高哲邦¹,冯云超¹,曾宪海¹,孙勇¹,唐兴¹,雷廷宙²,林鹿¹

• 1:厦门大学 能源学院，福建省生物质清洁高值化技术工程研究中心，厦门市生物质清洁高值化利用重点实验室，福建 厦门 361102
• 2:河南省生物质能源重点实验室，河南 郑州 450008

摘要(Abstract)：

对二甲苯（p-Xylene，pX）是一种十分重要的化工原料，其主要用途是生产对苯二甲酸（terephthalic acid，TA）和对苯二甲酸酯等聚合物单体产品。pX目前主要从石油化工路径制备得到。为了利用生物质资源绿色可持续地生产pX，从生物质基2，5-二甲基呋喃（2，5-Dimethylfuran，DMF）经Diels-Alder和脱水反应制备pX近年来逐渐成为研究热点。研究综述了近年来以生物质基DMF制备pX的研究进展，分析了该技术路线中催化体系和溶剂体系等方面的现状，并对生物质pX合成路径的发展趋势和前景进行展望。

关键词(KeyWords)： 生物质;2,5-二甲基呋喃;对二甲苯;催化;溶剂体系

Abstract:

Keywords:

基金项目(Foundation): 国家自然科学基金（21506177，21676223）；厦门大学校长基金（20720160077；20720160087；20720170062）；福建省自然科学基金（2016J01077）。

作者(Author): 高哲邦¹,冯云超¹,曾宪海¹,孙勇¹,唐兴¹,雷廷宙²,林鹿¹

DOI: 10.3969/j.issn.1003-9015.2019.02.001

参考文献(References)：

• [1] ESPOSITO D, ANTONIETTI M. Redefining biorefinery:the search for unconventional building blocks for materials[J]. Chemical Society Reviews, 2015, 44(16):5821-5835.
  [2] CHEN L, XIN J Y, NI L L, et al. Conversion of lignin model compounds under mild conditions in pseudo-homogeneous systems[J]. Green Chemistry, 2016, 18(8):2341-2352.
  [3] VLACHOS D G, CHEN J G, GORTE R J, et al. Catalysis center for energy innovation for biomass processing:research strategies and goals[J]. Catalysis Letters, 2010, 140(3-4):77-84.
  [4] TOMAS R A, BORDADO J C, GOMES J F. p-Xylene oxidation to terephthalic acid:a literature review oriented toward process optimization and development[J]. Chemical Reviews, 2013, 113(10):7421-7469.
  [5] FONG Y Y, ABDULLAH A Z, AHMAD A L, et al. Development of functionalized zeolite membrane and its potential role as reactor combined separator for para-xylene production from xylene isomers[J]. Chemical Engineering Journal, 2008, 139(1):172-193.
  [6] MANEFFA A, PRIECEL P, LOPEZ-SANCHEZ J A. Biomass-derived renewable aromatics:selective routes and outlook for p-xylene commercialisation[J]. ChemSusChem, 2016, 9(19):2736-2748.
  [7] 刘俊霞, 陈景润, 王军峰, 等. 生物质基呋喃制备对二甲苯研究进展[J]. 工业催化, 2017, 25(4):13-16. LIU J X, CHEN J R, WANG J F, et al. Research progress in the preparation of p-xylene from biomass-based furan[J]. Industrial Catalysis, 2017, 25(4):13-16.
  [8] ZHAO P P, ZHANG Y Y, WANG Y, et al. Conversion of glucose into 5-hydroxymethylfurfural catalyzed by acid-base bifunctional heteropolyacid-based ionic hybrids[J]. Green Chemistry, 2018, 20(7):1551-1559.
  [9] 刘迎新, 曾茂, 楼炯涛, 等. 5-羟甲基糠醛选择性加氢制备2,5-二甲基呋喃研究进展[J]. 高校化学工程学报, 2018, 32(2):255-265. LIU Y X, ZENG M, LOU J T, et al. Review on 2,5-dimethylfuran synthesis via selective hydrogenation of 5-hydroxymethylfufural[J]. Journal of Chemical Engineering of Chinese Universities, 2018, 32(2):255-265.
  [10] BRANDVOLD T A. Carbohydrate route to para-xylene and terephthalic acid:US, 8314267 B2[P]. 2012-11-20.
  [11] WILLIAMS C L, VINTER K P, CHANG C C, et al. Kinetic regimes in the tandem reactions of H-BEA catalyzed formation of p-xylene from dimethylfuran[J]. Catalysis Science & Technology, 2016, 6(1):178-187.
  [12] NIKBIN N, FENG S, CARATZOULAS S, et al. p-Xylene formation by dehydrative aromatization of a Diels-Alder product in Lewis and brønsted acidic zeolites[J]. The Journal of Physical Chemistry C, 2014, 118(42):24415-24424.
  [13] XIONG R C, SANDLER S I, VLACHOS D G, et al. Solvent-tuned hydrophobicity for faujasite-catalyzed cycloaddition of biomass-derived dimethylfuran for renewable p-xylene[J]. Green Chemistry, 2014, 16(9):4086-4091.
  [14] WALKER T W, CHEW A K, LI H X, et al. Universal kinetic solvent effects in acid-catalyzed reactions of biomass-derived oxygenates[J]. Energy & Environmental Science, 2018, 11(3):617-628.
  [15] MELLMER M A, SENER C, GALLO J M R, et al. Solvent effects in acid-catalyzed biomass conversion reactions[J]. Angewandte Chemie, 2014, 53(44):11872-11875.
  [16] SALAVATI-FARD T, CARATZOULAS S, DOREN D J. Solvent effects in acid-catalyzed dehydration of the Diels-Alder cycloadduct between 2,5-dimethylfuran and maleic anhydride[J]. Chemical Physics, 2017, 485-486:118-124.
  [17] WILLIAMS C L, CHANG C C, DO P, et al. Cycloaddition of biomass-derived furans for catalytic production of renewable p-xylene[J]. ACS Catalysis, 2012, 2(6):935-939.
  [18] WIJAYA Y P, SUH D J, JAE J. Production of renewable p-xylene from 2,5-dimethylfuran via Diels-Alder cycloaddition and dehydrative aromatization reactions over silica-alumina aerogel catalysts[J]. Catalysis Communications, 2015, 70:12-16.
  [19] CHIAPPE C, MALVALDI M, POMELLI C S. The solvent effect on the Diels-Alder reaction in ionic liquids:multiparameter linear solvation energy relationships and theoretical analysis[J]. Green Chemistry, 2010, 12(8):1330-1339.
  [20] AGGARWAL A, LANCASTER N L,SETHI A R, et al. The role of hydrogen bonding in controlling the selectivity of Diels-Alder reactions in room-temperature ionic liquids[J]. Green Chemistry, 2002, 4(5):517-520.
  [21] VIDIŠ A, OHLIN C A, LAURENCZY G, et al. Rationalisation of solvent effects in the Diels-Alder reaction between cyclopentadiene and methyl acrylate in room temperature ionic liquids[J]. Advanced Synthesis & Catalysis, 2005, 347(2-3):266-274.
  [22] NI L L, XIN J Y, DONG H X, et al. A simple and mild approach for the synthesis of p-xylene from bio-based 2,5-dimethyfuran by using metal triflates[J]. ChemSusChem, 2017, 10(11):2394-2401.
  [23] NI L L, XIN J Y, JIANG K, et al. One-step conversion of biomass-derived furanics into aromatics by brønsted acid ionic liquids at room temperature[J]. ACS Sustainable Chemistry & Engineering, 2018, 6(2):2541-2551.
  [24] CHANG C C, GREEN S K, WILLIAMS C L, et al. Ultra-selective cycloaddition of dimethylfuran for renewable p-xylene with H-BEA[J]. Green Chemistry, 2014, 16(2):585-588.
  [25] TEIXEIRA I F, LO B T W, KOSTETSKYY P, et al. From biomass-derived furans to aromatics with ethanol over zeolite[J]. Angewandte Chemie, 2016, 55(42):13061-13066.
  [26] WECKHUYSEN B M, YU J H. Recent advances in zeolite chemistry and catalysis[J]. Chemical Society Reviews, 2015, 44(20):7022-7024.
  [27] YU J Y, ZHU S Y, DAUENHAUER P J, et al. Adsorption and reaction properties of SnBEA, ZrBEA and H-BEA for the formation of p-xylene from DMF and ethylene[J]. Catalysis Science & Technology, 2016, 6(14):5729-5736.
  [28] PATET R E, FAN W, VLACHOS D G, et al. Tandem Diels-Alder reaction of dimethylfuran and ethylene and dehydration to para-xylene catalyzed by zeotypic Lewis acids[J]. ChemCatChem, 2017, 9(13):2523-2535.
  [29] PACHECO J J, DAVIS M E. Synthesis of terephthalic acid via Diels-Alder reactions with ethylene and oxidized variants of 5-hydroxy-methylfurfural[J]. Proceedings of the National Academy of Sciences of the United States of America, 2014, 111(23):8363-8367.
  [30] PACHECO J J, LABINGER J A, SESSIONS A L, et al. Route to renewable PET:reaction pathways and energetics of Diels-Alder and dehydrative aromatization reactions between ethylene and biomass-derived furans catalyzed by Lewis acid molecular sieves[J]. ACS Catalysis, 2015, 5(10):5904-5913.
  [31] PATET R E, CARATZOULAS S, VLACHOS D G. Tandem aromatization of oxygenated furans by framework zinc in zeolites:a computational study[J]. The Journal of Physical Chemistry C, 2017, 121(40):22178-22186.
  [32] NIKBIN N, CARATZOULAS S, VLACHOS D G. On the Bronsted acid-catalyzed homogeneous hydrolysis of furans[J]. ChemSusChem, 2013, 6(11):2066-2068.
  [33] PATET R E, KOEHLE M, LOBO R F, et al. General acid-type catalysis in the dehydrative aromatization of furans to aromatics in H-[Al]-BEA, H-[Fe]-BEA, H-[Ga]-BEA, and H-[B]-BEA zeolites[J]. The Journal of Physical Chemistry C, 2017, 121(25):13666-13679.
  [34] CHO H J, REN L M, VATTIPALLI V, et al. Renewable p-xylene from 2,5-dimethylfuran and ethylene using phosphorus-containing zeolite catalysts[J]. ChemCatChem, 2017, 9(3):398-402.
  [35] ROHLING R Y, USLAMIN E, ZIJLSTRA B, et al. An active alkali-exchanged faujasite catalyst for para-xylene production via the one-pot Diels-Alder cycloaddition/dehydration reaction of 2,5-dimethylfuran with ethylene[J]. ACS Catalysis, 2018, 8(2):760-769..
  [36] PATET R E, NIKBIN N, WILLIAMS C L, et al. Kinetic regime change in the tandem dehydrative aromatization of furan Diels-Alder products[J]. ACS Catalysis, 2015, 5(4):2367-2375.
  [37] ENNAERT T, AELST J V, DIJKMANS J, et al. Potential and challenges of zeolite chemistry in the catalytic conversion of biomass[J]. Chemical Society Reviews, 2016, 45(3):584-611.
  [38] LUO H Y, LEWIS J D, ROMAN-LESHKOV Y. Lewis acid zeolites for biomass conversion:perspectives and challenges on reactivity, synthesis, and stability[J]. Annual Review of Chemical and Biomolecular Engineering, 2016, 7:663-692.
  [39] MOLINER M. State of the art of Lewis acid-containing zeolites:lessons from fine chemistry to new biomass transformation processes[J]. Dalton Transactions, 2014, 43(11):4197-4208.
  [40] NIKBIN N, DO P T, CARATZOULAS S, et al. A DFT study of the acid-catalyzed conversion of 2,5-dimethylfuran and ethylene to p-xylene[J]. Journal of Catalysis, 2013, 297:35-43.
  [41] FENG X Q, SHEN C, TIAN C C, et al. Highly selective production of biobased p-xylene from 2,5-dimethylfuran over SiO₂-SO₃H catalysts[J]. Industrial & Engineering Chemistry Research, 2017, 56(20):5852-5859.
  [42] KIM J C, KIM T W, KIM Y J, et al. Mesoporous MFI zeolites as high performance catalysts for Diels-Alder cycloaddition of bio-derived dimethylfuran and ethylene to renewable p-xylene[J]. Applied Catalysis B:Environmental, 2017, 206:490-500.
  [43] KIM T W, KIM S Y, KIM J C, et al. Selective p-xylene production from biomass-derived dimethylfuran and ethylene over zeolite beta nanosponge catalysts[J]. Applied Catalysis B:Environmental, 2016, 185:100-109.
  [44] FENG X Q, SHEN C, JI K Y, et al. Production of p-xylene from bio-based 2,5-dimethylfuran over high performance catalyst WO₃/SBA-15[J]. Catalysis Science & Technology, 2017, 7(23):5540-5549.
  [45] WANG D, OSMUNDSEN C M, TAARNING E, et al. Selective production of aromatics from alkylfurans over solid acid catalysts[J]. ChemCatChem, 2013, 5(7):2044-2050.
  [46] YIN J B, SHEN C, FENG X Q, et al. Highly selective production of p-xylene from 2,5-dimethylfuran over hierarchical NbO_x-based catalyst[J]. ACS Sustainable Chemistry & Engineering, 2017, 6(2):1891-1899.
  [47] KOZHEVNIKOV I V. Sustainable heterogeneous acid catalysis by heteropoly acids[J]. Journal of Molecular Catalysis A:Chemical, 2007, 262(1-2):86-92.
  [48] WANG S S, YANG G Y. Recent advances in polyoxometalate-catalyzed reactions[J]. Chemical Reviews, 2015, 115(11):4893-4962.
  [49] LU R, LU F, CHEN J Z, et al. Production of diethyl terephthalate from biomass-derived muconic acid[J]. Angewandte Chemie, 2016, 55(1):249-253.
  [50] WIJAYA Y P, WINOTO H P, PARK Y K, et al. Heteropolyacid catalysts for Diels-Alder cycloaddition of 2,5-dimethylfuran and ethylene to renewable p-xylene[J]. Catalysis Today, 2017, 293-294:167-175.
  [51] BOKADE V V, YADAV G D. Heteropolyacid supported on montmorillonite catalyst for dehydration of dilute bio-ethanol[J]. Applied Clay Science, 2011, 53(2):263-271.
  [52] ALHARBI W, BROWN E, KOZHEVNIKOVA E F, et al. Dehydration of ethanol over heteropoly acid catalysts in the gas phase[J]. Journal of Catalysis, 2014, 319:174-181.
  [53] SETTLE A E, BERSTIS L, RORRER N A, et al. Heterogeneous Diels-Alder catalysis for biomass-derived aromatic compounds[J]. Green Chemistry, 2017, 19(15):3468-3492.
  [54] TAO M L, XUE L F, SUN Z, et al. Tailoring the synergistic Bronsted-Lewis acidic effects in heteropolyacid catalysts:applied in esterification and transesterification reactions[J]. Scientific Reports, 2015, 5:13764.
  [55] KISHIDA T, YAMAUCHI T, KUBOTA Y, et al. Rare-earth metal triflates as versatile catalysts for the chloromethylation of aromatic hydrocarbons[J]. Green Chemistry, 2004, 6(1):57-62.
  [56] SARMA D, KUMAR A. Rare earth metal triflates promoted Diels-Alder reactions in ionic liquids[J]. Applied Catalysis A:General, 2008, 335(1):1-6.
  [57] SONG S, WU G J, DAI W L, et al. Diels-Alder and dehydration reactions of furan derivatives with ethylene catalyzed by liquid Brønsted acids and Lewis acids[J]. Journal of Molecular Catalysis A:Chemical, 2016, 420:134-141.
  [58] SHUAI L, LUTERBACHER J. Organic solvent effects in biomass conversion reactions[J]. ChemSusChem, 2016, 9(2):133-155.
  [59] SHIRAMIZU M, TOSTE F D. On the Diels-Alder approach to solely biomass-derived polyethylene terephthalate (PET):conversion of 2,5-dimethylfuran and acrolein into p-xylene[J]. Chemistry, 2011, 17(44):12452-12457.
  [60] MAHMOUD E, WATSON D A, LOBO R F. Renewable production of phthalic anhydride from biomass-derived furan and maleic anhydride[J]. Green Chemistry, 2014, 16(1):167-175.
  [61] XIAO Y, MALHOTRA S V. Diels-Alder reactions in pyridinium based ionic liquids[J]. Tetrahedron Letters, 2004, 45(45):8339-8342.