蒋雨希,魏茜文,任傲天,吕喜蕾,吕秀阳

• 1:浙江大学生物质化工教育部重点实验室
• 2:浙江大学化学工程与生物工程学院
• 3:浙江恒逸石化研究院有限公司

摘要(Abstract)：

乳酸甲酯(MLA)是重要的生物质基平台化合物。Snβ分子筛催化生物质糖醇解制备MLA技术具有重要的工业化应用前景。针对Snβ分子筛催化剂制备工艺对其活性和重复使用性能影响的研究非常不系统、不全面等问题，详细考察了Snβ分子筛催化剂制备过程中脱铝、浸渍和焙烧等3步的工艺参数对其结构及催化果糖转化生成MLA性能的影响。结果表明，Snβ分子筛制备过程中市售Hβ分子筛脱铝步骤需要强酸，其中硝酸较佳；Hβ分子筛的硅铝比(物质的量比(n(Si):n(Al))、酸处理过程中酸浓度、浸渍液中SnCl_2浓度和焙烧温度都存在较佳条件，具体为：以n(Si):n(Al)=60的Hβ分子筛为原料、经质量分数为47%的HNO_3脱铝、再在浓度为0.1 mol·L~(-1)的SnCl_2乙醇溶液中浸渍、最后在550℃下焙烧得到的催化剂具有较佳的反应活性，用该催化剂180℃下催化果糖反应6 h时MLA收率最高可达53.6%；此外，该催化剂还具有良好的重复使用性能；表征结果显示，采用上述工艺制备的催化剂，Sn可以进入β分子筛骨架。本研究可为生物质非均相催化醇解制备MLA技术的工业化提供参考。

关键词(KeyWords)： 果糖;乳酸甲酯;Snβ分子筛;催化剂制备工艺

Abstract:

Keywords:

基金项目(Foundation): 国家自然科学基金(22078290,22278358)

作者(Author): 蒋雨希,魏茜文,任傲天,吕喜蕾,吕秀阳

参考文献(References)：

• [1] DUSSELIER M, VAN WOUWE P, DEWAELE A, et al. Lactic acid as a platform chemical in the biobased economy:The role of chemocatalysis[J]. Energy&Environmental Science, 2013, 6(5):1415-1442.
• [2] DATTA R, HENRY M. Lactic acid:Recent advances in products, processes and technologies:A review[J]. Journal of Chemical Technology&Biotechnology, 2006, 81(7):1119-1129.
• [3] LYU X L, WANG L X, CHEN X J, et al. Enhancement of catalytic activity by γ-NiOOH for the production of methyl lactate from sugars in near-critical methanol solutions[J]. Industrial&Engineering Chemistry Research, 2019, 58(9):3659-3665.
• [4] LU X L, FU J, LANGRISH T, et al. Simultaneous catalytic conversion of C6 and C5 sugars to methyl lactate in near-critical methanol with metal chlorides[J]. BioResources, 2018, 13(2):3627-3641.
• [5] YAN Y, ZHANG Z H, BAK S-M, et al. Confinement of ultrasmall cobalt oxide clusters within silicalite-1 crystals for efficient conversion of fructose into methyl lactate[J]. ACS Catalysis, 2019, 9(3):1923-1930.
• [6] M?KI-ARVELA P, AHO A, MURZIN D Y. Heterogeneous catalytic synthesis of methyl lactate and lactic acid from sugars and their derivatives[J]. ChemSusChem, 2020, 13(18):4833-4855.
• [7] YANG L S, YANG X K, TIAN E, et al. Mechanistic insights into the production of methyl lactate by catalytic conversion of carbohydrates on mesoporous Zr-SBA-15[J]. Journal of Catalysis, 2016, 333:207-216.
• [8] TANG B, LI S, SONG W C, et al. Fabrication of hierarchical Sn-beta zeolite as efficient catalyst for conversion of cellulosic sugar to methyl lactate[J]. ACS Sustainable Chemistry&Engineering, 2020, 8(9):3796-3808.
• [9] JIANG Y X, LYU X L, CHEN H, et al. Catalytic conversion of high fructose corn syrup to methyl lactate with CoO@silicalite-1[J].Catalysts, 2022, 12(4):442.
• [10] MURILLO B, ZORNOZA B, DE LA IGLESIA O, et al. Chemocatalysis of sugars to produce lactic acid derivatives on zeolitic imidazolate frameworks[J]. Journal of Catalysis, 2016, 334:60-67.
• [11] MURILLO B, ZORNOZA B, DE LA IGLESIA O, et al. Tin-carboxylate MOFs for sugar transformation into methyl lactate[J].European Journal of Inorganic Chemistry, 2019, 2019(21):2624-2629.
• [12] LU X L, WANG L X, LU X Y. Catalytic conversion of sugars to methyl lactate over Mg-MOF-74 in near-critical methanol solutions[J]. Catalysis Communications, 2018, 110:23-27.
• [13] LIU Z, LI W, PAN C Y, et al. Conversion of biomass-derived carbohydrates to methyl lactate using solid base catalysts[J]. Catalysis Communications, 2011, 15(1):82-87.
• [14] LYU X L, XU L, WANG J C, et al. New insights into the NiO catalytic mechanism on the conversion of fructose to methyl lactate[J].Catalysis Communications, 2019, 119:46-50.
• [15]王立新,吕喜蕾,阮厚航,等.近临界甲醇中Ni O催化生物质糖转化制备乳酸甲酯的研究[J].高校化学工程学报, 2017, 31(4):841-847.WANG L X, LüX L, RUAN H H, et al. A study on catalytic conversion of biomass-derived carbohydrates to methyl lactate by NiO in near-critical methanol[J]. Journal of Chemical Engineering of Chinese Universities, 2017, 31(4):841-847.
• [16] LYU X L, XU M, CHEN X J, et al. Beneficial effect of water on the catalytic conversion of sugars to methyl lactate in near-critical methanol solutions[J]. Industrial&Engineering Chemistry Research, 2019, 58(27):12451-12458.
• [17] DE CLIPPEL F, DUSSELIER M, VAN ROMPAEY R, et al. Fast and selective sugar conversion to alkyl lactate and lactic acid with bifunctional carbon-silica catalysts[J]. Journal of the American Chemical Society, 2012,134(24):10089-10101.
• [18] ZHANG J, WANG L, WANG G X, et al. Hierarchical Sn-beta zeolite catalyst for the conversion of sugars to alkyl lactates[J]. ACS Sustainable Chemistry&Engineering, 2017, 5(4):3123-3131.
• [19] ZHANG Y F, LUO H, ZHAO X P, et al. Continuous conversion of glucose into methyl lactate over the Sn-beta zeolite:Catalytic performance and activity insight[J]. Industrial&Engineering Chemistry Research, 2020, 59(39):17365-17372.
• [20] HOLM M S, SARAVANAMURUGAN S, TAARNING E. Conversion of sugars to lactic acid derivatives using heterogeneous zeotype catalysts[J]. Science, 2010, 328(5978):602-605.
• [21] LI P, LIU G Q, WU H H, et al. Postsynthesis and selective oxidation properties of nanosized Sn-beta zeolite[J]. The Journal of Physical Chemistry C, 2011, 115(9):3663-3670.
• [22] HU W D, CHI Z X, WAN Y, et al. Synergetic effect of Lewis acid and base in modified Sn-β on the direct conversion of levoglucosan to lactic acid[J]. Catalysis Science&Technology, 2020, 10(9):2986-2993.
• [23] WOLF P, HAMMOND C, CONRAD S, et al. Post-synthetic preparation of Sn-, Ti-and Zr-beta:A facile route to water tolerant,highly active Lewis acidic zeolites[J]. Dalton transactions, 2014, 43(11):4514-4519.
• [24] PADOVAN D, TOLBORG S, BOTTI L, et al. Overcoming catalyst deactivation during the continuous conversion of sugars to chemicals:Maximising the performance of Sn-beta with a little drop of water[J]. Reaction Chemistry&Engineering, 2018, 3(2):155-163.
• [25] VAN DER GRAAFF W N P, LI G N, MEZARI B, et al. Synthesis of Sn-beta with exclusive and high framework Sn content[J].ChemCatChem, 2015, 7(7):1152-1160.
• [26] YANG X M, LV B, LU T L, et al. Promotion effect of Mg on a post-synthesized Sn-beta zeolite for the conversion of glucose to methyl lactate[J]. Catalysis Science&Technology, 2020, 10(3):700-709.
• [27] MORAIS E K L, JIMèNEZ-SàNCHEZ S, HERNANDO H, et al. Catalytic copyrolysis of lignocellulose and polyethylene blends over H-beta zeolite[J]. Industrial&Engineering Chemistry Research, 2019, 58(16):6243-6254.
• [28]文韬. SnO2基酸碱两性催化剂的设计、改性及其催化生物质糖制乳酸甲酯[D].武汉：华中农业大学, 2019.WEN T. SnO2-based acid-base amphoteric catalysts:design, modification and catalysis of biomass sugar converting into methyl lactate[D]. Wuhan:Huazhong Agricultural University, 2019.
• [29] IGLESIAS J, MORENO J, MORALES G, et al. Sn–Al-USY for the valorization of glucose to methyl lactate:Switching from hydrolytic to retro-aldol activity by alkaline ion exchange[J]. Green Chemistry, 2019, 21(21):5876-5885.
• [30] TANG B, DAI W L, WU G J, et al. Improved postsynthesis strategy to Sn-beta zeolites as lewis acid catalysts for the ring-opening hydration of epoxides[J]. ACS Catalysis, 2014, 4(8):2801-2810.
• [31] PADOVAN D, BOTTI L, HAMMOND C. Active site hydration governs the stability of Sn-beta during continuous glucose conversion[J]. ACS Catalysis, 2018, 8(8):7131-7140.
• [32] FILICIOTTO L, BALU A M, VAN DER WAAL J C, et al. Catalytic insights into the production of biomass-derived side products methyl levulinate, furfural and humins[J]. Catalysis Today, 2018, 302:2-15.