1295691 九、發明說明： 【發明所屬之技術領域】 本創作屬於環境保護及廢棄物資源再生技術領域。 【先前技術】 國内使用脫硝觸媒為工業界常見之氮氧化物控制技術，由於環保法 規對氮氧化物排放量之規定日益嚴謹，所以脫硝觸媒之廢棄量亦會逐年 成長，這些廢棄脫補媒吸附有害廢氣且本身含有飢、鎢金屬，但國内 目前並無相關之處理設施與技術；另中華民國專利公告5〇8277號(回收 廢車綱媒中_金屬之方法)中，主要是針對_金狀資源回收； 而中華民國專利公告367369號(自含有使用過之觸媒之殘餘物中回收有 用之鈷/猛/溴之方法)中，主要是針對鈷、錳等金屬之資源回收，上述之 先前技術並未指出廢棄脫硝觸媒之回收方法或釩、鎢金屬之回收方法。 【發明内容】 由於工業發達與都市發展，使得工廠四處林立，它們所排放出來的 廢氣，使空氣品質惡化。空氣污染的種類很多，其中氮氧化物（Ν〇χ) 為主要常見的空氣污染源之一，不僅會傷害到人類的健康，更會造成酸 雨的形成，使生態系統的平衡被破壞。工業界目前最常使用去除氮氧化 物(De-ΝΟχ)之控制技術為選擇性觸媒還原法(jgeiective Catalytic Keduetion，SCH) ’ SCR之操作係使用脫硝觸媒以去除N0X，而脫硝觸媒 1295691 的成分包含_紐叙，加上含有二氧減(™2)、ϋ氧化物、 釩氧化物等物質之活性物質。脫石肖觸媒在操作時會產生物理破壞，以及 堵塞與毒鱗現象即成為廢觸，現在台灣地隨_媒的廢棄量約每 年麵t由於國内環保法規對氮氧化物排放量之規定日益嚴謹，故 脫硝觸媒之廢棄2：齡逐钱長，這絲棄之朗_目崎有害廢氣 且本身含有m金屬，如任紐意棄置將會造成環境污染問題，而廢 脫摘媒所含之有價金屬(飢、鶴），如無法回收，亦會使環境上之整體 資源浪費。 有鑑於此，本發明乃針對廢脫硝觸媒中之飢、鶴有價金屬進行回收 工作’本發_容主要是將廢脫侧媒與咖％以i ]混合後，在 800°C下培燒2小時，再以水為浸潰液，固液比為2〇g/2〇〇mi，浸潰溫度 為70°C，浸潰1小時後，可獲得飢、鶴之最佳浸潰效果。触集最佳 浸潰液以萃取劑為5 Vol· %之T〇A(Tri-〇ctylamine)，〇/A體積比為i ·· 1，亞硫酸鈉添加量為4_096mg/L，浸潰液之pH值以硫酸調整為〇 5， 然後予以賴萃取2〇分鐘，可於油相巾萃取得齡屬，祕水相中獲 得鈒金屬。溶媒萃取後之油相以〇 25 N的氨液佩㈣，〇/a體積比為 1 : ；1 ’進行反萃取2〇分鐘，可以於反萃後之水相得到鶴金屬。反萃取 後所得之含鶴水相溶液，則利用沉澱法，亦即添加375 ‘之65 %鹽 酸，加熱迴流2小時後，使鎢生成鶴酸氨(NH4WO4 · 3H20)沉澱，以售 予專業之鎢資源回收精煉廠。1295691 IX. Description of the invention: [Technical field to which the invention belongs] This creation belongs to the field of environmental protection and waste resource recycling technology. [Prior Art] Domestic use of denitrification catalysts is a common nitrogen oxide control technology in the industry. As environmental regulations have become more stringent in terms of nitrogen oxide emissions, the amount of denitrification catalysts will increase year by year. Waste dissolving medium absorbs harmful waste gas and contains hunger and tungsten metal. However, there is no relevant treatment facility and technology in China. In addition, the Republic of China Patent Announcement No. 5〇8277 (Recycling Waste Vehicle Medium_Metal Method) , mainly for the recovery of _ gold resources; and the Republic of China Patent Bulletin No. 367369 (from the method of recovering useful cobalt / argon / bromine from the residue containing used catalyst), mainly for metals such as cobalt and manganese The resource recovery, the prior art mentioned above does not indicate the recovery method of the waste denitration catalyst or the recovery method of vanadium or tungsten metal. [Summary of the Invention] Due to industrial development and urban development, the factories are everywhere, and the exhaust gases they emit deteriorate the air quality. There are many types of air pollution. Among them, nitrogen oxides (Ν〇χ) is one of the most common sources of air pollution, which not only harms human health, but also causes the formation of acid rain, which destroys the balance of ecosystems. The industry's most commonly used control technology for the removal of nitrogen oxides (De-ΝΟχ) is the selective catalytic reduction (SCH). The SCR operation system uses denitrification catalyst to remove N0X, while denitrification The composition of the medium 1295691 includes _News, plus an active material containing a substance such as dioxin (TM2), cerium oxide, vanadium oxide or the like. The desulfurization catalyst will cause physical damage during operation, and the phenomenon of clogging and toxic scales will become a waste. Nowadays, the amount of waste in Taiwan is about the annual amount of NOx emissions due to domestic environmental regulations. Increasingly rigorous, so the denitration catalyst is abandoned 2: the age is long, the silk is abandoned _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The valuable metals (hunger, crane), if not recycled, will also waste the overall resources in the environment. In view of this, the present invention is directed to the recovery of hunger and crane valuable metals in waste denitrification catalysts. 'This hair is mainly prepared by mixing waste off-side media with coffee% i] and then culturing at 800 °C. After burning for 2 hours, the water is used as the impregnation solution. The solid-liquid ratio is 2〇g/2〇〇mi, the immersion temperature is 70°C, and after 1 hour of immersion, the best immersion effect of hunger and crane can be obtained. . The optimal impregnation solution is T 〇A (Tri-〇ctylamine) with an extractant of 5 Vol· %, the volume ratio of 〇/A is i ··1, the amount of sodium sulfite added is 4_096 mg/L, and the pH of the immersion solution The value is adjusted to 〇5 with sulfuric acid, and then extracted for 2 minutes, and the ruthenium metal can be obtained from the oil phase towel. After the solvent extraction, the oil phase is obtained by extracting (4) ammonia solution of 〇 25 N and 体积/a volume ratio of 1 :; 1 ' for 2 〇 minutes, and obtaining the crane metal in the aqueous phase after stripping. After the back extraction, the solution containing the aqueous phase of the crane is precipitated, that is, 375' of 65% hydrochloric acid is added, and the mixture is heated under reflux for 2 hours, and then tungsten is produced to precipitate ammonium hexanoate (NH4WO4 · 3H20) for sale to professional tungsten. Resource recycling refinery.
另、、至/合媒萃取後之含飢水相溶液則以晶析法，亦即添加mg/L Γ29569ΐ 之氣化氨(NH^Cl)，濃縮加熱溫度為90 °C，以5 °C冷凝迴流2〇分铲 可獲得釩酸氨(NH4VO3)之結晶物，以售予專業之釩資源回收精煉廠。 廢脫硝觸媒經本發明之資源再生方法處理後，可達成釩、鎢金屬資源回 &再利用之目的。 【實施方式】 本發明之較佳方法稀第，首先將收集之廢脫俩媒其外觀 如第二圖所示），經研磨篩分2步驟直至其通過5〇 mesh大小之筛網， 再將小於50 mesh之脫硝觸媒進行焙燒3，培燒3步驟主要是添加等比 例之叫⑺3與脫石肖觸媒樣品混合，在⑽叱下，予以培燒2小時，^ 將經培燒3步驟後所收集之培燒後固體3卜以純水為浸潰液，在浸潰 ⑽度7〇C ’浸潰時間1小時及固液比2〇g/2〇〇ml的條件下，進行水浸潰 ’、’呈水4步驟後’所收集到之浸潰液Μ中含飢及鎢金屬，其叙浸 潰回收率為95.6 〇/〇，而鎢浸潰回收率為93.63 %，而水浸潰4後所收集 到之殘渣42，可直接進行最_置作·糊43。 八 本發明將所轉之浸魏41進行· 5步驟，還原5步驟之操作 條件主要疋.添加4撕咏之亞麵鈉紐潰液μ巾。經還原5步 驟後即產生還原後浸漬液&’再將還原後浸潰液Μ以硫酸進行調整阳 值6之步驟’直至還原後浸潰液5丨之阳值至〇.5。 將丄調整pH值6後所收集之阳調整浸潰液w進行溶媒萃取7步 驟’溶媒萃取7步歡要的操作條件為： 以 5 Vol % 之 TOA，〇/八=1/卜 10 Γ295691 萃取時間2咖，_嘛7峨，侧辦繼相η， 鎢金屬經溶媒萃取7步驟後之細議㈣％，浸親Μ經添加 儀雄之亞硫酸納，在不同阳值下經溶媒萃取7後，叙、鶴金屬 於油相中之萃取回收率如第三圖所示。 接著將含有鶴金屬之油相71進行反萃取8步驟，反萃取8步驟主 要之操作條件為：錢25N之魏献萃劑，（Μ,，反萃取時間 刀鐘可將油相71中之僞金屬反萃至水相幻中，鎢金屬經反萃取$步In addition, the solution containing the hunger aqueous phase after the extraction to the medium is crystallization, that is, adding mg/L Γ29569ΐ of vaporized ammonia (NH^Cl), and the heating temperature is 90 °C to 5 °C. Condensation reflux 2 〇 shovel can obtain crystals of vanadic acid ammonia (NH4VO3) for sale to a professional vanadium resource recovery refinery. After the waste denitrification catalyst is treated by the resource regeneration method of the present invention, the vanadium and tungsten metal resources can be recycled and reused. [Embodiment] The preferred method of the present invention is dilute, firstly, the collected waste dissociation medium has the appearance as shown in the second figure), and is sieved by grinding 2 steps until it passes through a screen of 5 〇mesh size, and then The denitration catalyst of less than 50 mesh is calcined 3, and the step of calcining 3 is mainly to add an equal proportion of the sample (7) 3 and the sample of the desulfurization catalyst, and under the (10) crucible, it is cooked for 2 hours, ^ will be burned 3 After the step, the solid after solidification was collected with pure water as the impregnation solution, and under the conditions of impregnation (10) degree 7〇C' impregnation time for 1 hour and solid-liquid ratio of 2〇g/2〇〇ml. The water immersion ', 'after 4 steps of water' collected the immersion liquid containing hunger and tungsten metal, the recovery rate of the immersion is 95.6 〇 / 〇, and the recovery rate of tungsten immersion is 93.63%, and The residue 42 collected after the water is immersed in 4 can be directly subjected to the most-preserved paste 43. Eight inventions will be transferred to the Wei 41 to carry out 5 steps, the operation of the reduction of 5 steps. Mainly 疋. Add 4 tears of the sub-surface sodium nucleus solution. After the reduction of 5 steps, the post-reduction immersion liquid &' is further subjected to the step of adjusting the positive value of 6 after the reduction of the immersion liquid 还原 by the sulfuric acid until the positive value of the immersion liquid after the reduction is 5 〇 to 5. The yttrium-adjusting immersion liquid w collected after adjusting the pH value of 6 is subjected to solvent extraction. 7 Steps 'The solvent extraction step 7 is the operating condition: 5 Vol % of TOA, 〇/8=1/卜 10 Γ295691 Time 2 coffee, _ Well 7 峨, side-by-side η, Tungsten metal after solvent extraction 7 steps (4)%, dip relatives by adding Yixiong sodium sulfite, after solvent extraction 7 under different positive values The extraction recovery rate of the Syrian and crane metals in the oil phase is shown in the third figure. Then, the oil phase 71 containing the crane metal is subjected to back extraction 8 steps, and the main operating conditions of the 8 steps of the back extraction are: money 25N Wei Xian extract, (Μ,, back extraction time, the knife clock can be used in the oil phase 71 Metal stripping to the water phase, tungsten metal is back extracted by $step
驟後之反萃取败轉".2 %，_ ?1林同反萃繼度下之嫣反萃 回收率如細騎示。而贿萃取8轉狀_ S2可最終處置或萃 取劑再利用83。 本發月將3鶴金屬之水相81收集後，利用沉澱1〇步驟進行嫣金屬 之回收滅10步驟主要之操作條件為：將經反萃取8後之水相幻加 入375 ml/L HC1溶液，加熱迴流2小時，可得含戰w〇4 · 3H2〇之沉 殿物(其外觀如第五圖卿），其齡狀職贼率可達㈣％，最後 經沉殺ίο後所留下之據液101可最終處置或鶴再回收1〇2。 φ 另經溶媒萃取7步驟後，綠屬會留於水相72，本發明將此含飢 金屬之水相72收集後，侧晶析9步驟進行飢金屬之回收玉作，晶析 9步驟主要之操作條件為：濃縮溫度％ t，冷凝溫度5 t，可將水相 72中之飢金屬晶析成為峽氨戰v〇3(其外觀如第六圖所示）。 為使本發明更加顯現出其進步性與實用性，兹將本發曰月之優點列舉 如下： 11 1295691 l可回收廢脫硝觸媒中之有價釩、鹤金屬。 2·達到廢脫硝觸媒資源再生利用與減量。 3·避免廢脫硝觸媒污染環境。 4·具安全性與進步性。 5·具工商界與產業界上利用價值。 综上所述’本發明誠已符合發明專利之申請要件，並依法提出申 請，祈請辆審查委員贿，觸予本翻專，實感德便。 【圖式簡單說明】 第一圖係本發明廢脫硝觸媒之資源再生方法流程圖。 第二圖係本發明所使用之廢脫硝觸媒外觀照片。 第二圖係本發明在不同PH值下釩、鎢金屬之萃取回收率。 第四圖係本發明在不同反萃劑濃度下之鎢反萃回收率。 第五圖係本發明以沉澱法回收之含NH4W04 · 3H20沉澱物外觀照片。 第六圖係本發明以晶析法回收之含见^〇3結晶物外觀照片。 【主要元件符號說明】 無 12After the sudden back-extraction defeat ".2%, _ ? 1 forest with the reverse extraction of the next sputum stripping recovery rate as fine riding. The bribe extract is 8 turns _ S2 can be finally disposed of or the extract is reused 83. After collecting the water phase 81 of the 3 crane metal in this month, the recovery step of the base metal is carried out by the step of sedimentation. The main operating conditions are as follows: the water phase after the back extraction is added to the 375 ml/L HC1 solution. After heating and refluxing for 2 hours, you can get the Shen Temple (including the appearance of the fifth figure) with the war w〇4 · 3H2〇, the rate of the age-related thief can reach (four)%, and finally after the killing ίο The liquid 101 can be finally disposed of or the crane can be recycled 1〇2. φ After another 7 steps of solvent extraction, the green genus will remain in the aqueous phase 72. After collecting the water phase 72 containing the starvation metal, the side crystallization is carried out in 9 steps to recover the jade metal, and the crystallization step 9 is mainly The operating conditions are: concentration temperature % t, condensation temperature 5 t, crystallizing the starvation metal in the water phase 72 into a gorge warfare v〇3 (the appearance is as shown in the sixth figure). In order to make the invention more progressive and practical, the advantages of the present invention are as follows: 11 1295691 l Valuable vanadium and crane metals in the waste denitration catalyst. 2. Recycling and depletion of waste denitrification catalyst resources. 3. Avoid waste denitrification catalysts polluting the environment. 4. Safety and progress. 5. Use value in the business community and industry. In summary, the invention has been in conformity with the application requirements of the invention patent, and has submitted an application in accordance with the law, praying for the bribery of the review committee, and touching the franchise. BRIEF DESCRIPTION OF THE DRAWINGS The first figure is a flow chart of the resource regeneration method of the waste denitrification catalyst of the present invention. The second figure is a photograph of the appearance of the spent denitrification catalyst used in the present invention. The second graph is the extraction recovery of vanadium and tungsten metal at different pH values of the present invention. The fourth graph is the tungsten stripping recovery of the present invention at different stripping agent concentrations. The fifth figure is a photograph of the appearance of the precipitate containing NH4W04 · 3H20 recovered by the precipitation method of the present invention. Fig. 6 is a photograph showing the appearance of crystals containing the crystals of the present invention recovered by crystallization. [Main component symbol description] None 12