1 Extraction of Maleic Acid and Phthalic Acid

1 Extraction of Maleic Acid and Phthalic Acid

1 Extraction of Maleic Acid and Phthalic Acid by scCO2 Saturated with Trioctylamine Hassan S. Ghaziaskar and Ahmad Rahmanian Chemistry Department Isfahan University of Technology, Isfahan, Iran Barcelona, Spain, May 4 7, 2008 2 Outline History Reactive Exn Experimental Section Separation and Determination of Extracted Samples Parameters Affecting the Exn Conclusion 3 Publications in the Field of SCF in Iran 1990-2008 ISI web of Scopus knowledge

Supercritical fluid 88 96 Supercritical carbon dioxide 116 78 Supercritical carbon dioxide AND Extraction 59 34 Supercritical carbon dioxide AND reaction 8 4 4

Reactive Exns When the extracting solvents are apolar, their ability to extract the polar compounds such as organic acids, amino acids, and phenols is low. About 30 years ago extraction with the help of a chemical reaction or strong physical interaction between the extracting solvent and the sample was used to solve the problem in LLE. In this method usually a small amount of a reactant is added to the extracting solvent to: 1) Increase solvent polarity 2) Have specific interactions with analyte 3) Increase the extraction selectivity 5 Applications of Reactive Extractions in LLE Systems 1) Separation and purification of heavy metal ions such as platinum, Ga (e.g. selective extraction of Ga from coal), etc using organic ligands or strong Lewis bases Amberlite, LA-2 LIX 54-N 2) Extraction of organic compounds from aqueous solutions have also been extensively studied: a) Separation of amino acids using bis(2-ethylhexyl) phosphoric acids b) Separation of Penicillin using Amberlite LA-2 6 Mechanisms of Reactive Extraction of Organic Acids

Using Amines Four major mechanisms for extraction of organic acids with amines has been proposed: 1- Ion exchange mechanism; in an aquous solution of an organic acid or its salt and extractant including an amine R4N+ X-org + HAaq R4N+ A-org + HXaq RnNH(3 - n)org + H+aq RnNH(4 - n)org + 2- Ion-pair formation; when the basic power of the extracting amine is equal or higher than the anion to be extracted. RnNH+ (4 - n) org + A-aq RnNH+4-n X-org + HAaq RnNH+ (4 - n) org A-org RnNH+4-n A-org + HXaq 3- Hydrogen bonding formation 4- Solvation mechanism 7

Reactive Extraction of Carboxylic Acids in a LLE system Organic extractants already used are divided into 3 major categories: 1- Hydrocarbons and oxygen containing extractants. 2- Solvents containing oxygen and phosphorous. 3- High molecular weight aliphatic amines a) higher efficiency b) cheaper than organophosphorous solvents c) reversible reaction with carboxylic acids d) high selectivity Use of amines in the reactive extraction is limited to tertiary amines with long alkyl chain primary amines are water soluble secondary amines are changed into imines when distilled or their pH is changed dramatically for separation of amine from acid 8 Experimental Section 9 Schematic diagram of SFE system CO2 1st Time Reactive Exn of Carboxylic Acids Using SCF Saturated from TOA 10

Microsampling Method Used BP R Pump BPR Pump Solvent a b 11 GC was used for quantitation of the extracted MA & PA MA decomposes at 135 oC at the GC injection port. 1 2. TOA-acid ion-pair Boiling point is higher than the injection port temperature 3. Direct determination of dicarboxylic acids needs very high polar columns. Normal columns leads to broadened and asymmetrical peaks which is not good for quantitative works. Therefore, the acids should be changed to compounds that could be easily separated 12

Determination of Extracted Samples via Derivatization Methanolic BH3 Benzyl bromide Acetic anhydride TFAA & butanol 13 Butanoic Acid (Z)/Maleic Acid Dibutyl Ester ROH = Butanol 14 O O O O 15 Phthalic Acid Dibutyl Ester ROH = Butanol O O

O OH + OH O O O O CF3 O + OR OR 2 ROH CF3 O CF3 + 2 CF3COOH

O O O O CF3 O O 2 (CF3CO)2O + 2 CF3COOH O 16 O O O O 17

Carrier gas = N2 OV-1, 15 m capillary column Injection port temp. = 240 oC FID temp. = 250 oC Temp. program; 1min at 70 oC with the rate of 10 oC/min to 250 oC for 5 min 18 Derivatization In 70 L glass capillary tubes. Three parameters affect the derivatization: 1) The amount of derivatizing agent/g of sample 2) Derivatization temperature 3) Derivatization time These stages were optimized using the GC peak area of the reaction products to the IS (dibenzyl ether) 19 Effect of the Derivatization Reagent (TFAA) Volume (L) on the Peak Area of Derivatized Maleic Acid (), and Phthalic Acid (), at 463 K and 20 min Reaction Time 1.2

Peak Area of Acid / Is 1 0.8 0.6 0.4 0.2 Maleic acid Phthalic acid 0 0 1 2 3 4 V TFAA (L) 5

6 7 20 Effect of the Derivatization Reaction Temperature on the Peak Area of Derivatized Maleic Acid (), and Phthalic Acid (), at 423 K. 1.4 Peak Area of Acid / Is 1.2 1 0.8 0.6 0.4 Maleic acid Phthalic acid 0.2 0 0

50 100 150 200 250 Temperature (oC ) 21 Effect of Derivatization Reaction Time on the Peak Area of Derivatized Maleic Acid (), and Phthalic Acid () at 190 oC 1.4 1.2 Peak Area of Acid / Is 1 0.8 0.6 Maleic acid 0.4

Phthalic acid 0.2 0 0 5 10 15 20 25 30 35 Time (min) 22 The effect of TOA on the Maleic Acid Derivatization 2 Peak area maleic acid / Is

1.8 1.6 1.4 1.2 1 0.8 0.6 0.4 0.2 0 0 0.2 0.4 0.6 0.8 1 1.2 g TOA per 5mL solute 23 The effect of TOA on the Phthalic Acid Derivatization

2 Peak area phthalic acid / Is 1.8 1.6 1.4 1.2 1 0.8 0.6 0.4 0.2 0 0 0.2 0.4 0.6 0.8 1 1.2 g TOA per m

5 L solute 24 1 Phthalic Acid Calibration Curve 0.8 0.6 y = 0.0002x - 0.0123 2 R = 0.9957 0.4 0.2 0 0 1000 2000 3000 4000

5000 6000 -1 Concentration (mg.L ) Maleic Acid Calibration Curve Peak Area of Maleic acid/IS Peak Area of Phthalic acid/IS 1.2 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 y = 0.0002x - 0.0077

R2 = 0.9985 0 1000 2000 3000 4000 Concentration (mg.L-1) 5000 6000 25 Parameters Affecting the Exn of Maleic and Phthalic Acid 26 The Effect of Dispersing Agent Crushed Glass Increases the repeatability and Exn Yield Increases the Contact Surface of the Solvent and Sample Reduces Channeling 83 82

81 y ie ld % 80 79 78 77 76 75 0 10 20 30 40 Glass beads% 50 60 70 Crushed Glass/Sample = 70 %; Mesh 40-60, and MA/PA = 1 27

The Effect of Static Time The sample is kept in contact with the solvent The higher the static time the higher the interaction between scCO2 and the sample and the higher the exn efficiency Static time of 30 min was chosen 28 Table 1 Amount of maleic acid and phthalic acid extracted in mole fraction (y), in g acid per L of scCO2 (S) at temperatures of 308 and 318 K and pressure range of (100-350) bar. Maleic acid Phthalic acid Temperature (oC) Pressure (bar) 105 y 10 S (g/L) 105 y 10 S (g/L)

35 100 7.00 0.59 1.32 0.11 4.14 0.31 1.10 0.08 150 9.35 0.65 2.01 0.14 3.85 0.29 1.17 0.09 200 12.18 0.39 2.78 0.09

12.45 0.68 4.02 0.22 250 94.46 3.95 22.46 0.98 12.95 0.80 4.35 0.27 300 91.17 2.37 22.48 0.59 12.73 0.61 4.41 0.21 350 90.05 2.79 22.61 0.70

12.31 0.48 4.37 0.17 100 10.98 0.69 1.44 0.09 4.03 0.32 1.12 0.06 150 11.65 0.61 2.28 0.12 4.27 0.25 1.18 0.07 200 20.06 1.54

4.30 0.33 13.63 0.86 4.13 0.26 250 110.26 5.58 24.94 1.26 14.27 1.01 4.56 0.32 300 118.94 5.11 27.94 1.20 14.20 0.72 4.71 0.24 350 120.51 5.79

29.17 1.40 14.13 0.82 4.83 0.28 45 29 Table 2 Amount of maleic acid and phthalic acid extracted in mole fraction (y), in g acid per L of scCO2 (S) at temperatures of 55 oC and pressure range of (100-350) bar. Temperature (oC) 55 Pressure (bar) Maleic acid Phthalic acid 105 y 10 S (g/L)

105 y 10 S (g/L) 100 17.39 0.70 1.49 0.06 4.52 0.72 1.12 0.09 150 13.51 0.52 1.61 0.09 4.93 0.33 1.20 0.80 200 31.89 1.45

6.35 0.29 14.79 0.82 4.19 0.23 250 133.95 6.82 28.68 1.23 15.35 0.99 4.64 0.30 300 131.91 3.83 29.60 1.53 15.49 0.92 4.91 0.29 350 139.43 3.19 32.43 0.79 15.07 0.55 4.95 0.18 30 Effect of Pressure on the Exn of Maleic Acid in the Pressure Range of (100-350) bar and Temperatures (oC) of 35 (), 45 (), 55 () 3500 Maleic acid(mg.L-1) 3000 2500 2000 1500

55 45 35 1000 o C C o C o 500 0 50 100 150 200 250 300 350

400 Pressure (bar) 31 Effect of Pressure on the Exn of Phthalic Acid in the Pressure Range of (100-350) bar and Temperatures (oC) of 35 (), 45 (), 55 () 550 Phthalic acid(mg.L-1) 450 phthalic acid 350 o 55 C 45 oC 250 o 35 C

150 50 50 100 150 200 250 300 350 400 Pressure (bar) 32 Effect of Temperature on the Exn of Maleic Acid in the Pressure Range of (100-350) bar 3500 3000

M aleic acid(m g.L-1) 2500 350 bar 300 bar 2000 250 bar 200 bar 1500 150 bar 100 bar 1000 500 0 30 40 50 60

Temperatuer (oC) times increase in exn of maleic acid 1.5 33 Effect of Temperature on the Exn of Phthalic Acid in the Pressure Range of (100-350) bar 600 Phthalic acid (m g.L-1) 500 400 350 bar 300 bar 300 250 bar 200 bar 150 bar 200 100 bar

100 0 30 40 Temperature (oC) 50 60 times increase in exn of phthalic acid 0.8 34 The Effect of scCO2 Density on the Exn 3.5 3 Maleic Acid 2 o 55 C 1.5 45 oC

1 o 35 C 0.5 0 300 400 500 600 700 800 900 1000 Density CO2 (g/L) 0.6 0.5

0.4 Phthalic Acid S (g/L) S (g/L) 2.5 o 55 C 0.3 45 oC 0.2 o 35 C 0.1 0 300 400 500

600 700 Density CO2 (g/L) 800 900 1000 35 Exn of Maleic Acid with TOA in Comparison with its Solubility in Neat scCO2 2.75 2.5 Solubility in pure SC-CO2 Extraction with TOA 2.25 2 1.75 1.5 S (g/L)

1.25 1 0.75 0.5 0.25 0 100 150 200 250 300 Pressure (bar) 36 Exn of Phthalic Acid with TOA in Comparison with its Solubility in Neat scCO2 0.5 0.45 Solubility in pure SC-CO2 Extraction with TOA

0.4 0.35 0.3 S (g/L) 0.25 0.2 0.15 0.1 0.05 0 100 150 200 250 300 Pressure (bar) 37 Selectivity of scCO2-TOA System for the Extraction of MA & PA Selectivity = MA / PA solubility y1

a y2 38 Variation of the Selectivity with Pressure at Different Temperatures 10.0 9.0 8.0 Selectivity () ) 7.0 6.0 5.0 o 55 C 4.0 o 45 C 3.0 o 35 C

2.0 1.0 0.0 50 100 150 200 250 Pressure (bar) 300 350 400 High selectivity of 9 in high pressures High acidity of maleic acid led to a stronger interaction with TOA 39 Conclusions 1. MA & PA was extracted using scCO2-TOA 2. Max. extracted acids at 55 oC and 350 bar were 3.2 and 0.5 g/L for MA and PA, respectively.

3. At 300 bar and 45 oC, 41 times increase in solubility of MA in scCO2-TOA compared to neat scCO2 was observed. For PA this was 7 times . 4. At 300 bar and 45 oC, the selectivity for MA/PA was 9. 40 Acknowledgment Isfahan University of Technology Colleagues: Mohammad Yalpani Yukata Ikushima Lourdes Calvo PhD Students: Ali Daneshfar Marzieh Rezayat Mohammad Kaboudvand Ali Sheibani Habib Eskandari G. Bagherian MSc Students: Mohammad Nikravesh Ahmad Rahmanian Farkhonde Daneshvar Masoumeh Amirabadi Somayeh Kouchaki 41 Thank you for your attention

42 O OH OH O g 79 g 100 ) (

43 . 44 oC131-130 ( ) g/mol 07.116 oC138 ( ) pH

1/0 ) 47.1( pKa1 ) 94.1 (oC25 pKa2 ) 23.6 (oC25 ) kPa 01.0 ( mmHg076.0 o C20 g/cm-359.1( )oC20 O OH OH O

) mg700 g100( . 45 ) 211-210 ( g/mol 16.166 ( 3950) KPa

pH ) 7/0% ( ) 47.1( pKa1 ) 95.2 (oC25 pKa2 ) 41.5 (oC25 )kPa 78.0 (mmHg 86.5 o C191 46 C527 o g/cm-359.1( )oC15

The structure of amine-dicarboxylic acid complex (1 1) ,(1 2) Triethylamine-Acetic acid complex Tridecyl amine-acetic acid) 1,3( 47 1990 - 48 1- . 2- .

3- . 49 1994 N -O ) (BSTFA 50 68/353

810 -39 357 4/0 ) 589 ( 4485/1

)(oC )(bar )g/ (mL 1/31 8/73 466/0 )(H2O 0/374 6/220 322/0 )(Xe 6/16 3/58

099/1 )(Ar -5/122 6/48 531/0 )(N2O 4/36 5/52 453/0 )(CO2 )(SF6 5/45 3/37 737/0

)(HI 7/150 0/83 - 0/90 5/85 - 4/132 2/113 235/0 )(HBr 51 )(NH3 ) ( E ) ( : 117

56 155 O 173 O 41 99 O 100 50 O 82 127 228 240 230

52 211 220 210 199 200 185 190 180 71 109 170 160 150 140 130 0

40 50 60 70 80 90 100 110 120 ( re p lib ) 2 - B u te n e d io ic a c id ( E ) - , d ib u ty l e s t e r - 1 ) ( - 2 ) ( - 3 )Solvent (SF Solute 53 :

: )Solvent (SF Solute 54 1822 -1880 1879 . 1896 . . 1960

. 1975-1985 . 55 . . .

. 56 57 32% 4% 5% 7% 9%

58 24% 19% . 100 1000 . ) ( . 59 10

. 10-3 . 10 . 5- . 60 1/0 . - . CO2 N2O

. 61 62 Reaction of Carbon Dioxide with the Primary Amine 63

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