اندازهگيریحالليت-2اتيل-1-هگزانول-2،اتيلهگزانوئيکاسيدو -2اتيلهگزيل -2-اتيلهگزانواتو بررسیواکنشهایاستریواتری شدنوابزداي يدردیاکسيدکربنفوقبحرانی و بررسیسينتيکواکنشانيدريداستيکباايزواميلالکلدر حاللالی 1 فهرستمطالب: مقدمه: )1تعريففوقبحرانی )2کاربردهایسيالفوقبحرانی بخشاول: (1اندارهگيریحالليت-2اتيل-1-هگزانولو-2اتيلهگزانوئيکاسيددرسامانههایدووسهتاي ی (2مطالعهتاثيرپيوندهيدروژنیبرحالليت (3بررسیحالليت -2اتيلهگزيل -2-اتيلهگزانوات درسامانههایدووچهارتاي ي بخشدوم: واكنشهاياستریواتریشدنوابزداي یدردياكسيدكربنفوقبحراني بخشسوم: مطالعهسينتيکیواكنشاستریشدنانيدريداستيکباايزواميلالکلدرحضورانزيم 2 P-T phase diagram for CO2 3 4 A typical SCF system 5 Deware sample collection 6 Effect of different parameters on solubility • • • • • • • Pressure Temperature Vapor pressure Intermolecular interaction Molecular structure Matrix effect Solvent 7 Reactions in SC-CO2 • Esterification • Etherification • Dehydration 8 Why esterification is important? Pharmaceutical •Esterification Food additives Cosmetics High-pressure lubricants Advantages of SC-CO2 as solvent for esterification •Reaction rate enhancement •Selective esterification 9 Esterification reaction in SC-CO2 T (oC) P (bar) 1-(p-chlorophenyl)-2,2,2Lipase trifluoroethanol with Vinyl acetate 31-60 91-145 Oleic acid with Oleyl alcohol Lipase 40 150 Oleic acid with Citronellol Lipase 30-41 76-193 Oleic acid with Methanol PTSA 40 165 Phthalic anhydride with Methanol No catalyst 50 97-165 Myristic acid with Ethanol Lipase 35-70 75 Butyric acid with Isoamyl alcohol Lipase 40 100 Fatty acid and Butanol Lipase 36 122 Anhydride acetic with Isoamyl alcohol Lipase 40 80-300 Decanoic acid with Methanol No catalyst 40 340 Reaction Catalyst 10 Section (I): Solubility Measurement in SC-CO2 11 Continuous flow apparatus for solubility measurement 12 Solubility of 2-ethyl-1-hexanol and 2-ethylhexanoic acid in SC-CO2 13 Literature values for the solubility of 1-hexanol in SC-CO2 at 311 K: Gregorowicz et.al. [28] and this work 102S Pressure (bar) This work Ref. [28] 66 0.1 0.08 74 0.15 0.13 78 0.22 0.23 14 The solubility of alcohol and acid versus expanded gas flow rate at 99 bar and 313 K 5.0 4.5 4.0 3.5 102S 3.0 2.5 2.0 1.5 1.0 Alcohol Acid 0.5 0.0 60 160 260 360 460 Flow rate (mL/min) 560 660 760 15 Solubility of alcohol and acid in SC-CO2 7.50 6.50 5.50 10 2 S 4.50 3.50 Alcohol 40 oC 2.50 Acid 40 oC 1.50 Alcohol 50 oC 0.50 Acid 50 oC -0.50 60 80 100 120 140 Pressure (bar) 160 180 200 16 Chrastil model evaluation for alcohol: (▲) 313 K; (■) 323 K 8.00 6.00 ln(c) 4.00 2.00 0.00 -2.00 5.0 5.5 6.0 6.5 ln(d) 7.0 7.5 17 Chrastil model evaluation for acid: (▲) 313 K; (■) 323 K 8.00 6.00 ln(c) 4.00 2.00 0.00 -2.00 5.0 5.5 6.0 ln(d) 6.5 7.0 18 Chrastil Parameters for alcohol and acid in SC-CO2 ln c k ln d a / T b Compound k a b R2 Alcohol 4.3 -12246.5 21.8 0.9899 Acid 3.9 -11535.7 15.3 0.9812 19 Role of Hydrogen Bonding on Solubility Diminution of Carboxylic Acids and Alcohols in SC-CO2 20 Binary and ternary solubility of alcohol at 313 K 5.00 102S 4.00 3.00 2.00 Binary Ternary 1.00 0.00 100 110 120 130 140 150 Pressure (bar) 160 170 180 190 21 Binary and ternary solubility of acid at 313 K 5.50 5.00 4.50 102S 4.00 Binary Ternary 3.50 3.00 2.50 2.00 1.50 100 110 120 130 140 150 Pressure (bar) 160 170 180 190 22 Solubility of alcohol and acid in SC-CO2 (ternary system) 3.50 Alcohol Acid 102S 3.00 2.50 2.00 1.50 100 120 140 160 Pressure (bar) 180 200 23 Selectivity of alcohol relative to acid in SC-CO2 2.00 Selectivity 1.50 1.00 0.50 0.00 90 110 130 150 Pressure (bar) 170 190 24 Selectivity of alcohol relative to acid in SC-CO2 1.40 1.20 Selectivity 1.00 0.80 0.60 0.40 0.20 0.00 0 5 10 15 20 25 Time (min) 30 35 40 45 50 25 FT-IR spectrum of alcohol, acid and their mixture 3700 3410 3120 2830 2540 2250 1960 1670 1380 1090 800 Absorbance, a.u. 2.7 2.3 2EHA 1.9 2E1H 1.5 2E1H + 2EHA 1.1 0.7 0.3 -0.1 Wavenumber, cm-1 26 3700 3600 3500 3400 3300 3200 3100 0.3 Absorbance, a.u. 2E1H 0.2 2E1H + 2EHA 0.1 0 -0.1 Wavenumber, cm-1 27 IR spectra of ethanol: 1) in hexane; 2) at 298 K 28 TFA spectra at 25 oC and 82.7 bar in CO2 29 Solubility of 2-ethyl-hexyl-2-ethyl hexanoate in binary and quaternary systems in SC-CO2 O O H3C C2H5 CH3 C2H5 30 Effect of flow rate on solubility of ester in SC-CO2 at pressure of 170 bar and temperature of 313 K 1.80 1.60 1.40 102S 1.20 1.00 0.80 0.60 0.40 100 150 200 Flow Rate (mL/min) 250 300 31 Solubility of ester in SC-CO2 at temperature of 313 K and flow rate of 250 ml/min 2.30 2.10 1.90 1.70 102S 1.50 1.30 1.10 0.90 0.70 0.50 0.30 100 150 200 Pressure (bar) 250 300 32 The solubility of ester in SC-CO2 at pressure of 170 bar and flow rate of 250 ml/min 1.80 1.60 102S 1.40 1.20 1.00 0.80 0.60 310 320 330 340 Temperature (K) 350 360 33 The solubility of alcohol, acid, and ester in SC-CO2 at temperature of 313 K and flow rate of 250 ml/min 1.20 Alcohol Acid Ester 1.00 2 10 S 0.80 0.60 0.40 0.20 0.00 80 130 180 Pressure (bar) 230 34 280 Assume mechanism for solubility diminution of ester O O H3C CH3 C2H5 C2H5 ...... H O H3C O C2H5 .O . . H CH3 C2H5 35 Solubility diminution of ester T (oC) P (bar) SD (%) 140 150 313 170 75 201 253 313 333 353 72 170 78 75 36 The solubility of alcohol, acid, and ester in SC-CO2 at pressure of 170 bar and flow rate of 250 ml/min 0.80 Alcohol Acid Ester 2 10 S 0.60 0.40 0.20 0.00 310 320 330 340 Temperature (K) 350 37 360 Section (II): Continuous esterification and dehydration reactions in SC-CO2 SC-CO2 H3C (CH2)3 CH CH2OH + H3C (CH2)3 CH COOH Cat. C2H5 C2H5 C2H5 H3C (CH2)3 CH O C CH H2 C O (CH2)3 CH3 + Water C2H5 38 Apparatus 39 Modified sample collection 40 Purge test for alcohol, acid, and ester Recovery (%) Purge Test Ester Alcohol Acid Glass beads 71.37 66.48 72.10 n-hexane 93.56 89.38 94.51 Modified 95.69 94.61 96.80 41 The effect of temperature on the continuous formation of ester in SC-CO2 Yield (%) T (oC) Ester Ether Alkene 75 15.2 ND 84.8 110 27.4 1.6 71.05 140 0.2 0.9 98.8 42 The effect of temperature on the continuous formation of ester in SC-CO2 Yield (%) T (oC) Ester Ether Alkene 140 0.2 0.9 98.8 110 7.1 1.5 91.5 43 The effect of pressure on the continuous formation of ester in SC-CO2 Yield (%) P (bar) Ester Ether Alkene 150 22.2 2.1 75.4 200 21.0 2.0 77.0 250 27.4 2.9 69.7 44 The effect of mole ratio on the continuous formation of ester in SC-CO2 Yield (%) r Ester Ether Alkene 0.5 24.6 3.4 72.0 1.0 22.5 2.1 75.4 2.0 31.9 11.6 56.6 45 The effect of flow rate on the continuous formation of ester in SC-CO2 Yield (%) F (mL.min-1) Ester Ether Alkene 0.4 15.2 N.D. 84.8 0.6 12.2 N.D. 87.8 0.8 16.2 N.D. 84.0 46 Usability of Amberlyt 15 on the continuous formation of ester in SC-CO2 Yield (%) Amberlyst 15 Ester Ether Alkene No used 22.2 2.1 75.4 Used 17.8 4.6 77.6 47 The effect of different parameters on the continuous formation of ester in SC-CO2 Parameter YieldAlkene (%) 75 84.8 T (oC) 110 71.05 140 98.8 150 75.4 P (bar) 200 77.0 250 69.7 0.5 72.0 r 1.0 75.4 2.0 65.6 0.4 84.8 F (mL.min-1) 0.6 87.8 0.8 84.0 48 1) Synthesis of dimethyl phthalate COOCH3 COOH + COOH 2 CH3OH + 2 H2 O COOCH3 49 2) The continuous formation of ester in SC-CO2 Yield (%) Catalytst ZrO2 Ester Ether Alkene 40.4 N.D. N.D. 50 Durability of ZrO2 Number of repeat Alcohol conversion (%) 1 34.4 2 8.9 3 6.8 51 Assumed mechanism for esterification RCOOH k1 Cat RCOO RCOO Cat k _1 Cat (Inhibition) k _3 k _2 k4 k3 k2 RCOO R'OH RCOOR' Cat RCOO OR' 52 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-CO2 with amberlyst 15 is very high. 53 Lipase-catalyzed esterification of acetic anhydride with isoamyl alcohol in n-hexane: a kinetic study H H3C C CH2CH2 OH CH3 + O O CH3 O n-Hexane HC Novozyme 3 CH3 CH3 O (CH2)2 C CH3 H O OH + H3C O 54 Mechanism enzyme reaction E+A EA FP F +P Ping-Pong B FB E + H2N-CHR-COOH E-NH2 + O=CR'-COOH EQ E E-NH2 E +Q + O=CR-COOH + H2N-CHR'-COOH 55 Experimental Typical capillary GC separation 56 Calibration curve for isoamyl acetate and isoamyl alcohol 12.0 10.0 yAlcohol = 1.9067x + 0.2 Conc. (M)/Conc.(M) Decane R2 = 0.9987 8.0 6.0 yAnhydride = 1.6193x + 0.1603 R2 = 0.9994 4.0 Alcohol 2.0 Acetate 0.0 0.0 1.0 2.0 3.0 4.0 Area/Area decane 5.0 6.0 7.0 57 Effect of speed of agitation on esterification yield 100 Yield (%) 80 100 RPM 200 RPM 300 RPM 60 40 20 0 0 10 20 30 Time (min) 40 50 60 58 Effect of substrate concentration on initial reaction 10.0 9.0 8.0 R (mmol.min-1.g-1) 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0 0 0.1 0.2 0.3 0.4 C (M) 0.5 0.6 0.7 59 Time course of isoamyl acetate concentration and conversion of isoamyl alcohol 0.35 0.30 Concentration (M) 0.25 0.20 Ester Alcohol 0.15 0.10 0.05 0.00 0 20 40 60 Time (min) 80 100 120 60 Effect of acetic anhydride concentration on initial reaction rate 0,4M Al 0,3M Al 0,2M Al 0,1M Al 0,075M Al 0,05M Al 12.0 R(mmol.min-1.g-1) 10.0 8.0 6.0 4.0 2.0 0.0 0.0 0.1 0.2 0.3 C (M) 0.4 0.5 0.6 61 Reciprocal initial reaction rate versus reciprocal acetic anhydride concentration 0.6 1/R (mmol.min-1.g-1) 0.5 0.4 0.3 0.2 0.05M Alc. 0.075M Alc. 0,1M Alc. 0,2M Alc. 0.1 0.0 0.0 5.0 10.0 15.0 1/C (M) 20.0 25.0 62 Effect of acetic acid concentration on isoamyl acetate yield 100.0 Yield(%) 80.0 60.0 0.0M Ac 0.1M Ac 0.3M Ac 40.0 20.0 0.0 0 20 40 60 Time (min) 80 100 120 63 Kinetic parameters for esterification reaction Rmax [ Al ][ An] R [ Al ][ An] K mAl [ An](1 [ An] / K iAn ) K mAn [ Al ] Parameter Value Dimension Rmax 52.9 Mmol.min-1.g-1 KmAl 0.825 Mmol.mL-1 0.361 Mmol.mL-1 0.592 Mmol.mL-1 KmAn KiAn 64 0,4M Al 0,3M Al 0,2M Al 0,1M Al 0,075M Al 0,05M Al 12.0 R(mmol.min-1.g-1) 10.0 8.0 6.0 4.0 2.0 0.0 0.0 0.1 0.2 0.3 C (M) 0.4 0.5 0.6 65 Conclusion The Isoamyl acetate synthesis with enzyme is very selective (100% selectivity). The reaction mechanism is Ping-Pong with anhydrid acetic as an inhibitor. 66 ازحضورشمادراينسمينارسپاسگزارم 67 پايان 68 Solubility of Naphthalene in SC-CO2 69 Solubility of MHET in various solvents at 130 oC COOCH2CH2OH COOH 70 Reaction rate enhancement O O O O C OMe C OH + MeOH O 71 Esterification: Selective ethoxylation of terephthalic acid CO2H COOCH2CH2OH + CO2H Terphtalic acid O CO2CH2CH2OH Catal. SCF CO2H SCF CO2CH2CH2OH MHTE 72 The effect of temperature on reaction rate T (oC) Reaction rate (mmol.min-1) 50 39.7 90 67.8 110 141.2 130 176.9 Ea= 227 Kcal.mol-1 73 Memory effect of enzyme in organic solvents 74 Hydrogenation: The dependence of the product distribution on the teperature of reactor wall 75 -2(-iD gniniatnoc )IIPA naxoleD( 2exyl( phosphoric acid h-lyhte EHPA( as ion exchanger2)D Deloxan ®, a polysiloxane material 76 Selectivity = SAcid/SAlcohol SDi = (Sb-Sq)×100/Sb AARD (1 / N )1 N Scalc Sexp Sexp 77 Schematic representation of an inferred enzyme-substrate complex (A: CO2 molecules) 78 Quadrupole-Quadrupole CO2/C10H8 interaction O C O 79 Schematic representation of relative solvent reorganization require for photodimerization leading to the syn versus anti configuration 80 ازحضورشمادراينسمينارسپاسگزارم 81 ازحضورشمادراينسمينارسپاسگزارم 82