{"title":"汽提结晶法从萃余酸中高效回收铝镁及高价值利用","authors":"Peilin Li, Yue Lan, Yanru Jin, Dehua Xu, Lin Yang","doi":"10.1007/s11814-025-00545-7","DOIUrl":null,"url":null,"abstract":"<div><p>Solvent extraction is a broadly employed method for removing impurities from wet-process phosphoric acid (WPA). However, the raffinate acid generated by this method remains underutilized due to its high viscosity and elevated metal impurity (Fe, Al, Mg) content and nonmetallic impurities (S, F), resulting in resource waste. This study employs P-15 as the extractant to purify raffinate acid and introduces an innovative stripping–crystallization process for the separation and recovery of Al<sup>3+</sup> and Mg<sup>2+</sup>, yielding high-value products. A comparative analysis of various stripping agents identified a sulfuric acid solution containing ammonium sulfate as the optimal system. Under the optimized conditions (temperature: 303.15 K, organic–aqueous phase ratio (O/A): 1:1, sulfuric acid concentration: 30 wt.%, reaction time: 30 min), the stripping efficiency reached its optimal value. Theoretical stage calculations using the McCabe–Thiele method and cascade simulation determined that a two-stage countercurrent operation is required. To address crystallization inhibition caused by aluminum–fluoride complexes, silicon or boron (introduced as sodium silicate or borax) was incorporated to form more stable SiF<sub>6</sub><sup>2−</sup>or BF<sub>4</sub><sup>-</sup> complexes, facilitating Al<sup>3+</sup> release and its subsequent precipitation as NH<sub>4</sub>Al(SO<sub>4</sub>)<sub>2</sub>·12H<sub>2</sub>O. Further addition of ammonium sulfate enabled the formation of (NH<sub>4</sub>)<sub>2</sub>Mg(SO<sub>4</sub>)<sub>2</sub>·6H<sub>2</sub>O. This study provides an efficient and environmentally friendly process for the valorization of raffinate acid from WPA production, offering significant industrial application potential and environmental benefits.</p></div>","PeriodicalId":684,"journal":{"name":"Korean Journal of Chemical Engineering","volume":"42 12","pages":"2967 - 2986"},"PeriodicalIF":3.2000,"publicationDate":"2025-08-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Efficient Recovery and High-Valued Utilization of Aluminum and Magnesium from Raffinate Acid via Stripping and Crystallization\",\"authors\":\"Peilin Li, Yue Lan, Yanru Jin, Dehua Xu, Lin Yang\",\"doi\":\"10.1007/s11814-025-00545-7\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Solvent extraction is a broadly employed method for removing impurities from wet-process phosphoric acid (WPA). However, the raffinate acid generated by this method remains underutilized due to its high viscosity and elevated metal impurity (Fe, Al, Mg) content and nonmetallic impurities (S, F), resulting in resource waste. This study employs P-15 as the extractant to purify raffinate acid and introduces an innovative stripping–crystallization process for the separation and recovery of Al<sup>3+</sup> and Mg<sup>2+</sup>, yielding high-value products. A comparative analysis of various stripping agents identified a sulfuric acid solution containing ammonium sulfate as the optimal system. Under the optimized conditions (temperature: 303.15 K, organic–aqueous phase ratio (O/A): 1:1, sulfuric acid concentration: 30 wt.%, reaction time: 30 min), the stripping efficiency reached its optimal value. Theoretical stage calculations using the McCabe–Thiele method and cascade simulation determined that a two-stage countercurrent operation is required. To address crystallization inhibition caused by aluminum–fluoride complexes, silicon or boron (introduced as sodium silicate or borax) was incorporated to form more stable SiF<sub>6</sub><sup>2−</sup>or BF<sub>4</sub><sup>-</sup> complexes, facilitating Al<sup>3+</sup> release and its subsequent precipitation as NH<sub>4</sub>Al(SO<sub>4</sub>)<sub>2</sub>·12H<sub>2</sub>O. Further addition of ammonium sulfate enabled the formation of (NH<sub>4</sub>)<sub>2</sub>Mg(SO<sub>4</sub>)<sub>2</sub>·6H<sub>2</sub>O. This study provides an efficient and environmentally friendly process for the valorization of raffinate acid from WPA production, offering significant industrial application potential and environmental benefits.</p></div>\",\"PeriodicalId\":684,\"journal\":{\"name\":\"Korean Journal of Chemical Engineering\",\"volume\":\"42 12\",\"pages\":\"2967 - 2986\"},\"PeriodicalIF\":3.2000,\"publicationDate\":\"2025-08-23\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Korean Journal of Chemical Engineering\",\"FirstCategoryId\":\"5\",\"ListUrlMain\":\"https://link.springer.com/article/10.1007/s11814-025-00545-7\",\"RegionNum\":4,\"RegionCategory\":\"工程技术\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Korean Journal of Chemical Engineering","FirstCategoryId":"5","ListUrlMain":"https://link.springer.com/article/10.1007/s11814-025-00545-7","RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Efficient Recovery and High-Valued Utilization of Aluminum and Magnesium from Raffinate Acid via Stripping and Crystallization
Solvent extraction is a broadly employed method for removing impurities from wet-process phosphoric acid (WPA). However, the raffinate acid generated by this method remains underutilized due to its high viscosity and elevated metal impurity (Fe, Al, Mg) content and nonmetallic impurities (S, F), resulting in resource waste. This study employs P-15 as the extractant to purify raffinate acid and introduces an innovative stripping–crystallization process for the separation and recovery of Al3+ and Mg2+, yielding high-value products. A comparative analysis of various stripping agents identified a sulfuric acid solution containing ammonium sulfate as the optimal system. Under the optimized conditions (temperature: 303.15 K, organic–aqueous phase ratio (O/A): 1:1, sulfuric acid concentration: 30 wt.%, reaction time: 30 min), the stripping efficiency reached its optimal value. Theoretical stage calculations using the McCabe–Thiele method and cascade simulation determined that a two-stage countercurrent operation is required. To address crystallization inhibition caused by aluminum–fluoride complexes, silicon or boron (introduced as sodium silicate or borax) was incorporated to form more stable SiF62−or BF4- complexes, facilitating Al3+ release and its subsequent precipitation as NH4Al(SO4)2·12H2O. Further addition of ammonium sulfate enabled the formation of (NH4)2Mg(SO4)2·6H2O. This study provides an efficient and environmentally friendly process for the valorization of raffinate acid from WPA production, offering significant industrial application potential and environmental benefits.
期刊介绍:
The Korean Journal of Chemical Engineering provides a global forum for the dissemination of research in chemical engineering. The Journal publishes significant research results obtained in the Asia-Pacific region, and simultaneously introduces recent technical progress made in other areas of the world to this region. Submitted research papers must be of potential industrial significance and specifically concerned with chemical engineering. The editors will give preference to papers having a clearly stated practical scope and applicability in the areas of chemical engineering, and to those where new theoretical concepts are supported by new experimental details. The Journal also regularly publishes featured reviews on emerging and industrially important subjects of chemical engineering as well as selected papers presented at international conferences on the subjects.