《低碳与生物质》PPT课件

单击此处编辑母版标题样式,单击此处编辑母版文本样式,第二级,第三级,第四级,第五级,*,简述低碳经济中,生物质化学的发展机会,1、选题求异（问题、方法、途径）,2、文字简练,3、附主要参考文献,（手写、打印均以一页,A4,纸为限；手写材料纸以3页为限）,聚乳酸,Poly(lactic acid); Polylactide,聚乳酸原料-产品循环图,乳酸,聚乳酸纤维,废弃物,二氧化碳,水,淀 粉,丙交酯开环聚合反应,Optical isomers of lactic acid,聚乳酸结构的复杂性,三种乳酸性质的比较,(+)-乳酸及(-)-乳酸的球棒模型,20,D,（水）,熔点/,pKa,（+）-乳酸,（-）-乳酸,（)-乳酸,+3.82,-3.82,0,53,53,18,3.79,3.79,3.86,D,-Lactide PDLA,DL,-Lactide PDLLA,DL,-Polylactide (Random),D,- Polylactide (-D-D-D-),L,- Polylactide (-,L-L-L-),D,-,L,- block (,D-D-D,-L-L-L),DL,-,L,-copolymer (,DLL-L),DL,-,D,-copolymer (,DLD-D),D,-,L,-complex (-D-D-D-/-,L-L-L-),Structures of polylactide (polylactic acid, PLA),光合作用的启示,nCO,2,+ nH,2,O (CH,2,O)n + nO,2,hv,1915年R.威尔斯泰特(德国)：,植物色素(叶绿素)的研究,1930年H.非舍尔(德国)：,血红素和叶绿素的性质及结构方面的研究,1961年M.卡尔文(美国)：,植物光合作用机理,1965年R.B.伍德沃德(美国)：,叶绿素全合成,1988年J.戴森霍弗，R.胡伯尔，H.米歇尔,(,德国)：,光合作用反应中心的三维结构,1992年R.A.马库斯(美国)：,溶液中的电子转移反应理论及在光合作用中的应用,1997年P.B.博耶(美国)，J.E.沃克尔(英国)，J.C.斯科(丹麦)：,ATP和ATP酶,与光合作用有关的Nobel化学奖,景天酸代谢途径,一、太阳能（光）利用：,太阳能转化成化学能,二、二氧化碳利用：,二氧化碳转化成碳水化合物,三、酶催化：,环境温度,光合作用中化学反应的特点,暗反应,光反应,启示一：人工模拟光合作用,NADPH: 烟酰胺腺嘌呤二核苷酸磷酸,Tabushi, Iwao; Yazaki, Akira; Koga, Noboru; Iwasaki, Keiji： Artificial photosynthesis system of bacteria type，,Tetrahedron Letters，,1980, 21(4)：373-6.,启示二：,光分解水制氧气和氢气,启示三：将二氧化碳转化成有机碳,maximum CO,2,conversion: 23.2%,Yields: 20%,Selectivity: 96%,byproduct,150,o,C,160 bar,K. M. Kerry Yu, Connie M. Y. Yeung, and Shik Chi Tsang：Carbon Dioxide Fixation into Chemicals (Methyl Formate) at High Yields by Surface Coupling over a Pd/Cu/ZnO Nanocatalyst，,JACS,2007, 129, 6360-6361,1,2,3,H,2,: 0.16mmol/h,CH,4,: 0.25mmol/h,Formation,rate,C,O,2,+,H,2,O,C,H,4,+,H,C,O,O,H,+,H,C,H,O,+,C,H,3,O,H,+,C,2,H,5,O,H,P,t,-,l,o,a,d,e,d,K,2,T,i,6,O,1,3,F,e,-,C,u,-,K,/,D,A,Y,S,u,n,l,i,g,h,t,TiO,2,U,V,C,H,4,+,H,2,+,C,O,N,i,/,N,i,O,M,W,C,H,4,+,C,2,H,6,+,C,H,3,O,H,+,C,H,3,C,O,C,H,3,+,C,3,C,4,a,l,c,o,h,o,l,s,1,Sci. Techn. Adv. Mater,.,2007, 8, 8992 and,Catalysis Today, 2006, 115, 269-273,2,Appl. Catal. B - Environ.,2003, 41, 387396,3,Res. Chem. Intermediat,.,1991, 16, 241-255.,Product formation from photocatalytic reduction of CO,2,with H,2,O using TiO,2,pellets,聚碳酸酯,启示四：基因工程,“利用胚胎干细胞把特定基因改性引入实验鼠的原理”,二、生物质热化学,转化将长期的地质化学过程转变为短时的化工生产过程。,Paul J. Dauenhauer, Bradon J. Dreyer, Nick J. Degenstein, and,Lanny D. Schmidt,: Millisecond Reforming of Solid Biomass for Sustainable: Fuels, Angew. Chem. Int. Ed. 2007, 46, 5864 5867,(University of Minnesota),“We proposed a process by which C(gr) could be extracted from CO,2,using high-temperature solar energy,.”,背景一、利用太阳能产生的高温将二氧化碳转化成碳,三、太阳能高温用于化学转化,希尔反应 (Hill reaction),：,1939年英国剑桥大学的希尔(Robert. Hill)发现在分离的叶绿体(实际是被膜破裂的叶绿体)悬浮液中加入适当的电子受体(如草酸铁)，照光时可使水分解而释放氧气：,其中的电子受体被称为希尔氧化剂(Hill oxidant)，铁氰化钾、草酸铁、多种醌、醛及有机染料都可作为希尔氧化剂。,The reduction of gaseous oxides such as CO,2,and H,2,O is an important concern in industrial processes and pollution control. Here we report the reduction of carbon dioxide to carbon with an efficiency of nearly 100% at 290,o,C using cation-excess magnetite (Fe,3+,d,O,4,d=0.127,). In this reaction, the oxygen in the CO,2,is transferred, in the form of O,2-, to the cation-excess magnetite, and no gas is evolved. The carbon in the CO,2,is reduced to carbon (zero valence) by the addition of an electron donated from the cation-excess magnetite to maintain electrical neutrality during the transfer of the O,2-,to the magnetite. When we used H,2,O in place of CO,2, hydrogen gas was evolved, indicating that the same mechanism can also reduce H,2,O.,YUTAKA TAMAURA & MASAHIRO TAHATA：,Complete reduction of carbon dioxide to carbon using cation-excess magnetite，,Nature,346, 255 - 256 (19 July 1990); doi:10.1038/346255a0,背景二、利用太阳能产生的高温将水分解成氧与氢,A. T-Raissi, N. Muradov, C. Huang, O. Adebiyi:,Hydrogen From Solar Via Light-Assisted High-Temperature Water Splitting Cycles,Journal of Solar Energy Engineering,2007, 129:185,Biomass Pyrolysis under Microwave Irradiation,Cellulose,Catalyst,Microwaves,/,150,o,C,150s,Charcoal + Tar 70%,Gases 30%,Wood,Catalyst,Microwaves/,150,o,C,150s,Charcoal + Tar 70%,Gases 30%,C%: 63.36; H%: 4.25,C%: 57.61; H%: 4.26,C%: 41.65; H%: 7.03,C%: 48.22; H%: 6.81,Conventional:,300,900,C,5.3,H,4.3,O,2,C,4.8,H,4.3,O,2,生物质的低能耗转化,2009年11月13日课堂讨论题目：,从生物质制燃油和大宗化学品,（聚乳酸、生物乙醇、生物乙烯、生物柴油、生物环氧氯丙烷等）,