Synthesis of Long-chain Alkylbenzenes on Superacidic Catalysts Containing Embedded Phosphotungstic Acid
Location
BEECH MTN. ROOM 120
Start Date
4-12-2019 2:20 PM
End Date
4-12-2019 2:35 PM
Faculty Sponsor’s Department
Chemistry
Name of Project's Faculty Sponsor
Dr. Aleksey Vasiliev
Type
Oral Presentation
Project's Category
Organic Chemistry
Abstract or Artist's Statement
Heteropolyacids (HPAs), such as phosphotungstic acid (PTA) and phosphomolybdic acid (PMA), with the Keggin structure are well known as solid superacids with estimated pKa of -13. High acidity of HPAs enabled their use as highly active homogeneous catalysts. However, homogeneous catalysis has many drawbacks, e.g. difficult and expensive separation of the used catalyst from the reaction mixture and its recycling. Application of pure HPAs in heterogeneous catalysis is limited by their low surface area and solubility in polar solvents. For increasing their surface area, HPAs should be immobilized on solid support. The objective of this work is the development of an active and stable HPA-containing catalyst for synthesis of long chain alkylbenzenes, which are essential precursors in the manufacture of surfactants. To prevent leachability of HPA from the support, it was covalently bonded into the silica matrix via Si‑O‑W bridges. The catalysts were obtained by co-condensation of tetraethoxysilane (TEOS) with PTA using sol-gel method in the presence of various surfactants as pore-forming agents. The synthesis was conducted by simultaneous addition of 20% HCl and ethanol solution of a mixture of TEOS and PTA to a solution of a surfactant. The reaction mixture was refluxed for 24 h. The obtained product was filtered, washed, air-dried, and calcined for total removal of a surfactant from pores. Use of Pluronic P123 as a non-ionic pore-forming agent produced the most acidic material. The synthesized mesoporous materials were tested as heterogeneous catalysts in liquid-phase alkylation of mesitylene by long-chain alkenes. They demonstrated higher activity than well-known zeolite HY. The analysis of catalyst recovered after the alkylation indicated no PTA leaching from silica matrix. Obtained superacidic mesoporous materials can potentially replace hazardous liquid Lewis acids currently used for long-chain alkylbenzene synthesis in petrochemical industry.
Synthesis of Long-chain Alkylbenzenes on Superacidic Catalysts Containing Embedded Phosphotungstic Acid
BEECH MTN. ROOM 120
Heteropolyacids (HPAs), such as phosphotungstic acid (PTA) and phosphomolybdic acid (PMA), with the Keggin structure are well known as solid superacids with estimated pKa of -13. High acidity of HPAs enabled their use as highly active homogeneous catalysts. However, homogeneous catalysis has many drawbacks, e.g. difficult and expensive separation of the used catalyst from the reaction mixture and its recycling. Application of pure HPAs in heterogeneous catalysis is limited by their low surface area and solubility in polar solvents. For increasing their surface area, HPAs should be immobilized on solid support. The objective of this work is the development of an active and stable HPA-containing catalyst for synthesis of long chain alkylbenzenes, which are essential precursors in the manufacture of surfactants. To prevent leachability of HPA from the support, it was covalently bonded into the silica matrix via Si‑O‑W bridges. The catalysts were obtained by co-condensation of tetraethoxysilane (TEOS) with PTA using sol-gel method in the presence of various surfactants as pore-forming agents. The synthesis was conducted by simultaneous addition of 20% HCl and ethanol solution of a mixture of TEOS and PTA to a solution of a surfactant. The reaction mixture was refluxed for 24 h. The obtained product was filtered, washed, air-dried, and calcined for total removal of a surfactant from pores. Use of Pluronic P123 as a non-ionic pore-forming agent produced the most acidic material. The synthesized mesoporous materials were tested as heterogeneous catalysts in liquid-phase alkylation of mesitylene by long-chain alkenes. They demonstrated higher activity than well-known zeolite HY. The analysis of catalyst recovered after the alkylation indicated no PTA leaching from silica matrix. Obtained superacidic mesoporous materials can potentially replace hazardous liquid Lewis acids currently used for long-chain alkylbenzene synthesis in petrochemical industry.