材料部分由前面文章知道由於 MSN 比起有磁性 MSN 的羥基還要多,所以 我們利用 MSN 當作基材來修飾磺酸做為酸性催化劑,雖然它是固體材料可以回 收,不過無法達到完全回收;可以試著把氧化鐵的粒徑變小,使他可以包覆在 MSN 裡面而不是分布在表面或是裡面,這樣的話可以讓被覆蓋住的羥基顯露出 來,使更多的磺酸根可以接上去,所有的催化劑都可以利用磁力回收。
纖維素轉換的部分,可以使 HMF 繼續轉換成 DMF,DMF 就是真正的生質 燃油可以直接和汽油混合使用,要先找出此步驟所需要的催化劑以及所適合的反 應系統,根據初步的實驗我們得知轉化 HMF 至 DMF 的催化劑需要羧酸根來催 化,所以可以找一個有羧酸根的矽烷類並用架接法接上磁性的 MSN;另外根據 文獻記載此反應所用的溶劑為 THF(tetrahydrofuran)並不是 DMSO,所以必須要 克服不同溶劑的問題,關於此問題的初步解決方法有數種,其一就是嘗試在 DMSO 下可否利用催化劑使 HMF 轉化成 DMF,另外則是嘗試在 THF 為溶劑下 可否在水的存在下使果醣轉換成 HMF,則 HMF 轉換成 DMF 就可以直接加入催 化劑做轉換;最後則可以利用萃取的方法將 HMF 從 DMSO 萃取至 THF,再加 入有羧酸根磁性 MSN 做催化劑轉換成 DMF;如此就可以使序列式反應達到最終 目標,也就是纖維素經過四步驟的序列反應轉換成 DMF,並且四種催化劑都可 以很簡易的利用磁力進行回收並做回收次數的測試。
69
參考文獻
1. Alonso, D. M.; Bond, J. Q.; Dumesic, J. A.: Catalytic Conversion of Biomass to Biofuels. Green Chem. 2010, 12, 1493-1513.
2. Peng, F.; Peng, P.; Xu, F.; Sun, R. C.: Fractional Purification and Bioconversion of Hemicelluloses. Biotechnol. Adv. 2012, 30, 879-903.
3. Riansa-ngawong, W.; Prasertsan, P.: Optimization of Furfural Production from Hemicellulose Extracted from Delignified Palm Pressed Fiber Using A Two-Stage Process. Carbohydr. Res. 2011, 346, 103-110.
4. Kosa, M.; Ragauskas, A. J.: Bioconversion of Lignin Model Compounds with Oleaginous Rhodococci. Appl. Microbiol. Biotechnol. 2012, 93, 891-900.
5. Dutta, S.; De, S.; Saha, B.: A Brief Summary of the Synthesis of Polyester Building-Block Chemicals and Biofuels from 5-Hydroxymethylfurfural.
ChemPlusChem 2012, 77, 259-272.
6. Chidambaram, M.; Bell, A. T.: A Two-Step Approach for the Catalytic Conversion of Glucose to 2,5-Dimethylfuran In Ionic Liquids. Green Chem. 2010, 12, 1253-1262.
7. Murphy, M.: Early Success in HMF to Cellulose Process. Chem. Ind. 2007, 10-10.
8. Yu, S.; Brown, H. M.; Huang, X. W.; Zhou, X. D.; Amonette, J. E.; Zhang, Z. C.:
Single-Step Conversion of Cellulose to 5-Hydroxymethylfurfural (HMF), A Versatile Platform Chemical. Appl. Catal. A-Gen. 2009, 361, 117-122.
9. Centi, G.; Perathoner, S.; Lanzafame, P.; Temi, M.; Macario, A.; Giordano, G.:
Second Generation Biodiesel: from Cellulose to 5-HMF Derivates. Abstr. Pap. Am.
Chem. Soc. 2010, 240.
10. Peng, W. H.; Lee, Y. Y.; Wu, C. N.; Wu, K. C. W.: Acid-base Bi-functionalized, Large-pored Mesoporous Silica Nanoparticles for Cooperative Catalysis of One-pot Cellulose-to-HMF Conversion. J. Mater. Chem. 2012, 22, 23181-23185.
11. Liu, L. Y.; Chen, H. Z.: Enzymatic Hydrolysis of Cellulose Materials Treated with Ionic Liquid BMIM Cl. Chin. Sci. Bull. 2006, 51, 2432-2436.
12. Chang, R. H. Y.; Jang, J.; Wu, K. C. W.: Cellulase Immobilized Mesoporous Silica Nanocatalysts for Efficient Cellulose-to-glucose Conversion. Green Chem. 2011, 13, 2844-2850.
13. Zhang, B.; Wang, L. J.; Shahbazi, A.; Diallo, O.; Whitmore, A.: Dilute-Sulfuric Acid Pretreatment of Cattails for Cellulose Conversion. Bioresour. Technol. 2011, 102, 9308-9312.
14. Yu, H. T.; Guo, Y. L.; Wu, D. L.; Zhan, W. C.; Lu, G. Z.: Immobilization of Glucose Isomerase onto GAMM Support for Isomerization of Glucose to Fructose. J.
Mol. Catal. B-Enzym. 2011, 72, 73-76.
15. Lima, S.; Dias, A. S.; Lin, Z.; Brandao, P.; Ferreira, P.; Pillinger, M.; Rocha, J.;
70
Calvino-Casilda, V.; Valente, A. A.: Isomerization of D-Glucose to D-Fructose over Metallosilicate Solid Bases. Appl. Catal. A-Gen. 2008, 339, 21-27.
16. Carniti, P.; Gervasini, A.; Marzo, M.: Absence of Expected Side-Reactions in the Dehydration Reaction of Fructose to HMF in Water over Niobic Acid Catalyst. Catal.
Commun. 2011, 12, 1122-1126.
17. Tsuneo Yanagisawa, T. S., Kazuyuki Kuroda, Chuzo Kato: Bulletin of the Chemical Society of Japan 1990, 988-992.
18. Trewyn, B. G. S., I. I.; Giri, S.; Chen, H.-T.; Lin, V. S. Y.: Acc. Chem. Res. 2007, 846-853.
19. Boote, B. S., H.; Ranjit, K. T.: chem. Comm. 2007, 4543-4545.
20. Kim, S. J.; Dwiatmoko, A. A.; Choi, J. W.; Suh, Y. W.; Suh, D. J.; Oh, M.:
Cellulose Pretreatment with 1-n-butyl-3-methylimidazolium Chloride for solid Acid-catalyzed hydrolysis. Bioresour. Technol. 2010, 101, 8273-8279.
21. Dadi, A. P.; Varanasi, S.; Schall, C. A.: Enhancement of Cellulose Saccharification Kinetics Using An Ionic Liquid Pretreatment Step. Biotechnol. Bioeng. 2006, 95, 904-910.
22. Sathitsuksanoh, N.; George, A.; Zhang, Y. H. P.: New Lignocellulose Pretreatments Using Cellulose Solvents: A Review. J. Chem. Technol. Biotechnol.
2013, 88, 169-180.
23. Himmler, S.; Konig, A.; Wasserscheid, P.: Synthesis of EMIM OH via Bipolar Membrane Electrodialysis - Precursor Production for the Combinatorial Synthesis of EMIM -Based Ionic Liquids. Green Chem. 2007, 9, 935-942.
24. Akerstedt, J.; Gorlov, M.; Kloo, L.: Room-Temperature Synthesis of the Bi-5 GaCl4 (3) Salt from Three Different Classes of Ionic Liquids. J. Clust. Sci. 2013, 24, 157-164.
25. Alfani, F.; Gallifuoco, A.; Saporosi, A.; Spera, A.; Cantarella, M.: Comparison of SHF and SSF Processes for the Bioconversion of Steam-exploded Wheat Straw. J. Ind.
Microbiol. Biotechnol. 2000, 25, 184-192.
26. Beguin, P.; Gilkes, N. R.; Kilburn, D. G.; Miller, R. C.; Oneill, G. P.; Warren, R. A.
J.: Cloning of Cellulase Genes. Crc Critical Reviews in Biotechnology 1987, 6, 129-162.
27. Ghose, T. K.: Cellulase Biosynthesis and Hydrolysis of Cellulosic Substances.
Advances in biochemical engineering 1976, 6, 39-74.
28. Bisaria, V. S.; Mishra, S.: Regulatory Aspects of Cellulase Biosynthesis and Secretion. Crit. Rev. Biotechnol. 1989, 9, 61-103.
29. Bhat, M. K.; Bhat, S.: Cellulose Degrading Enzymes and Their Potential Industrial Applications. Biotechnol. Adv. 1997, 15, 583-620.
30. Bisaria, V. S.; Ghose, T. K.: Biodegradation of Cellulosic Materials - Substrates,
71
Microorganisms, Enzymes And Products. Enzyme Microb. Technol. 1981, 3, 90-104.
31. Maurer, S. A.; Brady, N. W.; Fajardo, N. P.; Radke, C. J.: Surface Kinetics for Cooperative Fungal Cellulase Digestion of Cellulose from Quartz Crystal Microgravimetry. J. Colloid Interface Sci. 2013, 394, 498-508.
32. Matano, Y.; Hasunuma, T.; Kondo, A.: Simultaneous Improvement of Saccharification and Ethanol Production from Crystalline Cellulose by Alleviation of Irreversible Adsorption of Cellulase with A Cell Surface-Engineered Yeast Strain.
Appl. Microbiol. Biotechnol. 2013, 97, 2231-2237.
33. Jagtar, S.: Production Of Carboxymethyl Cellulase by Bacillus Sphaericus JS1 Strain in Low Cost Agriculture Waste Medium. Res. J. Biotechnol. 2013, 8, 11-20.
34. Maeda, R. N.; Barcelos, C. A.; Anna, L.; Pereira, N.: Cellulase Production by Penicillium Funiculosum and Its Application in the Hydrolysis of Sugar Cane Bagasse for Second Generation Ethanol Production by Fed Batch Operation. J. Biotechnol.
2013, 163, 38-44.
35. Ding, Z. Y.; Cao, X. J.: Affinity Precipitation of Cellulase Using Ph-Response Polymer with Cibacron Blue F3GA. Sep. Purif. Technol. 2013, 102, 136-141.
36. Gaikwad, S. M.; Rao, M. B.; Deshpande, V. V.: D-glucose Xylose Isomerase from Streptomyces - Differential Roles of Magnesium and Cobalt Ions. Enzyme Microb.
Technol. 1992, 14, 317-320.
37. Tashpulatova, B. A.; Davranov, K. A.: Effect of Metal Ions on the Activity and Stability of Glucose Isomerase from Streptomyces Atratus. Khimiya Prirodnykh Soedinenii 1991, 838-842.
38. Bhosale, S. H.; Rao, M. B.; Deshpande, V. V.: Molecular and Industrial Aspects of Glucose Isomerase. Microbiol. Rev. 1996, 60, 280.
39. Smith, C. A.; Rangarajan, M.; Hartley, B. S.: D-xylose (D-glucose) Isomerase from Arthrobacter Strain NRRL B3728 - Purification and Properties. Biochem. J.
1991, 277, 255-261.
40. Whitlow, M.; Howard, A. J.; Finzel, B. C.; Poulos, T. L.; Winborne, E.; Gilliland, G. L.: A Metal-mediated Hydride Shift Mechanism for Xylose Isoemrase Based on the 1.6 A Streptomyces-rubginosus Structures with Xylitol and D-Xylose. Proteins 1991, 9, 153-173.
41. Zittan, L.; Poulsen, P. B.; Hemmingsen, S. H.: Sweetzyme-new Immobilized Glucose Isomerase. Starke 1975, 27, 236-241.
42. Pastinen, O.; Visuri, K.; Schoemaker, H. E.; Leisola, M.: Novel Reactions of Xylose Isomerase from Streptomyces Rubiginosus. Enzyme Microb. Technol. 1999, 25, 695-700.
43. Caratzoulas, S.; Vlachos, D. G.: Converting Fructose to 5-Hydroxymethylfurfural:
A Quantum Mechanics/Molecular Mechanics Study of the Mechanism and Energetics.
72
Carbohydr. Res. 2011, 346, 664-672.
44. Amarasekara, A. S.; Williams, L. D.; Ebede, C. C.: Mechanism of the Dehydration of D-fructose to 5-Hydroxymethylfurfural in Dimethyl Sulfoxide at 150 Degrees : An NMR Study. Carbohydr. Res. 2008, 343, 3021-3024.
45. Clark, J. H.; Macquarrie, D. J.; Tavener, S. J.: The Application of Modified Mesoporous Silicas in Liquid Phase Catalysis. Dalton Trans. 2006, 4297-4309.
46. Zhai, S.; Wei, L.; Yang, D.; Wu, D.; Sun, Y.: Preparation and Applications of Silica/Aluminum-Based Micro/Mesoporous Composite Molecular Sieves. Prog.
Chem. 2006, 18, 1330-1337.
47. Trewyn, B. G.; Slowing, II; Giri, S.; Chen, H. T.; Lin, V. S. Y.: Synthesis and Functionalization of A Mesoporous Silica Nanoparticle Based on the Sol-gel Process and Applications in Controlled Release. Accounts Chem. Res. 2007, 40, 846-853.
48. Pang, J.; Luan, Y.; Yang, X.; Jiang, Y.; Zhao, L.; Zong, Y.; Li, Z.: Functionalized Mesoporous Silica Particles for Application in Drug Delivery System. Mini-Rev. Med.
Chem. 2012, 12, 775-788.
49. Li, Z. X.; Barnes, J. C.; Bosoy, A.; Stoddart, J. F.; Zink, J. I.: Mesoporous Silica Nanoparticles in Biomedical Applications. Chem. Soc. Rev. 2012, 41, 2590-2605.
50. Li, H.; Zhang, Q. Y.; Liu, X. F.; Chang, F.; Hu, D. Y.; Zhang, Y. P.; Xue, W.; Yang, S.: InCl3-ionic Liquid Catalytic System for Efficient and Selective Conversion of Cellulose into 5-Hydroxymethylfurfural. RSC Adv. 2013, 3, 3648-3654.
51. Zukal, A.; Pastva, J.; Cejka, J.: MgO-modified Mesoporous Silicas Impregnated by Potassium Carbonate for Carbon Dioxide Adsorption. Microporous Mesoporous Mat. 2013, 167, 44-50.
52. Ispas, C.; Sokolov, I.; Andreescu, S.: Enzyme-functionalized Mesoporous Silica for Bioanalytical Applications. Anal. Bioanal. Chem. 2009, 393, 543-554.
53. Popat, A.; Hartono, S. B.; Stahr, F.; Liu, J.; Qiao, S. Z.; Lu, G. Q.: Mesoporous Silica Nanoparticles for Bioadsorption, Enzyme Immobilisation, and Delivery Carriers. Nanoscale 2011, 3, 2801-2818.
54. Takahashi, H.; Li, B.; Sasaki, T.; Miyazaki, C.; Kajino, T.; Inagaki, S.: Catalytic Activity in Organic Solvents and Stability of Immobilized Enzymes Depend on the Pore Size and Surface Characteristics of Mesoporous Silica. Chem. Mat. 2000, 12, 3301-3305.
55. Takahashi, H.; Li, B.; Sasaki, T.; Miyazaki, C.; Kajino, T.; Inagaki, S.:
Immobilized Enzymes in Ordered Mesoporous Silica Materials and Improvement of Their Stability and Catalytic Activity in An Organic Solvent. Microporous Mesoporous Mat. 2001, 44, 755-762.
56. Wang, Y. J.; Caruso, F.: Mesoporous Silica Spheres as Supports for Enzyme Immobilization and Encapsulation. Chem. Mat. 2005, 17, 953-961.
73
57. Chen, Y. P.; Chen, C. T.; Hung, Y.; Chou, C. M.; Liu, T. P.; Liang, M. R.; Chen, C.
T.; Mou, C. Y.: A New Strategy for Intracellular Delivery of Enzyme Using Mesoporous Silica Nanoparticles: Superoxide Dismutase. J. Am. Chem. Soc. 2013, 135, 1516-1523.
58. Hartono, S. B.; Qiao, S. Z.; Liu, J.; Jack, K.; Ladewig, B. P.; Hao, Z. P.; Lu, G. Q.
M.: Functionalized Mesoporous Silica with Very Large Pores for Cellulase Immobilization. J. Phys. Chem. C 2010, 114, 8353-8362.
59. Functionalized Mesoporous Silica Boosts Enzyme Activity. Chem. Eng. News 2002, 80, 35-35.
60. Kim, M. I.; Kim, J.; Lee, J.; Jia, H.; Bin Na, H.; Youn, J. K.; Kwak, J. H.;
Dohnalkova, A.; Grate, J. W.; Wang, P.; Hyeon, T.; Park, H. G.; Chang, H. N.:
Crosslinked Enzyme Aggregates in Hierarchically-Ordered Mesoporous Silica: A Simple and Effective Method for Enzyme Stabilization. Biotechnol. Bioeng. 2007, 96, 210-218.
61. Hasanzadeh, M.; Shadjou, N.; Eskandani, M.; de la Guardia, M.: Mesoporous Silica-Based Materials for Use in Electrochemical Enzyme Nanobiosensors.
Trac-Trends Anal. Chem. 2012, 40, 106-118.
62. Murai, K.; Kato, K.: Development of Cholesterol Biosensor with High Sensitivity Using Dual-Enzyme Immobilization into the Mesoporous Silica Materials.
Appl. Surf. Sci. 2011, 258, 1725-1732.
63. Frein, E. M.; Montenecourt, B. S.; Eveleigh, D. E.: Cellulase Production by Trichoderma-Reesei Immobilized on Kappa-carrageenan. Biotechnol. Lett. 1982, 4, 287-292.
64. Kashiwagi, Y.; Magae, Y.; Sasaki, T.: Preparation And Some Properties of Immobilized Cellulase on Cyanogen-Bromide Activated Sepharose. J. Jpn. Soc. Food Sci. Technol.-Nippon Shokuhin Kagaku Kogaku Kaishi 1984, 31, 86-91.
65. Kumakura, M.; Kaetsu, I.; Nisizawa, K.: Cellulase Production from Immobilized Growing Cell Composites Prepared by Radiation Polymerization. Biotechnol. Bioeng.
1984, 26, 17-21.
66. Takeuchi, T.; Makino, K.: Cellulase Immobilized on Poly-L-Glutamic Acid.
Biotechnol. Bioeng. 1987, 29, 160-164.
67. Jain, P.; Wilkins, E. S.: Cellulase Immobilized on Modified Nylon for Saccharification of Cellulose. Biotechnol. Bioeng. 1987, 30, 1057-1062.
68. Sheng, C.; Zhiyue, H.; Yanru, L.: Study on Chitosan-Immobilized Cellulase. Prog.
Biochem. Biophys. 1996, 23, 250-254.
69. Tebeka, I. R. M.; Petri, D. F. S.: CELL 255-Hydrolytic Activity of Immobilized Cellulase onto Silicon Wafers. Abstr. Pap. Am. Chem. Soc. 2008, 235.
70. Kelly, F. H. C.: Phase Equilibria in Sugar Solutions .4. Ternary System of
74
Water-glucose-fructose. Journal of Applied Chemistry 1954, 4, 409-411.
71. Strandbe.Gw; Smiley, K. L.: Free and Immobilized Glucose Isomerase from Streptomyces-phaeochromogenes. Applied Microbiology 1971, 21, 588-&.
72. Yokote, Y.; Kimura, K.; Samejima, H.: Production of High Fructose Syrup by Glucose Isomerase Immobilized on Phenol-Formaldehyde Resin. Starke 1975, 27, 302-306.
73. Weidenbach, G.; Bonse, D.; Richter, G.: Glucose-isomerase Immobilized on SiO2-carrier with High Productivity. Starke 1984, 36, 412-416.
74. Lee, Y. Y.; Fratzke, A. R.; Wun, K.; Tsao, G. T.: Glucose Isomerase Immobilized on Porous-Glass. Biotechnol. Bioeng. 1976, 18, 389-413.
75. Messing, R. A.; Filbert, A. M.: Immobilized Glucose Isomerase for Continuous Conversion of Glucose to Fructose. J. Agric. Food Chem. 1975, 23, 920-923.
76. Antrim, R. L.; Auterinen, A. L.: A New Regenerable Immobilized Glucose-isomerase. Starch-Starke 1986, 38, 132-137.
77. Chen, F. S.; Weng, H. S.; Lai, C. L.: The Performance of Immobilized Glucose-isomerase Supported by Shrimp Chitin in Various Types of Reactors.
Biotechnol. Bioeng. 1983, 25, 725-733.
78. Dehkordi, A. M.; Tehrany, M. S.; Safari, I.: Kinetics of Glucose Isomerization to Fructose by Immobilized Glucose Isomerase (Sweetzyme IT). Ind. Eng. Chem. Res.
2009, 48, 3271-3278.
79. Yu, D. H.; Wu, H.; Zhang, A. J.; Tian, L.; Liu, L. D.; Wang, C. M.; Fang, X. X.:
Microwave Irradiation-assisted Isomerization of Glucose to Fructose by Immobilized Glucose Isomerase. Process Biochem. 2011, 46, 599-603.
80. PonRani, V. M.; Rajendran, L.: Mathematical Modelling of Steady-State Concentration in Immobilized Glucose Isomerase of Packed-Bed Reactors. J. Math.
Chem. 2012, 50, 1333-1346.
81. Martinez, L.: Fibrous Cellulose Support Containing Adhered Yeast for Converting Sucrose to Glucose And Fructose. 2000.
82. Storey, K. B.; Chakrabarti, A. C.: One-Step Conversion of Cellulose to Fructose Using Coimmobilized Cellulase, Beta-Glucosidase, and Glucose-Isomerase. Appl.
Biochem. Biotechnol. 1990, 23, 139-154.
83. Li, C. Z.; Zhang, Z. H.; Zhao, Z. B. K.: Direct Conversion of Glucose and Cellulose to 5-Hydroxymethylfurfural in Ionic Liquid under Microwave Irradiation.
Tetrahedron Lett. 2009, 50, 5403-5405.
84. Daorattanachai, P.; Khemthong, P.; Viriya-empikul, N.; Laosiripojana, N.;
Faungnawakij, K.: Conversion of Fructose, Glucose, and Cellulose to 5-Hydroxymethylfurfural by Alkaline Earth Phosphate Catalysts in Hot Compressed Water. Carbohydr. Res. 2012, 363, 58-61.