Dennis Miller, Carl Lira, Aspi Kolah Department of Chemical Engineering & Materials Science Michigan State University, East Lansing, 48824 MI, USA
millerd@msu.edu (517)353-3928
Systems Studied
Lactic acid esterification to ethyl lactate
Succinic acid esterification to di-ethyl succinate Citric acid esterification to tri-ethyl citrate Levulinic acid esterification to ethyl-levulinate and butyl-levulinate Propionic acid esterification to ethyl propionate Dilute acetic acid removal from aqueous streams Acetalization for separation of ethylene glycol and propylene glycol Acetalization reactions for acetaldehyde and formaldehyde Separation of close boiling compounds like cyclohexene and cyclohexane by esterifcation with acetic acid Separation of iso-butylene from C3 - C4 alkane mixtures and oligomerization to isooctene Dihydroxyacetone from glycerol Transesterification reactions like methyl-stearate to butyl-stearate Proprietary reactions with industrial partners and national laboratories
O HO O
Katapak SP-11
Water + Ethanol
OH
OH k-1
HO
O O
Succinic acid + Ethanol
H2O
Succinic Acid
O HO O O
Ethanol
k2
Mono-Ethyl Succinate
O O O O
Ethanol
OH
H2O
k-2
Mono-Ethyl Succinate
2 k3
Di-EthylEthanol Succinate
H2O
Diethyl succinate
Column specifications
Diethyl succinate
Lab capabilities
Catalysis Reaction kinetics Multiphase reactors Phase equilibria Aspen process modeling Molecular modeling
Di-Ethyl Ether
Height of vented enclosure 10.8 m (35 ft) 50 mm Glass column (Vacuum to 0.1 MPa) 50 mm SS-316 column (0.1 to 2.0 MPa) 8 m Reactive section 1 m Non reactive enriching 1 m Non reactive stripping
Reactive distillation for diethyl succinate formation and simultaneous removal of acetate byproduct
Feed to Pre-reactor
Wt % Succinic Acid 25.0 Acetic Acid 2.5 Ethanol 72.5 115 C Flow, g/min Temp, oC Wt % Ethanol Water Diethyl Ether Acetic Acid Ethyl Acetate
Run 14B
Distillate
Expt. 46.5 115 Expt. 89.74 6.15 1.82 0.01 2.20 Aspen 48.6 116.5 Aspen 89.80 5.59 1.13 0.01 2.30
Diethyl Succinate
50 lit 70oC
Top Feed
30.93 g/min 90 C
Wt % Succinic Acid 1.21 Mono-et Succ 18.90 Di-et Succ 14.92 Acetic Acid 0.45 Ethyl Acetate 3.00 Ethanol 55.70 Water 5.86 Diethyl Ether 0.01
45 Psig
3.8 m Katapak SP11 1 m Sulzer BX Stripping 0.6 m Suzer BX Enriching Bottom Feed 28.7 g/min 86 C
Wt % Ethanol 100.0
Bottom
Expt. 245 C Flow, g/min Temp, oC Wt % 11.7 245 Expt. Aspen 11.00 238.8 Aspen 0.00 2.10 96.70 1.22 0.00 0.00 0.01
Overall Succinic acid conv: Diethyl succinate yield: Total mass balance: Succinate balance:
Small loss of Ethanol to Diethyl ether DES of technical grade can be sold directly
Succinic Acid 0.16 Mono-et Succ 0.58 Di-et Succinate 97.36 Ethanol 1.55 Water 0.21 Acetic Acid 0.14 Ethyl Acetate 0.00
Summary
Michigan State University has full capabilities for developing, characterizing, demonstrating new reactive distillation technologies Process and molecular modelling provide rapid evaluation of new systems New succinate acid recovery process synthesizes esters directly from fermentation broth without isolating free acid Reactive distillation produces pure diethyl succinate at nearly 100% yield from mixed acid feed
Acknowledgment
Financial support from DOE, USDA, NCGA, Chemical Companies