(583cl) Catalytic Hydrogenation of Bio-Based Succinic Acid for the Production of 1,4-Butanediol Through the Indirect Pathway

Authors: 
Chung, S. H., Korea University
Kim, M. S., Korea university
Eom, H. J., Korea University
Lee, K. Y., Korea University



Catalytic Hydrogenation of Bio-based Succinic Acid

For the Production of 1,4-Butanediol Through the Indirect Pathway

Sang-Ho
Chung1, Min-Sung Kim1, Hee-Jun Eom1,
Kwan-Young Lee1,*

1Department of Chemical and Biological Engineering, Korea
University, 5-1, Anam-dong, Sungbuk-ku, Seoul 136-701, Republic of Korea

1,4-Butanediol (BDO) is the valuable C4 chemical compound with the
formula of C4H10O2 (HO-(CH2)4-OH,
MW = 90.12 g/mol) and this colorless viscous liquid is used as a solvent due to
its high boiling point (235°) with the miscibility to water and ethanol.

BDO could be used in the manufacture of some types of plastics
such as polybutylene terephthalate, co-polyester ethers, elastic fibers,
polyurethanes and applied as a precursor to for the synthesis of
g-butyrolactone (GBL) and tetrahydrofuran (THF) which could be facilitated to
produce chemical solvents, cleaning agent for electronics and various
biomedical pharmaceuticals [1-6]. Also the demand for solely BDO has steadily increased,
especially in Japan, owing to its use in the manufacture of polytetramethylene
glycol (PTMEG) and polybutylene terephthalate resin, along with a steady
increase in the use of polyurethane.

BDO is now currently produced based on the petro-chemical routes,
such as the Reppe [2], Davy McKee [1] and Acro processes [4]. BDO and its derivatives are highly needed by several related
industries and the production amount of BDO is steadily grown. The growth rate
of world market of BDO is suppress that of world average GDP and reached at
1250000 ton at late 2007. BDO is mainly produced in developed countries like
USA, west Europe and Japan with each portion of total BDO producing amount is
37%, 44% and 12%.

As discussed above, the entire quantity of BDO is currently
produced using petrochemical resources: typical processes such as Reppe process
using acetylene as starting material, Lyondell process using propylene oxide,
Davy process using maleic anhydride and Mitsubishi-BASF process using
butadiene. The main BDO production processes are Reppe and Lyondell process,
but the processes use the acetylene and propylene oxide which chemicals are
denoted as Group A as an exploit materials which in higher explosion rate than
ethylene, ethane and benzene [7]. There were repeatedly accidents in handling or storage in
various nations such as explosion in reaction vessel in Germany in 1996 in
reaction of acetylene and explosion in storage depot in Netherland in
2003. 

Moreover, the price of petrochemical resources continually
increased up to the $100 crude oil price dollar per barrel in 2012 which
increased about 10 times than the price of oil in 1998 [8]. Therefore, the alternative technology for the sustainable
production of BDO should be developed for these above mentioned reasons.

Succinic acid (SA) was recognized as one of the important platform
chemicals which could be produced from the carbohydrates and SA was re-selected
the top platform chemicals in 2010 [5]. SA is a 1,4-dicarboxylic acid in its chemical structure
and SA could be produced from petrochemical process through the partial
oxidation of n-butane but it is recently produced by the fermentation of
various biomass feedstocks using wheat, corn wastes and several others. 

BDO could be obtained from the succinic acid using hydrogenation
process (chemical transformation) with the heterogeneous catalysis. There were
several researchers studying this hydrogenation of SA and one of the pioneers
of the chemical reaction was R.V. chanduhari et al. and they applied the
ruthenium-cobalt catalyst for the production of BDO [9]. Several years later, the Minh group studied the binary
catalysts consisted of the palladium-rhenium catalysts with the highest yield
of BDO of 60% [6]. This direct hydrogenation of diacids like SA to diol
compounds such as BDO have been considered as a hard work as described in the
several literatures even they using the carefully designed homogeneous
catalysis.

Therefore, the indirect pathway for the production of BDO was
suggested in this study (scheme 1). After the dehydration of SA to SAN
(succinic anhydride), the BDO was produced by the hydrogenation of SAN and GBL
(g-butyrolactone) and GBL to BDO, which were the objective of this study. The
hydrogenation of SAN to GBL using ruthenium nanoparticle embedded silica catalysts
(Fig. 1) [10, 11] and GBL to BDO using copper-zinc binary catalysts (Fig. 2) [12] would be discussed
using various heterogeneous catalysts and using thermodynamic and reaction
kinetic analysis. By using this indirect pathway, the yield of BDO increased up
to 73%.

Scheme 1. Indirect pathway for the
production of 1,4-butanediol (BDO). SAC: succinic acid, SAN: succinic
anhydride, GBL: g-butyrolactone (GBL).

Figure 1. High-angle annular
dark-field scanning transmission electron microscopy (HAADF-STEM) images of
RuNPs/SiO2 catalysts and molar concentrations of succinic anhydride
(SAN, open symbol) and g-butyrolactone (GBL, solid symbol) as functions of
reaction time during the hydrogenation of SAN. Reaction conditions: 0.5 mol/L
of succinic anhydride; 50 mL of 1,4-dioxane; 0.3 g of RuNPs/SiO2-300R
catalyst; 50 bar H2; stirring speed: 750 rpm..

 

 

Figure 2. Molar
concentration profile of experimental GC-data for g-butyrolactone (GBL, black open symbol)
and the calculated reaction coordinate at the reaction condition (red solid
line) during the hydrogenation of GBL. Reaction conditions: 0.09 mol/L of
g-butyrolactone; 200 mL of 1,3-dioxolane; 3.0 g of CuZnO catalyst; 180 ± 1°;
50 ± 1 bar; 1,010 ± 20 rpm.

 

 

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In preparation.

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