1 اندازه ‌ گيری حلاليت 2 - اتيل هگزانول، 2 - اتيل هگزانوئيک اسيد و 2 - اتيل هگزيل اتيل هگزانوآت و بررسی واکنشهای ‌ استری و اتری شدن و آب ‌ زدايي در دی ‌ اکسيدکربن فوق بحرانی 2 - اتيل هگزيل اتيل هگزانوآت و بررسی واکنشهای ‌ استری و اتری شدن و آب ‌ زدايي در دی ‌ اکسيدکربن فوق بحرانیو بررسی سينتيک واکنش انيدريد استيک با ايزوآميل الکل در حلال آلی

2 فهرست مطالب :   مقدمه : 1 ) تعريف فوق بحرانی 2 ) کاربردهای سيال فوق بحرانی   بخش اول : 1) 1) انداره گيری حلاليت 2 - اتيل هگزانول و 2 - اتيل هگزانوئيک اسيد در سامانه های دو و سه تايی 2) 2) مطالعه تاثير پيوند هيدروژنی بر حلاليت 3) 3) بررسی حلاليت 2 - اتيل هگزيل اتيل هگزانوآت درسامانه های دو و چهارتايي   بخش دوم : واكنشهاي استری و اتری شدن و آب ‌ زدايی در دي ‌ اكسيدكربن فوق بحراني   بخش سوم : مطالعه سينتيکی واكنش استری شدن انيدريد استيک با ايزوآميل الکل در حضور آنزيم

3 P-T phase diagram for CO 2

4

5 A typical SCF system

6 Deware sample collection

7 Pressure Temperature Vapor pressure Intermolecular interaction Molecular structure Matrix effect Solvent Effect of different parameters on solubility

8 Esterification Etherification Dehydration Reactions in SC-CO 2

9 Why esterification is important? Esterification Pharmaceutical Food additives Cosmetics High-pressure lubricants Advantages of SC-CO 2 as solvent for esterification Reaction rate enhancement Selective esterification

10 P (bar)T ( o C)CatalystReaction Lipase1-(p-chlorophenyl)-2,2,2- trifluoroethanol with Vinyl acetate 15040LipaseOleic acid with Oleyl alcohol LipaseOleic acid with Citronellol 16540PTSAOleic acid with Methanol No catalystPhthalic anhydride with Methanol LipaseMyristic acid with Ethanol 10040LipaseButyric acid with Isoamyl alcohol 12236LipaseFatty acid and Butanol LipaseAnhydride acetic with Isoamyl alcohol 34040No catalystDecanoic acid with Methanol Esterification reaction in SC-CO 2

11 Section (I): Solubility Measurement in SC-CO 2

12 Continuous flow apparatus for solubility measurement

13 Solubility of 2-ethyl-1-hexanol and 2-ethylhexanoic acid in SC-CO 2

S Pressure (bar) Ref. [28]This work Literature values for the solubility of 1-hexanol in SC-CO 2 at 311 K: Gregorowicz et.al. [28] and this work

15 The solubility of alcohol and acid versus expanded gas flow rate at 99 bar and 313 K

16 Solubility of alcohol and acid in SC-CO 2

17 Chrastil model evaluation for alcohol: (▲) 313 K; (■) 323 K

18 Chrastil model evaluation for acid: (▲) 313 K; (■) 323 K

19 R2R2 bakCompound Alcohol Acid Chrastil Parameters for alcohol and acid in SC-CO 2

20 Role of Hydrogen Bonding on Solubility Diminution of Carboxylic Acids and Alcohols in SC-CO 2

21 Binary and ternary solubility of alcohol at 313 K

22 Binary and ternary solubility of acid at 313 K

23 Solubility of alcohol and acid in SC-CO 2 (ternary system)

24 Selectivity of alcohol relative to acid in SC-CO 2

25 Selectivity of alcohol relative to acid in SC-CO 2

26 FT-IR spectrum of alcohol, acid and their mixture

27

28 IR spectra of ethanol: 1) in hexane; 2) at 298 K IR spectra of ethanol: 1) in hexane; 2) at 298 K

29 TFA spectra at 25 o C and 82.7 bar in CO 2

30 Solubility of 2-ethyl-hexyl-2-ethyl hexanoate in binary and quaternary systems in SC-CO 2

31 Effect of flow rate on solubility of ester in SC-CO 2 at pressure of 170 bar and temperature of 313 K

32 Solubility of ester in SC-CO 2 at temperature of 313 K and flow rate of 250 ml/min

33 The solubility of ester in SC-CO 2 at pressure of 170 bar and flow rate of 250 ml/min

34 The solubility of alcohol, acid, and ester in SC-CO 2 at temperature of 313 K and flow rate of 250 ml/min

35 Assume mechanism for solubility diminution of ester

36 SD (%)P (bar)T ( o C) Solubility diminution of ester

37 The solubility of alcohol, acid, and ester in SC-CO 2 at pressure of 170 bar and flow rate of 250 ml/min

38 Section (II): Continuous esterification and dehydration reactions in SC-CO 2

39 Apparatus

40 Modified sample collection

41 Recovery (%) Purge Test AcidAlcoholEster Glass beads n-hexane Modified Purge test for alcohol, acid, and ester

42 Yield (%) T ( o C) AlkeneEtherEster 84.8ND The effect of temperature on the continuous formation of ester in SC-CO 2

43 Yield (%) T ( o C) AlkeneEtherEster The effect of temperature on the continuous formation of ester in SC-CO 2

44 Yield (%) P (bar) AlkeneEtherEster The effect of pressure on the continuous formation of ester in SC-CO 2

45 Yield (%) r AlkeneEtherEster The effect of mole ratio on the continuous formation of ester in SC-CO 2

46 Yield (%) F (mL.min -1 ) AlkeneEtherEster 84.8N.D N.D N.D The effect of flow rate on the continuous formation of ester in SC-CO 2

47 Yield (%) Amberlyst 15 AlkeneEtherEster No used Used Usability of Amberlyt 15 on the continuous formation of ester in SC-CO 2

48 Yield Alkene (%)Parameter T ( o C) P (bar) r F (mL.min -1 ) The effect of different parameters on the continuous formation of ester in SC-CO 2

49 1) Synthesis of dimethyl phthalate

50 Yield (%) Catalytst AlkeneEtherEster N.D. 40.4ZrO 2 2) The continuous formation of ester in SC-CO 2

51 Alcohol conversion (%)Number of repeat Durability of ZrO 2

52 Assumed mechanism for esterification

53 Conclusion In bibnary system solubility of alcohol is greater than acid but in ternary one there is similar solubility. This may be due to hydrogen bonding. Binary solubility of ester is more than quaternary solubility. The yield of alkene in SC-CO 2 with amberlyst 15 is very high.

54 Lipase-catalyzed esterification of acetic anhydride with isoamyl alcohol in n-hexane: a kinetic study

55 Ping-Pong Mechanism enzyme reaction

56 Typical capillary GC separation Experimental

57 Calibration curve for isoamyl acetate and isoamyl alcohol

58 Effect of speed of agitation on esterification yield

59 Effect of substrate concentration on initial reaction

60 Time course of isoamyl acetate concentration and conversion of isoamyl alcohol

61 Effect of acetic anhydride concentration on initial reaction rate

62 Reciprocal initial reaction rate versus reciprocal acetic anhydride concentration

63 Effect of acetic acid concentration on isoamyl acetate yield

64DimensionValueParameter Mmol.min -1.g R R max Mmol.mL K K mAl Mmol.mL K K mAn Mmol.mL K iAn Kinetic parameters for esterification reaction

65

66 Conclusion The Isoamyl acetate synthesis with enzyme is very selective (100% selectivity). The reaction mechanism is Ping-Pong with anhydrid acetic as an inhibitor.

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68 پايان

69 Solubility of Naphthalene in SC-CO 2

70 Solubility of MHET in various solvents at 130 o C

71 Reaction rate enhancement

72 Esterification: Selective ethoxylation of terephthalic acid

73 Reaction rate (mmol.min -1 )T ( o C) The effect of temperature on reaction rate E a = 227 Kcal.mol -1

74 Memory effect of enzyme in organic solvents

75 Hydrogenation: The dependence of the product distribution on the teperature of reactor wall

76 (Deloxan APII) containing Di-(2- ethyl-h2exyl) phosphoric acid (D2EHPA) as ion exchanger a polysiloxane material, ® Deloxan

77 SD i = (S b -S q )×100/S b Selectivity = S Acid /S Alcohol

78 Schematic representation of an inferred enzyme-substrate complex (A: CO 2 molecules)

79 Quadrupole-Quadrupole CO 2 /C 10 H 8 interaction

80 Schematic representation of relative solvent reorganization require for photodimerization leading to the syn versus anti configuration

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