Study on the performance of CF3SO3H modified sulfonic polymer-based catalyst in formaldehyde carbonylation reaction
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摘要: 采用水热合成、原位磺化法制备了固体磺酸型聚合物PDS-1.0催化剂，以三氟甲烷磺酸对其进行接枝改性得到PDS-1.0-F催化剂；采用N2吸附-脱附、TG、FT-IR、31P MAS NMR和XPS等技术对催化剂的物理和化学性质进行了表征，以甲醛羰基化制乙醇酸为探针反应对其催化性能进行了评价研究。结果表明，与PDS-1.0催化剂相比，氟磺酸改性后的PDS-1.0-F催化剂的比表面积、孔容积和酸量均降低，但是酸强度和热稳定性显著增加，由此对甲醛羰基化反应具有较好的催化性能，乙醇酸收率达到91.2%。Abstract: A sulfonic polymer-based catalyst (PDS-1.0) was synthesized by the hydrothermal and in situ sulfonation method, which is further modified by grafting with CF3SO3H, to get the PDS-1.0-F catalyst. The physical and chemical properties of the PDS-1.0 and PDS-1.0-F catalysts were characterized by N2 sorption, TG, FT-IR, 31P MAS NMR and XPS; the effect of CF3SO3H modification on the catalytic performance of PDS-1.0-F in the carbonylation of formaldehyde to glycolic acid was then investigated. The results show that after the CF3SO3H modification, the framework of PDS-1.0-F catalyst was grafted with strong electron withdrawing groups. In comparison with PDS-1.0, the CF3SO3H-modified PDS-1.0-F catalyst has a lower surface area, pore volume and concentration of acid sites, but much stronger acidity and higher thermal stability. As a result, the PDS-1.0-F catalyst exhibits excellent performance in the carbonylation of formaldehyde and over it the yield of glycolic acid reaches 91.2%.
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图 1 催化剂的N2吸附-脱附曲线和孔径分布
Figure 1 N2 adsorption-desorption isotherms and pore size distribution curves of the PDS-1.0 and PDS-1.0-F catalysts
图 2 PDS-1.0(a)、(c)和PDS-1.0-F(b)、(d)的SEM照片
Figure 2 SEM images of PDS-1.0 ((a), (c)) and PDS-1.0-F ((b), (d))
图 4 催化剂FT-IR谱图(a)和XPS谱图((b)、(c)、(d))
Figure 4 FT-IR spectra (a) and XPS spectra ((b), (c), (d)) of the PDS-1.0 and PDS-1.0-F catalysts
图 5 吸附TMPO的固体31P MAS NMR谱图
Figure 5 31P MAS NMR spectra of the TMPO-adsorbed PDS-1.0 and PDS-1.0-F catalysts
图 6 PDS-1.0-F催化甲醛羰基化乙醇酸可能的反应机理
Figure 6 Proposed reaction mechanism for PDS-1.0-F catalyzed carbonylation of HCHO to glycolic acid
图 7 条件实验：(a)反应压力的影响，(b)反应时间的影响，(c)反应温度的影响，(d)催化剂用量的影响
Figure 7 Optimization of reaction conditions (a): influence of reaction pressure; (b): influence of reaction time; (c): influence of reaction temperature; (d): influence of catalyst dosage
表 1 催化剂的织构性质及表面酸性
Table 1 Textural and acidic parameters of various catalysts
Catalyst ABET/(m2·g-1) vp/(cm3·g-1) dp/nm S contenta /(mmol·g-1) Acid sitesb /(mmol·g-1) PDS-1.0 320 0.65 7.7 1.95 1.90 PDS-1.0-F 226 0.67 10.1 3.69 1.65 ABET: BET surface area; vp: BJH pore volume; dp: average pore diameter; a: measured by CHNS elemental analysis; b: measured by acid-base titration 
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表 2 催化剂的甲醛羰基化反应的评价
Table 2 Catalytic performance of PDS-1.0 and PDS-1.0-F in the carbonylation of formaldehyde
Catalyst Conversion /% Yield /% STY None 0 0 - PDS-1.0 99.9 68.8 36.9 PDS-1.0-F 99.9 91.2 46.0 CF3SO3H 99.8 94.8 10.9 reaction conditions: 120℃, 6.0MPa, reaction time = 12h, TOX:Catalyst:HAc (mass) = 1:0.4: 9, conversion: formaldehyde conversion, yield: glycolic acid yield, STY: space time yield
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