Page 102 - 《精细化工》2021年第8期
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·1596·                            精细化工   FINE CHEMICALS                                 第 38 卷

                 从图 4 可以看出，对于苯酚和 DMC 制苯甲醚                      催化剂的重复使用性还需进一步考察。催化剂活性
            的反应，MgAl-LDO 和 KF/MgAl-LDO 的总碱量与                   与碱性关系的研究表明，苯甲醚收率与总碱量呈线
            活性的关系一致，苯甲醚收率与总碱量基本呈线性                             性正相关，且碱强度在 11.0~15.0 的强碱性位拥有更
            正相关。且相同总碱量下，KF/MgAl-LDO 上的苯甲                       高的催化效率。
            醚收率远高于 MgAl-LDO。显示 KF/MgAl-LDO 中
                                                               参考文献：
            单位碱性位的催化效率高于 MgAl-LDO。
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            和 MgAl-LDO 两个固体碱催化剂的碱性位分布如图                            Organic Process Research & Development, 2005, 9(2): 206-211.
            5 所示。从图 5 可以看出，弱碱性位占比相差不大，                         [2]   ACHET  D,  ROCRELLE D, MURENGEZI I,  et al. Reactions  in
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            但相比 MgAl-LDO，KF/MgAl-LDO 中碱强 度在
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            9.3~11.0 内的中等碱性位占比减少，而碱强度在                         [3]   OUK S, THIEBAUD S, BORREDON E,  et al. O-methylation  of
            11.0~15.0 的强碱性位占比增加。说明高效率的碱性                           phenolic compounds with dimethyl carbonate under solid/liquid phase
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               图 5  MgAl-LDO 和 KF/MgAl-LDO 的碱性位分布                  the presence of Mn 2(CO) 10, W(CO) 6, and Co 2(CO) 8[J]. Russian Journal
            Fig. 5    Base sites distribution of MgAl-LDO and KF/MgAl-   of Organic Chemistry, 2015, 51(3): 330-334.
                   LDO                                         [8]   SHEN Z L, JIANG X Z, MO W M, et al. Catalytic O-methylation of
                                                                   phenols with dimethyl carbonate to aryl  methyl ethers using
                 活性测试显示，KF/MgAl-LDO 和 MgAl-LDO                     [BMIm]Cl[J]. Green Chemistry, 2005, 7(2): 97-99.
                                                               [9]   DONG Y M (董燕敏), ZHAO Y (赵燕), ZHAO W S (赵万胜), et al.
            的苯甲醚收率分别为 95.2%和 96.2%，基本相同，
                                                                   Methylation of phenols and dimethyl carbonate to aryl methyl ether
            但 KF/MgAl-LDO 的催化剂用量减少 2/3，反应时间                        over ionic liquid catalysts[J]. Chemical Reaction Engineering and
            缩短一半，苯甲醚时空收率提高了 5 倍。表 7 显示                             Technology (化学反应工程与工艺), 2010, 26(4): 332-337.
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            性位增加了近 4 倍，进一步说明碱强度在 11.0~15.0                     [11] CHEN  B  (陈冰), XIAO F K (肖福魁), ZHAO N (赵宁),  et al. A
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            苯甲醚的反应显示出较好的催化活性。XRD 和                                 2010, 23(10): 1376-1380.
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            时，KF/MgAl-LDO 催化剂显示出最佳的催化性能，                       [14]  JYOTHI T M, RAJA T, TALAWAR M B, et al. Selective O-methylation
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            在 DMC/苯酚物质的量比为 2∶1，催化剂用量为苯                             hydrotalcites[J]. Applied Catalysis A :General, 2001, 211(1): 41-46.
            酚质量的 1%，200  ℃下反应 4 h，苯酚转化率达                       [15]  ZHANG W H, GUO X D, HE J, et al. Preparation of Ni(Ⅱ)/Ti(Ⅳ)
            98.6%，苯甲醚收率 95.2%，较相关报道             [13] 中效果最          layered double hydroxide at high supersaturation[J]. Journal of the
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            好的固体碱 F/Mg(Al)O 的催化剂用量减少 2/3，反应                    [16]  JYOTHI T M, RAJA T, TALAWAR M B, et al. Selective methylation
            时间缩短了一半，但苯甲醚收率仅降低了 3.8%。显                              of phenol, aniline and catechol with dimethyl carbonate over calcined
                                                                   Mg-Al hydrotalcites[J]. Synthetic Communications, 2000, 30(21):
            示优化条件制备的 KF/MgAl-LDO 催化剂在苯酚和
                                                                   3929-3934.
            DMC 合成苯甲醚的反应中有较好的应用前景，但该                                                         （下转第 1620 页）
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