α-磷酸锆@磺酸基固体酸催化剂的表征及其催化酯化反应的研究
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摘要
以层状结构的α-磷酸锆为载体,用四正丁基氢氧化铵对其剥离改性,再连接上γ-巯丙基三乙氧基硅烷(KH-580),通过氧化和酸化两步,制备出一种新型的固体酸催化剂α-磷酸锆@磺酸基。通过XRD、SEM、BET、TGA、FT-IR等手段对该催化剂进行表征。结果表明:制备的催化剂比表面积增大,结晶度降低,酸强为2. 43 mmol/g; FT-IR表征显示—SO_3H的存在,证明α-磷酸锆被成功磺化。将该催化剂应用于月桂酸与甲醇的催化酯化反应中,对反应条件进行优化,发现在反应温度90℃、反应时间5 h、酸醇摩尔比1∶30、催化剂用量3%(以月桂酸质量计)时,酯化率达到97%以上。该催化剂使用3次后,仍然保持着较高的催化活性,酯化率为87. 48%。
The layered α-Zr P was exfoliated by tetra-n-butylammonium hydroxide,masked as E-Zr P,then KH-580 was gifted on the surface of it,after oxidation and acidification,α-Zr P@SO_3 H was successfully prepared. The catalyst was characterized by XRD,SEM,BET,TGA and FT-IR. The results showed that the prepared catalyst had a larger specific surface area and a lower crystallinity,and its acid strength was 2. 43 mmol/g. FT-IR analysis indicated that —SO_3H was successfully gifted on α-Zr P. The catalyst was used in the esterification of lauric acid and methanol,and the esterification conditions were optimized as follows: temperature 90 ℃,time 5 h,molar ratio of acid to methanol 1:30,catalyst dosage 3% (on the basis of lauric acid mass). Under the optimal conditions,the esterification rate was more than 97%. After used for three times,the catalyst still maintained high catalytic activity,and the esterification rate was 87. 48%.
The layered α-Zr P was exfoliated by tetra-n-butylammonium hydroxide,masked as E-Zr P,then KH-580 was gifted on the surface of it,after oxidation and acidification,α-Zr P@SO_3 H was successfully prepared. The catalyst was characterized by XRD,SEM,BET,TGA and FT-IR. The results showed that the prepared catalyst had a larger specific surface area and a lower crystallinity,and its acid strength was 2. 43 mmol/g. FT-IR analysis indicated that —SO_3H was successfully gifted on α-Zr P. The catalyst was used in the esterification of lauric acid and methanol,and the esterification conditions were optimized as follows: temperature 90 ℃,time 5 h,molar ratio of acid to methanol 1:30,catalyst dosage 3% (on the basis of lauric acid mass). Under the optimal conditions,the esterification rate was more than 97%. After used for three times,the catalyst still maintained high catalytic activity,and the esterification rate was 87. 48%.
引文
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[2]孙昆仑,刘素环,何建英,等.碳基固体酸催化剂的制备及催化合成油酸甲酯[J].应用化工,2014(5):856-863.
[3]ANASTAS P T,KIRCHHOFF M M.Origins,current status,and future challenges of green chemistry[J].Accounts Chem Res,2002,35(9):686-694.
[4]MACHT J,CARR R T,IGLESIA E.Functional assessment of the strength of solid acid catalysts[J].J Catal,2009,264(1):54-66.
[5]CARR R T,NEUROCK M,IGLESIA E.Catalytic consequences of acid strength in the conversion of methanol to dimethyl ether[J].J Catal,2011,278(1):78-93.
[6]SIMONETTI D A,CARR R T,IGLESIA E.Acid strength and solvation effects on methylation,hydride transfer,and isomerization rates during catalytic homologation of C-1species[J].J Catal,2012,285(1):19-30.
[7]TODA M,TAKAGAKI A,OKAMURA M,et al.Biodiesel made with sugar catalyst[J].Nature,2005,438(10):178-179.
[8]PARK J W,PARK Y J,JUN C H.Post-grafting of silica surfaces with pre-functionalized organsilanes:new synthetic equivalents of conventional trialkoxy-silanes[J].Chem Commun,2011,47(17):4860-4871.
[9]CANO-SERRANO E,CAMPOS-MARTIN J M,FIER-RO J L G.Sulfonic acid-functionalized silica through quantitative oxidation of thiol groups[J].Chem Commun,2003,39(2):246-247.
[10]WEI L,CHRISTOPHER W J.Hybrid sulfonic acid catalysts based on silica-supported poly(styrene sulfonic acid)brush materials and their application in ester hydrolysis[J].J Catal,2011,278(1):674-681.
[11]WEI X,ZHAO H P,YAO J,et al.Esterification of cyclohexene with formic acid over a peanut shell-derived carbon solid acid catalyst[J].Chin J Catal,2016,37(5):769-777.
[12]傅相锴,马学兵,龚成斌,等.活性基团的空间分布对混合磷酸锆-钯催化剂羰化反应催化活性的影响[J].西南师范大学(自然科学学报),2000(4):414-419.
[13]CLEARFIED A,COSTANTINO U.Comprehensive supramolecular chemistry:Vol 7[M].UK Oxford:Elsevier,1996:107-150.
[14]ZHOU Y J,HUANG R C,DING F C,et al.Sulfonic acid-functionalizedα-zirconium phosphate single-layer nanosheets as a strong solid acid for heterogeneous catalysis applications[J].Appl Mater Int,2014,6:7417-7425.
[15]倪邦庆,刘慧,范明明,等.双酸位SO2-4/Zr O2-Si O2固载离子液体催化剂的构筑及性能[J].无机化学学报,2017,33(1):97-115.
[16]WANG L,WU X J,XU W H,et al.Stable organic-inorganic hybrid of polyaniline/α-zirconium phosphate for efficient removal of organic pollutants in water environment[J].Appl Mater Int,2012,4:2686-2692.
[17]HUISKEN F,KALOUDIS M,KULCKE A.Infrared spectroscopy of small size-selected water clusters[J].Chem Phys,1996,104:17-25.
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