Study On The Application Of Organic Sulfonic Acid Series Catalysts In The Synthesis Of CL-20

In order to solve the drawbacks of much waste acid using nitric/sulfuric acid and improve the yield using N2O5/HNO3 to nitrify TAIW to CL-20,the organic sulfonic acids,lanthanide metal salts,benzyl sulfonic acid MCM-41 molecular sieves(BSA-MCM-41)and perfluorosulfonic acid MCM-41 molecular sieves(SA-MCM-41)were applied as catalysts.The effect of these catalysts on the synthesis of CL-20 by using N2O5/HNO3 to nitrify TAIW was studied.The specific contents were as follows:The effects of catalyst species,dosage,reaction time and cycle times on the nitration performance were studied to explore an efficient synthetic route with high yield and high purity.The effects of lanthanum metal salts such as methanesulfonic acid,benzenesulfonic acid,p-toluenesulfonic acid,2-naphthalenesulfonic acid and trifluoromethanesulfonic acid on the synthesis of CL-20 were studied.The results show that both the yield and the purity of CL-20 are improved by Lanthanide organosulfonate metal salts,and the catalytic effect of Sm(Tos)3 is the best,with 95.2%yield and 98.6%purity.The optimal reaction conditions were:TAIW 3g,N2O5 4g,HNO3 15mL,Sm(Tos)3 catalyst 0.30g,reaction temperature 65?75?,reaction time 4h,.The benzyl group was grafted onto the surface of MCM-41 molecular sieves and sulfonated to give the catalyst of BSA-MCM-41.The BSA-MCM-41 catalyst was used to synthesize CL-20.The results show that the prepared BSA-MCM-41 retains the typical molecular structure of the original molecular sieve,and the yield and purity of CL-20 are greatly increased.The best reaction conditions were as follows:TAIW 3g,N2O5 4g,HN0315mL,BSA-MCM-41 catalyst 0.50g,reaction temperature 65?75? and reaction time 5h,the highest yield of CL-20 was 92.5%and the purity was 98.3%.The perfluorinated(1-methyl-ethane)sulfonic acid was grafted onto the surface of MCM-41 molecular sieves to prepare the catalyst of perfluorosulfonic acid MCM-41 molecular sieve(SA-MCM-41).The SA-MCM-41 was used to synthesize CL-20.The results show that the prepared SA-MCM-41 maintains the typical crystal structure of the original molecular sieve,and the yield and purity of CL-20 are greatly increased.The optimal reaction conditions were as follows:TAIW 3g,N2O5 4g,HNO3 15mL,SA-MCM-41 catalyst 0.50g,reaction temperature 65?75? and reaction time 5h,the highest yield of CL-20 was 93.9%and the purity was 98.4%.All the synthetic route of CL-20 catalyzed by SDm(Tos)3,BSA-MCM-41 and SA-MCM-41 in N2O5/HNO3 system achieved the current technological level and avoided the use of sulfuric acid.The catalyst could be recycled and reused after reaction and the spent acid was easy to handle.The methods are very potential in industrial application.