution 9 in the system 2 via the valve 9a to adjust the concentration. Up to now, there are many countercurrents, and the regeneration project will perform water washing at this position for 7 ° h. After that, it will be separated from the upper and lower valves of the tower and replaced by valves 5b, 5c, 6b, 6c, 7c, 8b, and 8c. Washed elsewhere.

第10頁 576753Page 10 576753

又J如已述者，將第一再生槽1之液體置入四價鉻（c (VI))向濃度液槽4，或回收至回收夜、、° 、、右旦土，> 從價1 z 或如何調節复液里者係仰賴於吸附於陰離子交換塔之樹脂之四價鉻^厂 (νυ)，其依實際情形將有不同之措施。又，其切換係四價鉻（cr (VI))高濃度液槽4内之四價鉻（Cr (VI))、高濃度液使用多少程度（對離子交換塔通流以多少量之液體）以檢知手段檢知並予以記憶而將該份量之第一再生槽丨之液體置入四價鉻（Cr (VI))高濃度液槽4，其後藉由閥門等之開閉切換而自動地實行對回收槽丨2之置入。As described above, the liquid in the first regeneration tank 1 is placed in the tetravalent chromium (c (VI)) to the concentration tank 4, or recovered to the recovery night, °, and right dendrite, > ad valorem 1 z or how to adjust the rehydration solution depends on the tetravalent chromium ^ factory (νυ) of the resin adsorbed on the anion exchange tower, which will have different measures depending on the actual situation. The switching is based on how much tetravalent chromium (Cr (VI)) and high-concentration liquid are used in the tetravalent chromium (cr (VI)) high-concentration liquid tank 4 (how much liquid is passed to the ion exchange tower) Detecting and memorizing by means of detection, the liquid in the first regeneration tank of the same amount is placed in a tetravalent chromium (Cr (VI)) high-concentration liquid tank 4, and then automatically opened and closed by switching the valve or the like Place the recovery tank 丨 2.

、作為參考，將依本發明之方法所得之回收液槽1 2之組成與濃度之一例與習知之方法一同記述於下述之表一中。表 1 四架鉻高濃度液槽 4(S，L) 氛 U/L) 四氧化硫卜/L) PH wx gq 所煜之回收液 5¾ ίιΠ -V 50.6 0.4 8.1 6.9 m ^ 段逆流再生所撂之回收液 10.7 5.0 7.3 10 .0 -- 匕“藉由實施本發明可自需求者使用完畢之陰離子交換樹曰。將四木路以咼濃度且在不純物為較少之狀態下回收。For reference, an example of the composition and concentration of the recovery liquid tank 12 obtained by the method of the present invention is described in Table 1 below together with a conventional method. Table 1 Four chromium high-concentration liquid tanks 4 (S, L) Aura U / L) Sulfur tetroxide / L) PH wx gq Soy's recovery liquid 5¾ ίΠ -V 50.6 0.4 8.1 6.9 m ^ section countercurrent regeneration plant The recovery liquid 10.7 5.0 7.3 10 .0-dagger "The anion exchange tree which can be used up by the demander by implementing the present invention. The Simu Road is recovered with a concentration of tritium and less impurities.

576753 圖式簡單說明第一圖為本發明有關之四價鉻之高濃度回收方法之說明圖。【圖式標號說明】 1 ------再生液槽 la------閥門 lb------閥門 2 ------再生液槽 2a------閥門 2b------閥門 3 ------再生液槽 3b------閥門 4 ------四價鉻高濃度液槽 4a------閥門 4b------門 5 ------樹脂塔 6 ------樹脂塔 7 ------樹脂塔 8 ------樹脂塔576753 Brief description of the diagram The first diagram is an explanatory diagram of a method for recovering a high concentration of tetravalent chromium according to the present invention. [Illustration of figure number] 1 ------ Regenerating liquid tank la ------ Valve lb ------ Valve 2 ------ Regenerating liquid tank 2a ------ Valve 2b ------ valve 3 ------ regenerating liquid tank 3b ------ valve 4 ------ tetravalent chromium high concentration liquid tank 4a ------ valve 4b- ----- Gate 5 ------ Resin tower 6 ------ Resin tower 7 ------ Resin tower 8 ------ Resin tower

5a 、5b 、5c 、5d------^ H 6a、6b、6c、6d------閥門 7a、7b、7c、7d------閥門 8a、8b、8c、8d------閥門 9------苛性蘇打溶液5a, 5b, 5c, 5d ------ ^ H 6a, 6b, 6c, 6d ------ valves 7a, 7b, 7c, 7d ------ valves 8a, 8b, 8c, 8d ------ Valve 9 ------ Caustic soda solution

第12頁 576753Page 12 576753

第13頁Page 13

Claims

576753 VI. Application for Yu'er 1. A method for recovering tetravalent chromium from an anion tetravalent chromium exchange resin tower, which is characterized by having at least saturated adsorption of tetravalent chromium, negative divalent sulfur tetraoxide, and negative one Ion exchange tower of two valence chlorine anion exchange resins, and high-concentration liquid of Cr-Cr, and launched a project that includes ions other than negative divalent sulfur tetraoxide and negative -2 ion tetravalent complexes. After this project, the K reverse machine Evening-level regeneration method recovers only tetravalent chromium at a high concentration. Retrieve 2 Receipts !: Self-anionic tetravalent complex exchange resin 4 = ΐ method in the first scope of the patent, which is characterized in that the aforementioned circulating tetravalent chromium high-concentration liquid system will reuse the liquid recovered by the countercurrent multi-stage regeneration method By. 3 · If the tower recovers four filled with anion 4.-1, it is specially attached to the tetravalent chromium resin; those with more anions: one exchange tower pass two: special: the scope of the first item of the anion tetravalent chromium exchange resin ># ^, which is characterized in that the regeneration system is a side-by-side replacement of resin ion ion towers and simultaneous regeneration. : ^ Anion tetraj chrome exchange resin tower recovers tetravalent chromium. It is packed in a two-ion ion exchange tower filled with at least saturated absorption: anion exchange regeneration of negative monovalent tetrasulphide and negative monovalent chloride ions. 'It is filled with the regeneration liquid used to regenerate the two resins in the ion exchange tower and used to carry out the counter-current multi-stage regeneration method = high-concentration chromium liquid tank.' ;-Recovery tank.