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Application of Acidic Ionic Liquid on the Catalyic Green Process 酸性離子液體在綠色催化製程之應用 吳榮宗

Application of Acidic Ionic Liquid on the Catalyic Green Process 酸性離子液體在綠色催化製程之應用 吳榮宗 ( 台灣中油公司綠能科技研究所 ) [ 雲林科技大學 ] 2011.11.17. Contents I. What is ionic liquid(IL)? II. Properties of ionic liquids III. Application of acidic IL Lewis acid IL

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Application of Acidic Ionic Liquid on the Catalyic Green Process 酸性離子液體在綠色催化製程之應用 吳榮宗

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  1. Application of Acidic Ionic Liquid on the Catalyic Green Process 酸性離子液體在綠色催化製程之應用 吳榮宗 (台灣中油公司綠能科技研究所) [雲林科技大學] 2011.11.17

  2. Contents I. What is ionic liquid(IL)? II. Properties of ionic liquids III. Application of acidic IL Lewis acid IL Bronsted acid IL IV. Conclusion

  3. 工業上常用之酸性觸媒 1.傳統酸觸媒: H2SO4 ,AlCl3 , HF CF3SO3H, PTSA 2.固態酸觸媒: Zeolite, H3PO4/SiO2 SO42-/ZrO2, SbF5/TiO2 3.高分子酸觸媒: Amberlyst, Nafion 4.異多體酸觸媒: H3PW12O40(TPA), TPA/S 5.離子液體酸觸媒: Lewis /Bronsted Acid IL

  4. Application Method of Conventional Strong Acid Catalyst (A) Lewis Acid Ionic Liquid (Water-sensitive, Biphasic System) (B) Bronsted Acid Ionic Liquid (Water-tolerable, Biphasic System) (C) Bronsted Acid Ionic Liquid/ Solid (Water-tolerable, Biphasic System) [PHC] [PPS] [PPS]

  5. What is ionic liquid (IL)? • ILs are salts composed entirely of ions, typically large organic cations and small anions, they are liquids at low temperature(<100℃). • ILs have been known since 1914, but have only been investigated as acid and transition metal catalysis for 20 years(chloroaluminate IL). • IL catalysis can be carried out in biphasic system with easy recovery of homogeneous catalyst and product separation. • ILs have no detectable vapor pressure and do not emit VOC, providing a basis for clean manufacturing---”Green Chemistry”.

  6. COLORFUL FUTURE Ionic liquids have a promising future in chemicals synthesis.

  7. R2 R2 + R1 R3 N N N N R2 R1 R4 R1 R1 R1 P+ R2 R2 S+ R3 R3 R4 R4 Typical Structure of Low Temperature IL Cations: Anions:BF4-,PF6-,SbF6-,NO3-,CF3SO3-,(CF3SO3)2N-, ArSO3-,CF3CO2-,CH3CO2-,Al2Cl7-,HSO4-

  8. Properties of Ionic Liquids • Low Vapor Pressure • Thermal Stability (up to 300~400℃) • Immiscible with Some Organic Solvents • Polarity and Hydrophilicity/Lipophilicity (Adjustable) • Superacidity of Chloroaluminate (H0= -18) (Adjustable)

  9. Characteristics of Ionic Liquids • (A)Melting Points • Melting Points with Different Cations

  10. Melting Points with Different Anions

  11. Asymmetry explains the low melting point

  12. (B) Solubility

  13. (C) Thermal Stability

  14. N N N N N N R R R R R R 2 2 2 1 1 1 (D)Acidity and Coordination Ability basic/strongly neutral/weakly acid/non- coordinating coordinating coordinating Cl- AlCl4- Al2Cl7- Ac- CuCl2- Al3Cl10- NO3- SbF6- SO42- BF4- Cu2Cl3- PF6- Cu3Cl4- AlCl3 AlCl3 Cl - AlCl4- Al2Cl7- basic/strongly neutral/weakly acid/non- coordinating coordinating coordinating

  15. Acid Strength of IL

  16. CH3CN與CH3CN-IL 之 FT-IR光譜 L acid B acid

  17. 離子液體PC1之pyridine FT-IR吸收光譜(X=0.50, 0.65)

  18. Synthesis of Ionic Liquid NR3 Step I + R’X [R’R3N]+X- • Step IIb • +Metal salt M+A- • -MX(precipitation) • +Bronsted acid H+A- • -HX(evaporation) • Ion exchange resin Step IIa +Lewis acid MXy [R’R3N]+[MXy+1]- [R’R3N]+[A]-

  19. Application of Ionic Liquids

  20. Catalytic Research on Ionic Liquids • Ionic Liquid Acid Catalysis(B & L acid) • Isomerization(Cycloalkane/n-Alkane) • Alkylation(Aromatic/Isobutane with C4 Olefin) • Polymerization(C4 Olefin) • Esterification(FAME)/ Transesterification • Ionic Liquid Organometallic Catalysis • Dimerization(C4 Olefin)/Oligomerization • Hydrogenation/Oxidation/Hydroformylation • Heck/Suzuki/Acylation/Esterification • Ionic Liquid Nanometal Catalysis • Selective Hydrogenation • PDMA/ Butadiene/ Isoprene/Cyclopentadiene

  21. Acidic Ionic Liquid Catalysis

  22. Acidic Ionic Liquid Catalysis(A)Lewis Acid Ionic Liquid • Polymerization of Butene • Alkylation of Olefin(C4 Olefin/i-C4) • Alkylation of Aromatics(Olefin/Aromatic) • Isomerization of Cycloalkane(JP-10 & Adamantane) (B)Bronsted Acid Ionic Liquid • Esterification of Bio-diesel Synthesis • Esterification of Polyol(Glycol & Glycerol)

  23. (A)Lewis Acid Ionic Liquid Polymerization of Butene Adavantage of acidic ionic liquid process: (i) Ease of separation of the product polymer from the catalytic component, further undesirable reaction could be avoided. (ii) The product formed need not to be water-washed, because of low level of the catalytic IL in the product. (iii) The catalyst can be recycled and thereby reduces operation cost. (iv) The higher molecular weight of polymer could be obtained with high yield, even at higher temperature.

  24. (A)Lewis Acid Ionic Liquid Alkylation of Olefin(i-C4/C4=) C4= + i-C4 i-C8(Alkylate fuel ) Conventional process: HF :(UOP &Phillips) /Toxic H2SO4:(Stratco &Kellogg) /Corrosion & waste acid treatment Acidic Ionic Liquid process( Biphasic process): [BMIM]Cl-AlCl3 (Chauvin , 1994)

  25. Alkylation of C4 Olefin with i-C4 Ionikylation Process BMIC/AlCl3 /CuCl

  26. (A)Lewis Acid Ionic Liquid Alkylation of Aromatics C6H6 + C2H4=  C6H5-C2H5  C6H5-C2H4( Styrene ) (AlCl3 or ZSM-5) C6H6 + C3H6=  C6H5-iC3H7  C6H5-OH ( Phenol ) (AlCl3 or ZSM-5) C6H6 + C12H24=  C6H5-C12H25 ( LAB )  ( Detergent ) [BMIM]Cl-AlCl3

  27. (A)Lewis Acid Ionic Liquid Isomerization of Cycloalkane Synthesis of JP-10 Synthesis of Adamantane Supported Ionic Liquid Pseudo-fixed-bed Ionic Liquid

  28. Isomerization of Cycloalkane ( Synthesis of JP-10 ) THDCPD：Tetrahydrodicyclopentadiene

  29. Representative Properties of Jet & Missile Fuels

  30. JP-10傳統合成方法 1.硫酸法(H2SO4) 缺點：伴隨開環、裂解及聚合反應，反應後生成很多黑色焦狀物。 2.氯化鋁(AlCl3) 缺點：反應後，經過鹼洗、水洗，氯化鋁變成不溶於水的氫氧化鋁，會產生大量油泥狀廢棄物，且觸媒無法重複使用。 3. Zeolites and Heteropoly Acids 缺點：操作溫度高(185-195℃)，易產生副產品。

  31. Experimental

  32. Synthesis of JP-10 不同離子液體JP-10合成反應活性比較 X=0.6 , IL/endo-THDCPD=1/12.8(mole ratio) , 50 C

  33. 離子液體中AlCl3莫耳分率對JP-10合成反應 活性影響 [IMC-1]AlCl3 , IL/feed=1/12.8 , 50 C

  34. Anionic Species in Chloroaluminate IL with Different AlCl3 Mole Fraction

  35. 不同AlCl3莫耳比值之CH3CN FT-IR光譜(PC-1)

  36. 觸媒再使用活性測定比較(JP-10合成) [IMC-1]AlCl3 , X=0.6 , IL/feed=1/12.8 , 50 C

  37. Synthesis of Adamantane

  38. 金剛烷(Adamantane) 三環癸烷(C10H16), 環狀四面體, 熔點2680C, 密度1.07. 無色, 無毒, 無味晶體, 具潤滑性且易昇華. 用於醫藥,功能性高分子, 潤滑劑, 界面活性劑, 感光材料, 光纖維材料, 電子材料, 農藥攜帶劑等. 被譽為新一代精細化工原料, 未來可與苯化學相媲美.

  39. 不同離子液體金剛烷合成反應活性比較 X=0.65 , IL/exo-THDCPD=1/1.28 , 70 C

  40. PHC/AlCl3中AlCl3莫耳分率對金剛烷合成反應活性影響PHC/AlCl3中AlCl3莫耳分率對金剛烷合成反應活性影響 [PHC]AlCl3 , IL/feed=1/1.28 , 70 C

  41. JP-10及Adamantane合成結論(I) 1.酸性氯化鋁酸鹽離子液體, 可有效應用於endo-THDCPD 異構成exo-THDCPD(JP-10),並進一步異構化成金剛烷(adamantane). 2.IL中之AlCl3莫耳分率X值, 以0.60~0.65(JP-10)及0.65~0.70 (adamantane)為宜, 反應溫度以 50~60C(JP-10)及60~75C (adamantane)為宜. 3.IL中X值愈高,反應活性愈高,但太高則易產生副產物, 且易 於反應 時生成黃色沉澱物.

  42. JP-10及Adamantane合成結論(II) 4.金剛烷合成反應轉化率不宜太高,否則會產生adamantane 沉澱, 造成連續操作上之困擾. 5.反應活性衰退 , 可能是進料中水含量及反應中產生之烯烴所造成. 6.金剛烷合成反應係先生成一中間產物, 此中間產物可生成金剛烷, 或經氫轉移反應生成decalin(C10H18), 比例約78/22~68/32, 溫度愈高比值愈低, 另外於反應液中加入decalin可降低其生成選擇性.

  43. Adamantane JP-10 [ US Pat 7488859 (2009) ] [ CNS Pat I 321128 (2010) ] [Catal. Communi., 10(13), 1747(2009) ] [ US Pat 7488860 (2009) ] [ CNS Pat I 314141 (2009) ] [ Fuel, (2011), in press]

  44. (A)Lewis Acid Ionic Liquid 擬固定床式離子液體反應器在JP-10合成反應之應用(Pseudo fixed-bed IL reactor)

  45. Feed 擬固定床式離子液體反應設備 Products Feed pump Feed Temp. controller (B)反應管裝填玻璃珠底部示意圖 (A)未裝填玻璃珠示意圖

  46. (A)Lewis Acid Ionic Liquid 負載型酸性離子液體 Supported Acidic Ionic Liquid

  47. Structure of Supported IL (Impregnation & Grafting)

  48. Supported ionic liquids 製備 製備方法 • 擔體 ＋ ionic liquid • 擔體 ＋ ionic liquid(in CH2Cl2), 抽乾CH2Cl2 • 擔體前處理 ＋ ionic liquid(in CH2Cl2), 抽乾CH2Cl2 • AlCl3 (in CH2Cl2), washed by CH2Cl2 • AlCl3＋ PHC(in CH2Cl2), wash by CH2Cl2 • Me3SiCl(in cyclohexae), reflux and washed by CH2Cl2

  49. Support : silica gel(80-120 mesh)Ionic Liquid : PHC/AlCl3(X=0.65) 圖一 擔體(SiO2)不同用量之異構化活性比較

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