糖類衍生物催化制液體烷烴燃料的基礎(chǔ)研究

馬隆龍 劉琪英

摘 要：該研究針對第三個關(guān)鍵科學(xué)問題“解聚產(chǎn)物催化轉(zhuǎn)化制備先進(jìn)液體燃料的機(jī)理及產(chǎn)物選擇性控制規(guī)律”開展基礎(chǔ)性研究工作。在糖類衍生物水相催化制液體烷烴燃料的反應(yīng)機(jī)理、產(chǎn)物控制規(guī)律研究和相關(guān)高效催化劑體系設(shè)計等方面進(jìn)行了探索。針對糖類衍生物水相催化合成HMF，發(fā)展了高效的類微乳反應(yīng)體系和NaHSO4-ZnSO4催化劑體系，可有效避免副產(chǎn)物生成和HMF的進(jìn)一步降解，獲得高達(dá)57%的HMF收率。發(fā)展MOFs內(nèi)嵌雜多酸和Ru粒子的高效催化劑，通過金屬與酸的功能匹配，實現(xiàn)了纖維素等一步轉(zhuǎn)化為山梨醇，山梨醇收率達(dá)到58%。制備了Ni基金屬-酸雙功能催化劑應(yīng)用于山梨醇/木糖醇轉(zhuǎn)化為C5/C6烷烴，通過金屬組分、載體等的調(diào)控作用和反應(yīng)機(jī)理研究，實現(xiàn)C5/C6烷烴產(chǎn)物的定向催化合成，收率超過90%。針對糠醛與丙酮的縮合反應(yīng)，設(shè)計合成了高效MgO/NaY固體堿催化劑，堿性質(zhì)及MgO與NaY的協(xié)同催化作用可有效活化糠醛與丙酮分子，加快反應(yīng)速率，獲得高達(dá)98%的C8-C15縮合產(chǎn)物，設(shè)計合成了Pt/SiO2-ZrO2催化劑，通過調(diào)控催化劑的組成結(jié)構(gòu)和產(chǎn)物加氫脫氧路徑分析，獲得收率達(dá)到70%的C8-C15烷烴產(chǎn)物，催化劑連續(xù)運行120 h不失活，具有較好的穩(wěn)定性。針對酚類衍生物催化制備液體烷烴燃料，設(shè)計合成了離子液共聚物負(fù)載的Ru催化劑，通過離子液共聚物穩(wěn)定Ru納米粒子的金屬-酸雙功能的協(xié)同催化作用（金屬中心的C-C鍵加氫飽和，酸中心的C-O斷裂），實現(xiàn)了苯酚及其衍生加氫脫氧高效轉(zhuǎn)化為液體烷烴。針對苯酚選擇性加氫制環(huán)己酮，設(shè)計合成了高效的聚苯胺修飾碳納米管負(fù)載Pd催化劑，通過聚苯胺修飾碳納米管的電子調(diào)控對苯酚及其衍生物的選擇性吸附和Pd活性組分的協(xié)同加氫作用，實現(xiàn)了苯酚及其衍生物定向轉(zhuǎn)化為環(huán)己酮衍生物，環(huán)己酮收率高達(dá)99%。在上述研究基礎(chǔ)上，我們率先在國內(nèi)建立了年產(chǎn)150噸規(guī)模的生物汽油驗證研究系統(tǒng)。

關(guān)鍵詞：糖 水相催化 液體烷烴 基礎(chǔ)研究

Abstract：Aiming to the third key scientific issue “transformation route and mechanism for advanced liquid fuel production from decomposed products by aqueous phase catalysis” of the project， we used sugar derivatives as the feedstock to synthesize liquid C5/C6 and C8-C15 alkanes with the emphasis on the reaction mechanism and goal products controlling methods， and relative catalysts designation. For biomass derived HMF platform， we developed the highly efficient analogue micro-emulsion reaction system and NaHSO4-ZnSO4 combined catalyst， which obtained the HMF yield of 57%. For one-step conversion of cellulose to sorbitol， we fabricated highly active MOFs encapsulated heteropolyacid and Ru nanoparticle as the catalyst and the 58% of sorbitol yield could be observed by mediating the acid-metal balance in the catalyst. We synthesized the efficient Ni based bi-functional catalysts for sorbtiol/xylitol conversion to C5/C6 alkanes. By choosing metal， support and their assembly together with the investigation on the hydrodeoxygenation （HDO） mechanism， more than 90% of C5/C6 alkanes yield could be obtained. For jet fuel with the carbon chain length of C8-C15 alkanes， we designed MgO/NaY for C-C bond coupling in furfural and acetone. The synergistic effect of MgO and NaY activated the α-H in acetone and carbonyl group in furfural， which accelerates the condensation rate and obtains the C8-C15 condensation products yield of more than 98%. To achieve production of C8-C15 alkanes， we used Pt/SiO2-ZrO2 for HDO of C8-C15 condensation products. Due to the weak acidity of the catalyst and high C-O bond cracking property of Pt， the catalyst possessed 70% of goal products yield and showed the excellent catalytic stability of more than 120 h. For phenol derivatives conversion to liquid alkane fuel， we fabricated Ru supported on ionic liquid contained copolymer as the catalyst. By using the cooperative effect between the Ru catalyzed C=C bond saturation and acid catalyzed C-O bond cracking. For selective hydrogenation of phenol to cyclopentanone， we synthesized Pd supported carbon nanotube modified with polyaniline. Due to the selective adsorption phenol on polyaniline and hydrogenation on Pd， more than 99% of cyclopentanone could be obtained. Based on the mentioned investigation， we built up a pilot scaled facility of 150t/a for bio-gasoline production for the first time in China， which demonstrated a platform for practical production of bio-fuel on a large scale.

Key Words：Sugar；Aqueous phase catalysis；Liquid alkane；Basic research

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