【摘要】：治理汽車(chē)尾氣最有效的方法是安裝以鉑族金屬為活性組分的汽車(chē)尾氣凈化催化劑,當(dāng)汽車(chē)運(yùn)行一定時(shí)間和里程后汽車(chē)尾氣凈化催化劑就失去了其催化活性,由此產(chǎn)生的廢料就成為了鉑族金屬最重要的二次資源。目前報(bào)道的提取工藝中主要有火法,濕法和火-濕聯(lián)用法3類(lèi)。這些方法要么存在設(shè)備要求高、投資大、生產(chǎn)成本高,要么提取效率低、環(huán)境污染嚴(yán)重等缺點(diǎn),急需開(kāi)發(fā)簡(jiǎn)單、少污染、鉑族金屬提取率高的浸出方法。論文在文獻(xiàn)數(shù)據(jù)的基礎(chǔ)上,對(duì)鉑鈀銠3種鉑族金屬在氯離子溶液體系中的穩(wěn)定形態(tài)進(jìn)行了熱力學(xué)分析研究,結(jié)果表明,當(dāng)溶液中酸度pH約為-1,將電極電勢(shì)提高至700mv時(shí),即可將鉑溶解浸出,鈀只需電極電勢(shì)為500mv,銠僅需420mv;提高溶液的酸度和配位劑氯離子的濃度均有利于鉑族金屬的浸出。從理論上證明了采用HCl-H_2SO_4-NaClO_3體系能夠?qū)崿F(xiàn)汽車(chē)催化劑中鉑鈀銠的浸出。通過(guò)實(shí)驗(yàn)研究了從失效汽車(chē)催化劑中回收鉑族金屬的濕法提取工藝,單因素實(shí)驗(yàn)結(jié)果表明,鉑族金屬的浸出率隨著浸出溫度、浸出液酸度、鹽酸硫酸比例的增大而增大,與氧化劑氯酸鈉濃度、預(yù)處理?xiàng)l件、粒度、攪拌速度等因素關(guān)聯(lián)不大,優(yōu)選出最優(yōu)的浸出工藝條件是:初始酸度[H+]=9mol·L-1,鹽酸硫酸比例為4㑳1,氧化劑氯酸鈉為原料量的5%,浸出溫度為105℃,攪拌速率為250rpm,浸出時(shí)間90min,液固比5㑳1。在上述工藝條件下連續(xù)二次浸出,鉑、鈀、銠的浸出率分別為90%、96.3%和81.2%。在單因素實(shí)驗(yàn)基礎(chǔ)上通過(guò)正交實(shí)驗(yàn)進(jìn)一步對(duì)浸出工藝條件進(jìn)行優(yōu)化,利用L9(34)正交表設(shè)計(jì)三水平四因子正交實(shí)驗(yàn)。然后在正交實(shí)驗(yàn)結(jié)果基礎(chǔ)上進(jìn)行極差分析,得到了影響鉑族金屬浸出率的因子主次排列順序。對(duì)鉑浸出率影響因素依次為,鹽酸硫酸比例酸度浸出時(shí)間溫度;對(duì)鈀浸出率影響因素依次為,酸度溫度鹽酸硫酸比例浸出時(shí)間;對(duì)銠浸出率因素依次為,酸度鹽酸硫酸比例溫度浸出時(shí)間。正交優(yōu)化得到的最佳工藝條件是:初始酸度[H+]11mol·L-1,浸出溫度105℃,鹽酸硫酸比例3㑳1,浸出時(shí)間90min。在上述工藝條件下連續(xù)二次浸出得到鉑、鈀、銠的浸出率分別為92.27%、96.69%和82.98%。相對(duì)單因素優(yōu)化的工藝條件,鉑、銠的浸出率均有所提高;同時(shí)通過(guò)XRD,SEM等現(xiàn)代表征手段證明,濕法浸出鉑族金屬浸出率較低的原因是失效汽車(chē)催化劑中的載體成分鎂質(zhì)堇青石結(jié)構(gòu)穩(wěn)定,對(duì)鉑族金屬產(chǎn)生了包裹。基于上述工藝條件的研究,結(jié)合液固反應(yīng)動(dòng)力學(xué)研究的特點(diǎn)對(duì)失效汽車(chē)催化劑中鉑、銠的浸出動(dòng)力學(xué)進(jìn)行了研究,通過(guò)考察液固比、氧化劑氯酸鈉用量、溫度、初始?xì)潆x子濃度、初始氯離子濃度對(duì)鉑、銠浸出速率的影響,研究了失效汽車(chē)催化劑在HCl-H_2SO_4-NaClO_3體系中鉑、銠的浸出反應(yīng)動(dòng)力學(xué)。結(jié)果表明,失效汽車(chē)催化劑中鉑、銠的浸出遵循“未反應(yīng)核縮減”模型,受化學(xué)反應(yīng)控制;提高反應(yīng)溫度,初始?xì)潆x子濃度及初始氯離子濃度均可提高鉑、銠的浸出率并加速鉑、銠的浸出速率;液固比及氧化劑NaClO_3用量對(duì)浸出速率影響不顯著;采用阿倫尼烏斯公式求出鉑浸出反應(yīng)活化能為45.34kJ·mol-1,氫離子反應(yīng)級(jí)數(shù)為1.712,氯離子反應(yīng)級(jí)數(shù)為0.613;銠浸出反應(yīng)活化能為66.719 kJ·mol-1,高于鉑的活化能,難浸出,氫離子反應(yīng)級(jí)數(shù)為0.779,氯離子反應(yīng)級(jí)數(shù)為0.296。針對(duì)低濃度鉑鈀銠浸出液采用常見(jiàn)的還原劑水合肼及硼氫化鈉進(jìn)行了還原富集的研究。水合肼優(yōu)選的最佳條件為,水合肼的用量為原料量的8%,原料液的酸度控制在1.2mol·L-1左右,反應(yīng)溫度維持在70℃左右,反應(yīng)時(shí)間為10min。經(jīng)驗(yàn)證鉑、鈀、銠的還原率分別為98.41%、99.84%、95.55%;硼氫化鈉還原浸出液的最佳條件為,反應(yīng)溫度40℃,原料液中酸度[H+]接近0mol·L-1,加入硼氫化鈉為原料量的5%,反應(yīng)時(shí)間10min。在此優(yōu)化工藝條件下鉑、鈀、銠的還原率分別為99.47%、99.67%、99.32%,其還原效果優(yōu)于水合肼,還原富集物中鉑族金屬品位高,便于后續(xù)溶解再造液。
[Abstract]:The most effective way to control automobile exhaust is to install the catalyst for purifying the automobile tail gas with the active component of the platinum group metal. When the car runs for a certain time and mileage, the catalyst of automobile exhaust purification loses its catalytic activity. The resulting waste is the two most important resource of the platinum group metal. The extraction process of the present report is reported. There are 3 main types of fire method, wet method and fire wet connection. These methods either have the disadvantages of high equipment requirements, large investment, high production cost, low extraction efficiency, serious environmental pollution and so on. It is urgent to develop a simple, less polluted and high extraction rate of platinum group metal. On the basis of literature, the platinum palladium rhodium 3 kinds of platinum group metals are on the basis of literature The stable morphology in the chloride solution system is studied by thermodynamic analysis. The results show that when the acidity of pH is about -1 and the electrode potential is increased to 700mV, the platinum is dissolved, the electrode potential is 500mv, the rhodium is only 420mv, and the acidity of the solution and the concentration of the chlorine ion of the coordination agent are beneficial to the leaching of the platinum group metal. The leaching of platinum, palladium and rhodium in automobile catalyst by HCl-H_2SO_4-NaClO_3 system was proved theoretically. The wet extraction process of platinum group metal recovered from the failure vehicle catalyst was studied by experiment. The results of single factor experiment showed that the leaching rate of platinum group metal was with the leaching temperature, the acidity of the leaching solution and the proportion of hydrochloric acid. The optimum extraction conditions are: initial acidity [H+]=9mol L-1, hydrochloric acid sulphuric acid ratio 4? 1, sodium chlorate of oxidizing agent 5%, leaching temperature of 105, stirring rate of 250rpm, leaching time 90min, liquid solid. The leaching rate of platinum, palladium and rhodium was 90%, 90%, 96.3% and 81.2%. respectively compared to 5? 1. under the above conditions. The leaching conditions were optimized by orthogonal experiment on the basis of single factor experiments. The orthogonal experiment was used to design the three level Four Factor orthogonal experiment on the basis of L9 (34) orthogonal table. Then the extreme difference was carried out on the basis of orthogonal experiment. The influencing factors of platinum leaching rate are in turn, the temperature of the acid leaching time of hydrochloric acid is in turn; the factors affecting the palladium leaching rate are in turn, the ratio of acid temperature to hydrochloric acid sulfuric acid leaching time, and the factor of rhodium leaching rate in turn, when the acidity hydrochloric acid sulfuric acid ratio is leached by temperature. The optimum process conditions are: initial acidity [H+]11mol L-1, leaching temperature 105 C, hydrochloric acid sulphuric acid ratio 3? 1, leaching time 90min. under the above conditions for two consecutive leaching of platinum, palladium, rhodium leaching rate is 92.27%, 96.69% and 82.98%. phase optimization process conditions, platinum, rhodium leaching rate are all At the same time, through the modern characterization means such as XRD and SEM, it is proved that the low leaching rate of the platinum group metal by wet leaching is the stable structure of the magnesium cordierite in the failure vehicle catalyst and the package of the platinum group metal. Based on the above technological conditions, the characteristics of the study on the kinetics of the bonding liquid solid reaction to the failure vehicle The leaching kinetics of platinum and rhodium was studied in the catalyst. The leaching kinetics of platinum and rhodium in the HCl-H_2SO_4-NaClO_3 body system was studied by investigating the liquid solid ratio, the dosage of sodium chlorate, the temperature, the initial hydrogen ion concentration, the initial chlorine ion concentration on the platinum and rhodium leaching rate. The leaching of platinum and rhodium in the vehicle catalyst follows the "unreacted nuclear reduction" model and is controlled by chemical reaction. Increasing the reaction temperature, the initial hydrogen ion concentration and the initial chloride concentration can increase the leaching rate of platinum, rhodium, accelerate the leaching rate of platinum, rhodium, and the amount of liquid to solid ratio and the amount of oxidant NaClO_3 have no significant effect on the leaching rate; The activation energy of platinum leaching reaction is 45.34kJ mol-1, hydrogen ion reaction series is 1.712, chlorine ion reaction series is 0.613, rhodium leaching activation energy is 66.719 kJ. Mol-1, higher than platinum activation energy, hard leaching, hydrogen ion reaction series 0.779, and chlorine ion reaction series 0.296. against low concentration platinum palladium rhodium leaching solution. Hydrazine hydrate and sodium borohydride have been reduced and enriched. The optimum condition for hydrazine hydrate is that the amount of hydrazine hydrate is 8% of the raw material, the acidity of the raw material is about 1.2mol L-1, the reaction temperature is about 70 C, the reaction time is 10min. empirical platinum, the reduction rate of palladium and rhodium is 98.41%, 99.84%, 95.55, respectively. %, the optimum condition for the reductive leaching solution of sodium borohydride is that the reaction temperature is 40 C, the acidity [H+] in the raw material is close to 0mol. L-1, the sodium borohydride is added to 5% of the raw material, and the reaction time 10min. is 99.47%, 99.67%, 99.32%, respectively, with the reduction rate of platinum, palladium and rhodium, under the optimized process conditions, and the reduction effect is better than hydrazine, and the platinum group metal in the reductive concentration is reduced. High grade, easy to dissolve reengineering solution.
【學(xué)位授予單位】：昆明貴金屬研究所
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類(lèi)號(hào)】：X734.2;TF83

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