Chem. Eng. Technol. 2008, 31, No.

5, 647–654 647

Inna Bechthold1 Review

Karlheinz Bretz1
Stephan Kabasci1 Succinic Acid: A New Platform Chemical for
Rodion Kopitzky1
Andrea Springer1 Biobased Polymers from Renewable
1
Fraunhofer Institute for
Resources
Enviromental, Safety and
Energy Technology UMSICHT, Succinic acid is predicted to be one of the future platform chemicals that can be
Oberhausen, Germany. derived from renewable resources. The improvements in biotechnological succi-
nic acid production are presented. Chemical conversion pathways to c-butyrolac-
tone, tetrahydrofuran, 1,4-butanediole, and pyrrolidones are reviewed. An over-
view of possible new biopolymers (e. g. polyesters, polyamides, and poly(ester
amide)s) based on succinic acid and its derivatives is given. Nevertheless, indus-
trial processes using purified succinic acid from fermentation broths are not state
of the art yet. Further improvements are needed until succinic acid-based chemi-
cal production will be economically favorable.

Keywords: Biopolymers, Renewable resources, Succinic acid

Received: January 31, 2008; accepted: March 03, 2008
DOI: 10.1002/ceat.200800063

1 Introduction Several countries have evaluated the potential of biobased

chemicals [3–7] or biobased polymers [8] by governmentally-
For more than 150 years, the chemical industry has been pro- funded projects. The main aspects of these reports – e.g. na-
ducing a large variety of products from coal, gas, and oil. The tional availability [3], integrated biorefinery concepts [7] or
resources in these fossil raw materials are limited and if these white biotechnology [6] – led to the identification of different
resources will further be used with the present consumption types and numbers of building blocks. In all these reports, suc-
rates, they will be running out in the forthcoming 100 years. cinic acid was identified as one of the most important plat-
The remaining oil resources are estimated to be 165 · 109 tons. form chemicals. The suitability of succinic acid as a platform
If crude oil consumption remains on the same level as today chemical is based on the ease of its biotechnological produc-
(in 2002, 3.3 · 109 tons) they will be depleted in a period of tion and on the huge variety of chemicals that can be produced
50 years [1]. Beside the limited repository, the use of fossil re- from it by chemical conversion (compare Fig. 1).
sources leads to worldwide environmental problems and in-
creasing CO2 concentrations in the atmosphere. These prob-
lems initiated an increasing demand for new CO2 neutral 2 Biotechnology
resources for the future.
Nature offers a wide range of resources mainly from plants Succinic acid has been used in the food industry since Robert
due to fast biomass building with low efforts. In comparison Koch proved that it has a positive influence on the human me-
to the contemporary naphtha chemistry, only a few industries tabolism without a risk of accumulation in the human body.
(e.g. biofuels, wood, and paper processing) are using this im- Today, succinic acid is mainly produced by chemical process
mense reservoir of resources. Still the diversity of biomass from n-butane/butadiene via maleic anhydride, utilizing the
feedstocks and the lack of conversion technology routes pre- C4-fraction of naphtha in quantities of about 15,000 tons per
vent an increased utilization of natural resources. Nevertheless, year with a price range of about 6–9 $/kg. Beyond fossil-based
biobased platform chemicals – building blocks for numerous chemistry, derivatives of succinic acid are announced to have a
chemical intermediates and end products [2] – are recognized potential of hundreds of thousand tons [6, 7, 9].
as a burning issue in research, politics, and the industry in the Succinic acid is an intermediate of the TCA cycle (tri-
last decade. carboxylic acid cycle, citric acid cycle) and one of the fermen-
tation end-products of anaerobic metabolism. The fact that
– carbon dioxide (CO2) is needed by the microorganisms for
Correspondence: Dr.-Ing. S. Kabasci ([email protected]), succinic acid production is another interesting feature.
Fraunhofer Institute for Enviromental, Safety and Energy Technology Many different microorganisms like fungi (different Asper-
UMSICHT, Osterfelder Str. 3, D-46047 Oberhausen, Germany. gillus stc., Byssochlamys nivea, Lentinus degener, Paecilomyces

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648 I. Bechthold et al. Chem. Eng. Technol. 2008, 31, No. 5, 647–654

cose-based cultivation. In addition, a

possibility for cost-effective succinic
acid production has been presented
using untreated whey, wood hydroly-
sate, and corn steep liquor, which are
much less expensive than refined car-
bohydrates and yeast extract, respec-
tively [21, 22]. Lee et al. [19] reported
a maximum succinic acid yield of
0.91 mol/mol and a maximum pro-
ductivity of 1.8 gL–1h–1.
Meynial-Salles et al. [23] observed
growth inhibition caused by the endpro-
ducts, succinic acid and acetic acid. The
introduction of a coupled mono-polar
electrodialysis for removing the end
products from the fermentation broth
enhanced growth, productivity, and final
product concentration. Biomass con-
centration could be increased to 42 gL–1,
the maximum productivity reached
10.4 gL–1h–1 and a final concentration
of 83 gL–1 could be achieved. The yield
of 1.35 mol/mol is even higher than Lee
et al. [20] reported using glycerol as car-
bon source. One of the workpackages in
Figure 1. Possible pathways for succinic acid production and products derived by chemical
conversion: 1) Acylic O-containing, 2) acyclic O,N-containing, 3) cyclic O-containing, 4) cy- a research project concerning succinic
clic O,N-containing. acid utilization as a platform chemical
conducted at Fraunhofer UMSICHT is
the optimization of fermentative pro-
duction with A. succiniciproducens [24].
varioti, Penicillium viniferum [10, 11]), yeast (Saccharomyces A. succinogenes was originally isolated from bovine ruminal
cerevisiae), and Gram-positive bacteria (Corynebacterium glu- contents. This organism metabolizes glucose to succinic acid,
tamicum, Enterococcus faecalis) have been screened and studied acetic acid, and formic acid [25]. The A. succinogenes 130Z
for succinic acid production. Most intensively studied are strain and its variant strains were able to produce larger
Anaerobiospirillum succiniciproducens [12] and Actinobacillus amounts of succinic acid and were more resistant to succinic
succinogenes [13] due to their ability to produce a compara- acid than any other previously reported succinic acid produc-
tively large amount of succinic acid. More recently, Mannhei- ers [26, 27]. Strain 130Z produced 66.4 gL–1 succinic acid by
mia succiniciproducens MBEL55E was isolated as a natural suc- consuming 98.3 gL–1 of glucose after 84–h fermentation. The
cinic acid overproducer from bovine rumen by Lee et al. [14]. batch cultivations were performed with 15 gL–1 of yeast extract
Additionally, there have been great efforts in developing re- and corn steep liquor. The main problems of A. succinogenes
combinant Escherichia coli strains, which are capable of en- fermentation are the high concentrations of byproducts like
hanced succinic acid production under aerobic and anaerobic acetic acid, propionic acid, and pyruvic acid which lead to
conditions [15–17]. high costs for product separation.

2.1 Natural Overproducers 2.2 Recombinant Producers

A. succiniciproducens and A. succinogenes were the first identi- More recently, a new succinic acid overproducing strain,
fied natural succinic acid overproducers. M. succiniciproducens MBEL55E, was isolated from bovine ru-
A. succiniciproducens was isolated from the throat and feces men [14]. A succinic acid productivity of 3.9 gL–1h–1 could be
of a beagle dog [18]. This microorganism produces succinic achieved, the highest value that has been reported so far.
and acetic acid as major fermentation products, and ethanol Furthermore, the efficient and economical production of suc-
and lactic acid as minor ones under strictly anaerobic condi- cinic acid was possible by fermentation of M. succiniciprodu-
tions [19]. A. succiniciproducens can utilize glucose, glycerol, cens using a whey-based medium containing corn steep liquor
sucrose, maltose, lactose, and fructose as carbon sources. Lee instead of yeast extract [12]. Metabolic engineering led to in-
et al. [20] reported the use of glycerol as carbon source which creased succinic acid production and yield with simultaneous
leads to an increased succinic acid yield (1.33 mol/mol) and a reduction of byproduct formation. The metabolic engineered
higher ratio of succinic acid to acetic acid compared to glu- strain produced 52.4 gL–1 succinic acid in 29 h in a fed-batch

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Chem. Eng. Technol. 2008, 31, No. 5, 647–654 Biopolymers 649

process. The yield is reported by Lee et al. [28] with 1.16 mol/ broths containing mixed acids could be achieved based on the
mol. Nevertheless, a growth stop after 19.5 h was observed pKa values of the acids and the operating pH. The overall pro-
when the succinic acid titer reached 36 gL–1. cess contains additional steps, such as vacuum distillation and
A wild-type strain of E. coli primarily produces ethanol, for- crystallization for high purity succinic acid production. By-
mic acid, acetic acid, and lactic acid together with merely trace product acids were effectively removed by reactive extraction
amounts of succinic acid from glucose under anaerobic condi- as primary separation step. In addition, crystallization was ap-
tions. The succinic acid yield on glucose typically obtainable plied without adding any salts to produce highly purified suc-
was no more then 0.2 mol/mol. A mutant strain, AFP111, cinic acid. Succinic acid with 99.8 % purity and 73.1 % yield
could grow on glucose with a succinic acid yield of 1.0 mol/ was obtained.
mol and a productivity of 0.87 gL–1h–1. Further metabolic im-
provement resulted in an enhanced productivity. The dual-
phase fermentation comprised of an aerobic growth phase fol- 3 Chemical Conversion
lowed by an anaerobic production phase led to a succinic acid
concentration of 99.2 gL–1 and a productivity of 1.3 gL–1h–1 Succinic acid has long been recognized to undergo a variety of
[15]. reactions. Therefore, extensive literature on reactions of succi-
Recently, a metabolically engineered E. coli strain, capable of nic acid exists. The general chemistry is summarized in [32].
aerobically producing succinic acid through the glyoxylate Succinic acid is often called a “Green” platform chemical be-
pathway and the oxidative branch of the TCA cycle, has been cause it represents a potential building block (see Fig. 1),
developed. The aerobic fed-batch fermentation of this strain which can be transformed into several commodity or specialty
resulted in the production of 58.3 gL–1 succinic acid in 59 h chemicals [7, 33]. The succinic acid-derived products discussed
with a succinic acid yield of 0.85 mol/mol glucose. However, which have industrial applications can be divided in 4 classes:
the production of pyruvic acid (6.1 gL–1) and acetic acid ● acyclic O-containing: 1,4-butanediol, succinic acid esters
(3.0 gL–1) could not be avoided [16, 17]. ● acyclic O,N-containing: 1,4-butanediamine, succinamide,
succinonitrile
● cyclic O-containing: tetrahydrofuran (THF), succinic acid
2.3 Downstream Processing anhydride, dihydrofuran-2(3H)-one (c-butyrolactone)
● cyclic O,N-containing: pyrrolidin-2-one (2-pyrrolidone)
The downstream purification cost for fermentation-based pro- and derivatives, pyrrolidine-2,5-dione (succinimide)
cesses normally amounts to more than 60 % of the total pro- It is obvious that many of these compounds differ in the de-
duction costs. In the case of succinic acid purification, the sep- gree of hydrogenation or that they can be transformed by sub-
aration of byproducts like acetic acid, formic acid, lactic acid, stitution of O/OH with NH/NH2.
and pyruvic acid have a crucial effect on process costs. Further- As shown in Fig. 1, succinic acid can be produced (and is
more, most specialty and commodity applications of succinic produced today) by oxidation of fossil-derived maleic acid
acid require the free acid form rather than the salt form. Sever- (anhydride). In biobased chemistry, succinates will be fermen-
al methods for purification of succinic acid, including electro- ted from carbohydrates like sugar. Nevertheless, only a few ar-
dialysis, precipitation, and extraction have been reported. ticles consider the fermentative nature of “green” succinic acid.
Glassner et al. [29] investigated the purification of succinic Taking the neutral and salty nature of fermentation broth
acid by coupled electrodialysis, consisting of conventional elec- into account, diammonium succinate (DAS) was identified as
trodialysis followed by water-splitting electrodialysis mem- a raw material for chemical syntheses. The production of
brane stacks, which removed most of the salt cations and pro- 2-pyrrolidone (2-PDO) from DAS in aqueous media by hydro-
duced a high purity acid stream. In order to separate the genation using active metal catalysts has been described by
residual cationic, anionic and amino acids, cation and anion Werpy et al. [33]. Hydrogenation in the presence of methanol
exchange resins were integrated into the above process as the using rhodium catalysts yields about 50 % N-methyl-2-pyrroli-
final step. A succinic acid purity of 80 % could be achieved. don (NMP) and 30 % 2-PDO. Using N-methylsuccinimide as
The purification of succinic acid by precipitation was re- starting material and appropriate catalysts (2.5 % Rh/2.5 %
ported by Datta et al. [30]. According to their method, succi- Re/C) and reaction conditions (200 °C, 8 h, 130 bar H2),
nic acid can be precipitated directly into the fermentation nearly pure NMP (NMP:2-PDO = 67:1) could be obtained
broth by addition of calcium dihydroxide, which simulta- [33, 34–37]. This method of production of pyrrolidones is also
neously neutralizes the fermentation broth. Calcium succinate described in [38]. It is claimed that the reactant composition
was recovered by filtration and converted to succinic acid by can be derived from fermentation broths and that the transfor-
adding sulfuric acid. Succinic acid was recovered by filtration mation to pyrrolidones can be done as a one-step or two-step
and further purified by acidic and basic ion exchangers. With reaction. Direct hydrogenation of an aqueous diammonium
this downstream processing method, a purity of 95 % could be succinate solution containing methanol and a Pd/ZrO2/C cat-
achieved. alyst at 265 °C and 130 bar H2 produces 2-PDO and NMP in a
The extraction of succinic acid with an amine-based extrac- ratio of about 1:2 and up to 90 % yield. In the two-step reac-
tant (tri-n-octylamine and 1-Octanol as diluent) has been in- tion, the diammonium succinate or succinimide reacts with
vestigated by Huh et al. [31]. This process is based on a revers- methanol, preferably at 280–320 °C without a catalyst followed
ible reaction between extractant and extracted carboxylic acid. by hydrogenation at preferably less than 230 °C with a carbon/
The selective separation of a specific acid from fermentation metal oxide catalyst at 130 bar H2.

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650 I. Bechthold et al. Chem. Eng. Technol. 2008, 31, No. 5, 647–654

The same working group has also developed a series of tex- lyst comprising of Ru, Rh, Fe, Os or Pd and an organic phos-
tured metal catalysts for the hydrogenation reactions in hydro- phine. The reaction is carried out in the presence of ≥ 1 % water
thermal conditions [39]. These catalysts include a porous hy- at a pressure of 35–140 bar and the product is stripped out
drothermally-stable support, a metal oxide precipitated on the of the reactor with hydrogen at 200–300 °C [47]. Improved bi-
support and a catalyst component. Highly selective aqueous metallic catalysts of Ru-Mo or trimetallic catalysts of Ru-Mo-Sn
phase hydrogenation of succinic acid to c-butyrolactone or Pt-Re-Sn with an inert support are used for hydrogenation of
(GBL) is shown as an example. Operating temperatures of precursors (c-butyrolactone, maleic anhydride, maleic acid,
150–175 °C with pressures ranging from 56–140 bar and succi- succinic acid) in an aqueous solution to produce BDO and THF
nate concentrations of 5–25 wt % have also been reported [48, 49]. BDO can be produced from succinic acid anhydride
[33]. It is said that fermentation byproduct, acetic acid, is not using Raney-type catalysts in the form of hollow spheres [50].
being reduced to ethanol. Additionally, a route from succinic A small review of current fossil-based technology for the
acid to 1,4-butanediole (BDO) via GBL is mentioned. The production of BDO, THF, and GBL starting with acetylene,
purified GBL can be catalytically hydrogenated over bimetallic propylene oxide or butane/butadiene is given in [33]. The ma-
catalysts (Ni and Pd coupled with Rh) supported by carbon. jority of GBL produced by cyclic dehydrogenation of BDO is
The catalysts yielded selectivities greater than 95 % of BDO used for the production of NMP.
from GBL. Operating temperatures range from 150–200 °C
with hydrogen pressures from 70–140 bar.
Some of the above noted results were published at an ACS 4 Polymerization
symposium [40].
Considering the disadvantages of purifying steps that are In addition to succinic acid, the production of polyamides
needed using the process described in [38], Fischer et al. have (PA), polyesters, and poly(ester amide)s requires components
presented a method for the production of succinimide and re- like diamines or diols. These products can also be obtained by
lated compounds by reactive distillation of nitrogen-contain- chemical conversion of succinic acid (Section 3).
ing succinate salts in fermentation broths [41]. The distillation
can take place with the addition of ammonia or diammonium
succinate or primary amines for the production of succinimide 4.1 Polyamides
or N-alkylated succinimides. Heat transfer media acting simul-
taneously as diluting agents are recommended. The distillate Polyamides are technical plastics with high performance levels.
fractions can be reduced to 2-pyrrolidones and derivatives. Their properties are characterized by high durability, and high
Without special considerations of the characteristics of fer- hardness and rigidity simultaneously.
mentative succinic acid, the conversion of succinates into the Carothers was the first researcher to perform systematic in-
interesting bulk chemicals, THF, GBL, and BDO has been de- vestigations of the polycondensation of dicarboxylic acids with
scribed in early publications, e.g. the reduction of succinates diamines [51, 52]. Methods for the production of polyamides
over Cu-Cr oxide by Wojcik and Adkins in 1933 [42]. Conse- by polycondensation of aliphatic diamines and dicarboxylic
quently, many publications can be found. A previous review is acids or the polyaddition of lactams are described on a large
given in [43]. Here, only the last five years are summarized. Al- scale in the literature. These articles are mostly dedicated to
kylesters of polycarboxylic acids were manufactured by reactive standard polyamides, from which the two “commodity poly-
distillation of ammonium salts of polycarboxylic acids with amides”, PA 66 and PA 6, constitute the predominant contin-
monoalkanols, e.g. dibutylsuccinate which was used for gas- gent. The established technical polyamides, PA 46, PA 11, and
phase hydrogenation to THF in a reactor at 250 °C and 13 bar PA 12 as well as special polyamides like PA 610, can also be
using CuO/Al2O3 as catalyst [44]. A process using a hydroge- widely found.
nation catalyst comprising one or more active hydrogen cata- PA 44 based on succinic acid and 1,4-butanediamine has
lyst components on a rutile support for the production of up to date only been manufactured on the laboratory scale
GBL, THF, and BDO is described by Bhattacharyya [45]. A [53, 54]. A technical synthesis of PA 44 has not been described
two-stage gas-phase hydrogenation process for the preparation in the literature yet. Publications can be found concerning
of THF, BDO, and GBL from C4 dicarboxylic acid is presented polyamides, either on the basis of 1,4-butanediamine (PA 4n)
in [46]. In the first stage, catalysts consisting of 5–95 % Cu ox- [55–58] or on the basis of succinic acid (PA n4) [56, 59–62].
ide and 5–95 % of an oxide with acid centers are used to pro- These polyamide types show interesting and unexpected prop-
duce an intermediate stream mainly consisting of GBL and erties.
THF. The by-product succinic acid anhydride can be separated For example PA 24 possesses the same properties such as
by partial condensation. THF, GBL, and water remaining in both silk proteins and commercial polyamides regarding IR
the gaseous phase are hydrogenated in a second reactor. Its absorption, solubility, and thermal behavior [62]. A short-
products, THF, GBL, BDO, and water are separated by distilla- chain aliphatic PA 42 manufactured by polycondensation of
tion; a GBL rich flow is optionally returned into the second re- 1,4-butanediamine with diethyl oxalate could be interesting
actor and the product ratios can be adjusted by varying the for use as fibers [56].
temperatures in the two hydrogenation reactors as well as the PA 46 was first produced in 1938 by Carothers [57] and is
GBL reflux. now distributed by DSM under the trade name Stanyl®. Car-
A homogeneous process is described for the hydrogenation of others reported a melting point of 278 °C, which later was con-
dicarboxylic acids and/or anhydrides in the presence of a cata- firmed by Coffman et al. [58]. Other authors present a range

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Chem. Eng. Technol. 2008, 31, No. 5, 647–654 Biopolymers 651

of the melting point of PA 46 as a function of the thermal his- their performance and processing facilities. For example,
tory from 283 °C to 319 °C [63–65]. BAK1095 is manufactured from e-caprolactam, adipic acid,
Katsarava et al. [59–61] suggested a new polycondensation and 1,4-butanediol. BAK2195 is a mixture of polyamide on
method for the synthesis of high-molecular weight polysuccin- the basis of 1,6-hexamethylenediamine and adipic acid with a
amides on mild reaction conditions. polyester from adipic acid and 1,4-butanediol [81]. The pro-
duction of BAK was stopped in 2001 due to economic reasons.
Novel biodegradable copolymers derived from succinic acid
4.2 Polyesters dialkyl ester, 1,4-butanediol, and 1,4-butanediamine were
synthesized by two-step polycondensation reactions. The ma-
Some homo- and copolyesters of succinic acid are manufactured terials obtained had a periodic sequence structure consisting of
industrially and are currently being introduced into the polymer ester and amide units. Melting temperatures of the periodic
market. Mitsubishi Chemical Corporation (Tokyo, Japan) has copolymers increased with an increase in amide content [82].
developed a new biodegradable plastic with the trade name GS The favorable combination of properties of poly(ester am-
Pla®, i.e. a poly(butylene succinate). Their goal is to produce a ide)s is used with the development of new thermoplastic mate-
“Green Sustainable Plastic” using succinic acid produced by bac- rials with good mechanical properties, processibility, and com-
terial fermentation of corn and 1,4-butanediol [66]. plete degradability.
Bionolle® (Showa Denko) is produced by polycondensation
of glycols such as ethylene glycol and 1,4-butanediol together
with aliphatic dicarboxylic acids such as succinic acid and 5 Discussion and Conclusions
adipic acid [67]. Bionolle® with a production capacity of
10,000 t/a is in the introductory market phase [68]. In this paper, a review of processes for succinic acid fermenta-
Polyester blown films have similar mechanical properties tion from renewable resources, its chemical conversion, and
to the widely-used films from high-pressure polyethylene the production of polymers based on succinic acid were pre-
(LDPE). The most important factors for the biodegradability sented.
of polyester films are the structure and physical properties of
the polymer, for example the morphology of crystals, the de-
gree of crystallinity and their orientation, as well as the thermal 5.1 Biotechnological Production and Downstream
and mechanical properties [69–71]. Processing
Polyesters (homo- and copolyester) can be manufactured
by polycondensation of dicarboxylic acid esters with diols Regarding literature today, four strains (A. succinogenes,
[70, 72–74]. A second way is the direct polycondensation of di- M. succiniciproducens MBEL55E, A. succiniciproducens, and
carboxylic acids with diols [63, 75–79] High-molecular weight E. coli) are potential candidates for industrial succinic acid pro-
polyesters are obtained by chain extensions from low-molecu- duction. Many problems like slow growth, high by-product for-
lar weight polyesters with hexamethylene diisocyanate as a mation, and low yield could be solved partially by metabolic engi-
chain-extender. neering. Nevertheless, a complete suppression of the by-products
has not been achieved yet. Another problem for industrial appli-
cation is the inhibitory effect of the cultivation product, succinic
4.3 Poly(ester amid)es acid itself. Lee et al. [28] reported a growth stop after 19.5 h for
the metabolic engineered strain of M. succiniciproducens when
Biodegradable polyesters have attracted industrial attention as the succinic acid titer reached 36 gL–1. Meynial-Salles et al. [23]
environmentally degradable thermoplastics used for a wide made an energetic characterization of A. succiniciproducens. Based
range of applications. Although polyesters are nowadays the on the very low YATP values, they assumed that the succinate
most important family of biodegradable polymers in general, export mechanism is ATP dependent. The A. succinogenes strain
their thermal and mechanical properties are not optimal for 130 Z has a higher tolerance for succinic acid and a concentration
industrial applications. Attempts have been made to regulate of 66.4 gL–1 could be achieved [26, 27].
the physical properties and biodegradation rate of polyesters Different methods were used for in-situ product removal to
by copolymerization with various monomeric units. The prop- overcome the inhibitory effect of succinic acid during fermen-
erties of the polymer can be improved by the introduction of tation. Guettler et al. [26, 27] added high amounts of MgCO3,
amide groups into the main chain, since these comonomers Meynial-Salles et al. [23] coupled a mono-polar electrodialysis
give rise to strong intermolecular hydrogen-bond interactions. to a cell recycle bioreactor. A final succinic acid concentration
The physical properties, such as melting temperature and of 83 gL–1 could be reached this way.
tensile strength of poly(ester amide)s, show a strong depen- The subsequent problem of the biotechnological process is
dence on both the content and the distribution of the amide product purification (downstream processing). Regarding the
units in the polyester chains. rising energy prices, electrodialysis may probably not the best
The first works were carried out in 1979 and were based on suited method. The power consumption is rather high for an
the amide-ester interchange reaction that takes place if a poly- intended bulk chemical. A second method for purification
amide/polyester mixture is heated at temperatures near 270 °C (Datta et al. [30]), precipitation, has the disadvantage of pro-
[80]. Different biodegradable poly(ester amide)s were com- ducing large amounts of waste. In the case of in-situ precipita-
mercialized (BAK®) with a wide range of applications due to tion using calcium hydroxide not only succinic acid, but also

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652 I. Bechthold et al. Chem. Eng. Technol. 2008, 31, No. 5, 647–654

phosphate and sulphate will be precipitated from the fermen- on the basis of the key component succinic acid with the final
tation medium. product PA 44 has not been pursued intensively, some charac-
Actually, the reactive extraction (tri-n-octylamine) reported teristics of PA 44 can be forecasted.
by Huh et al. [31] seems to be the most promising method. In From aliphatic high-melting PA 46 and PA 66, it is well-
comparison to other processes, it requires less energy and pro- known that they have a relatively small time and temperature
duces less waste. Nevertheless, the long-term stability of such a range during processing. Thus, a narrow processing window is
combined process has to be proved because of the possible also to be expected for PA 44.
toxic or inhibitory effects of extractant and solvent for the mi- The academic literature describes the melting temperature
croorganisms. of PA 44 ambiguously. In the fundamental publication about
In order to get competitive with oil-based succinic acid pro- PA 44 by Dreyfuss [54], a melting temperature of > 260 °C is
duction, further improvements in the composition of the fer- reported. Other papers state that PA 44 – as well as PA 42 –
mentation medium have to be made. Regarding the media com- will decompose before reaching the melting point [83]. How-
positions reported in the literature, especially costly factors like ever, Koning et al. reported a melting temperature of PA 42 of
peptone and tryptone must be removed from the raw materials. 390 °C [84]. Our work in this area at Fraunhofer UMSICHT,
Furthermore, the amount of yeast extract should be reduced. where PA 44 is being synthesized, indicated a range of the
Screenings for cheaper carbon sources than glucose have al- melting point between 300 and 350 °C [85].
ready been performed. Literature shows that it is possible to The technical synthesis of PA 44 cannot be easily performed.
use glycerol and wood hydrolysate as cheap carbon sources. Due to economic criteria, a mass polymerization is preferable,
Summarizing the above, the future of fermentative pro- since the reactants are present as acid and amine. Concerning
duction of succinic acid is promising considering the increasing 1,4-butanediamine, it is well-known that a critical secondary
acceptance of renewable raw materials, a large potential market reaction, the formation of the cyclic pyrrolidine, takes place
size, the advantage of carbon dioxide fixation in the fermenta- and thus the stoichiometry of the polymerization is changed.
tion, and advances in the development of strategies for strain However, this side reaction can be reduced like the industrial
improvement, fermentation, and downstream processing. synthesis of the PA 46 (Stanyl®, DSM) reveals; or like it is also
described by Pipper et al [55]. If the synthesis of high-molecu-
lar weight polysuccinamides runs over special esters of succinic
5.2 Chemical Conversion acid, the chain growth stopping reaction of the aminolysis can
almost be suppressed completely [59–61].
The utilization of N-containing succinates from fermentation The properties of the homo polyamide are determined by
broths for the production of N-containing derivatives of succi- the strong polar amide groups along the polymer chain in reg-
nic acid seems to be a favorable method. Nevertheless, the ular consequence and the hydrocarbon residues. The water ab-
above noted patents (see Section 3) for the production of pyr- sorption depends on the structure and the processing of the
rolidones are not describing processes with real fermentation polyamides.
broths because: Gaymans et al. [65] examined the water adsorption of cast
● The separation of proteins and contaminants [38] or the use films from PA 42 and showed that the material was very hygro-
of “processed” aqueous fermentation solutions [41] is re- scopic (7.5 % at 65 % RH). PA 42 with a crystallinity of 70 %
commended. has exhibited lower water absorption (3.1 % by 50 % RH)
● Extraction with (chlorinated) organics of semiproducts e.g. [56]. From these results we can assume that PA 44 will show
succinimide prior to hydrogenation is preferred [38]. similar behavior concerning water absorption.
● In an example in [41], the fermentation broth containing Polyester: The properties of polyesters depend on their com-
about 13 gL–1 diammonium succinate has been enriched with position. Pure aliphatic polyesters have low melting points and
a fourfold amount of synthetically diammonium succinate. are mostly crystalline. The melting points increase with in-
It has to be revealed if the conversion reactions described creasing number of methylene groups between the ester func-
will work in technical processes, or if the downstream process- tions. On the other hand, polyesters which are composed of
ing of succinate fermentation broths will lead to other solu- aromatic or cyclic-aliphatic dicarboxylic acids and diols, pos-
tions in terms of energy, sustainability, and cost efficiency. It is sess different properties [86].
one of the challenges to develop new integrated processes. The For example, Bionolle® (Showa Denko) is a typical thermo-
development of new catalysts providing water resistance, plastic polyester with good manufacturing properties, flexibil-
stability, and high transformation rates is very important for ity, and tenacity, which are comparable to those from LDPE
new raw material feedstocks from fermentation. Energy- and [67]. GS Pla® (Mitsubishi Chemical Corporation, Japan) is a
time-consuming processes for water removal thus could be poly(butylene succinate) (PBS) [66]. It is flexible, has high
avoided. heat-seal strength and is permeable to oxygen and moisture. It
is more flexible and has higher tensile elongation and notched
izod impact than PLA, according to Mitsubishi. It has recently
5.3 Polymerization been introduced in Japan, where it is currently used in agricul-
tural applications. GS Pla® is reported to be as soft as polyeth-
Polyamide: Although only a few works in the field of PA 44 ylene but can be made harder like polypropylene by adding
have been published in the literature to date and the process fillers. It can also be processed to fibers, suggesting non-wo-
chain biomass – C4-chemistry – high-performance polymers vens and synthetic papers as applications.

© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim http://www.cet-journal.com

Chem. Eng. Technol. 2008, 31, No. 5, 647–654 Biopolymers 653

The properties of polymers can be changed by copolymeri- Acknowledgement

zation with aromatic monomers. The increasing content of the
phenyl side chain reduces the melting temperature and crystal- The project is supported by the German government (BMELV/
linity, but increases the glass transition temperature of the ali- FNR: FKZ 22024905).
phatic polyesters. The tensile strength, the elongation, and the
tear resistance of polyester-26 decreased with an increase of
the phenyl content. However, the increase in the phenyl con- References
tent increased the elongation and tear resistance of polybuty-
lene succinate considerably [78, 79, 87]. [1] R. Busch et al., Chem. Ing. Tech. 2006, 78 (3), 219. DOI:
Poly(ester amide): Succinic acid and their derivatives are not 10.1002/cite.200500178
only basic molecules for polyesters and polyamides, they can [2] T. M. Carole, J. Pellegrino, M. D. Paster, Appl. Biochem. Bio-
also be used for the synthesis of poly(ester amide)s. technol. 2004, 115, 872.
Novel biodegradable copolymers with a periodic sequential [3] E. Archambault (Ed.), F. Bertrand, G. Côté, O. Craig-Du-
structure of ester and amide groups could be synthesized by pont, V. Larivière, É. Vignola Gagné, Towards a Canadian
two-step polycondensation reactions from dimethyl succinate, R&D Strategy for Bioproducts and Bioprocesses, for National
1,4-butanediol and 1,4-butanediamine [82]. These periodic co- Research Council of Canada 2004.
polyester-amides have high thermal stability comparable with http://www.science-metrix.com/pdf/
the PBS homopolyester. This suggests that the copolyester-am- SM_2003_014_NRC_Canadian_R&D_Strategy.pdf
ides form different chain packing structures due to the forma- [4] B. Hüsing, G. Angerer, S. Gaisser, F. Marscheider-Weide-
tion of the intermolecular hydrogen bonds coming from the pe- mann, Ber.- Umweltbundesamt (Ger), 2003.
riodic amide units introduced into the polyester chains. The [5] M. D. Paster, J. Pellegrino, T. M. Carole, Industrial Biopro-
melting temperature of the periodic copolymers increased with ducts: Today and Tomorrow, for the Office of the Biomass
an increase of the amide content from 140 °C for homopoly(bu- Program, Office of Energy Efficiency and Renewable Energy,
tylene succinate) to 260 °C for poly(butylene succinamide). US Department of Energy. Washington, DC 2003.
The introduction of ester segments can lead to the reduction [6] M. Patel, M. Crank, V. Dornburg, B. Hermann, B. Hüsing,
of crystallinity of the polyamide as a function of size and con- L. Overbeek, F. Terragni, E. Recchia, Medium ang Long-Term
centration of the ester segments. The combination of good Opportunities and Risks of the Biotechnological Production of
physical properties, biocompatibility, and controlled degrad- Bulk Chemicals from Renewable Resources –The Potential of
ability of poly(ester amide)s makes it possible to use these ma- White Biotechnology: The Brew Project, European Commis-
terials in medicine as absorbable seams or temporary implants. sion’s GROWTH Programme (DG Research), Utrecht 2006.
Like PET, semicrystalline polyamides are only very slowly http://www.chem.uu.nl/brew/
biodegradable. In contrast, aliphatic poly(ester amide)s are [7] T. A. Werpy, G. Petersen (Ed.), Top Value Added Chemicals
biodegradable with sufficient ester content and a statistic dis- From Biomass, for the U.S. Department of Energy (DOE) by
tribution of the amide and ester functions. Copolymers National Renewable Energy Laboratory (NREL), 2004.
of e-caprolactam (approx. 60 wt %), adipic acid, and 1,4-buta- (http://www.osti.gov/bridge)
nediol exhibit similar mechanical properties and melting [8] M. Crank, M. Patel, F. Marscheider-Weidemann, J. Schleich,
points as LDPE and are suitable for applications like films. B. Hüsing, G. Angerer, Techno-economic Feasibility of Large-
Due to their higher strength, copolymers from 1,6-hexamethy- scale Production of Bio.based Polymers in Europe (Pro-BIP),
lenediamine, adipic acid, 1,4-butanediol, and diethylene glycol for the European Commissions’s Institute for Prospective
(amide content 40 wt %) are suitable for injection moulding Technological Studies (IPTS), Sevilla, Spain 2004.
articles, like flower pots or one-way cutleries, as well as fibers. [9] J. G. Zeikus, M. K. Jain, P. Elankovan, Appl. Microbiol. Bio-
Polymers like polyamides, polyesters, and poly(ester amide)s technol. 1999, 51, 545.
based on succinic acid and its derivatives today are fossil-based [10] E. T. M. Ling et al., Appl. Environ. Microbiol. 1978, 35, 1213.
products. For economical and ecological reasons, it is advisable [11] C. Rossi, J. Hauber, T. P. Singer, Nature 1964, 204, 167.
to substitute oil-based polymers in as many applications as pos- [12] P. C. Lee, S. Y. Lee, S. H. Hong, H. N. Chang, Bioprocess. Bio-
sible. In order to be competitive with fossil-based materials, all syst. Eng. 2003, 26, 63.
biopolymers need to have a good processibility on conventional [13] M. V. Guettler, D. Rumler, M. K. Jain, Int. J. Syst. Bacteriol.
machines and a broad and excellent range of characteristics. 1999, 49, 207.
As an example, PA 44 based on fermentative succinic acid [14] P. C. Lee, S. Y. Lee, S. H. Hong, H. N. Chang, Appl. Microbiol.
offers an alternative to oil-based polyamides for use in special Biotechnol. 2002, 58, 663.
applications. Regarding the properties of PA 44, three product [15] G. N. Vemuri, M. A. Eiteman, E. Altman, J. Ind. Microbiol.
groups seem to be interesting: Biotechnol. 2002, 28, 325.
● Parts demanding high thermal stability and mechanical [16] H. Lin, G. N. Bennett, K.-Y. San, Metab. Eng. 2005, 7, 116.
strength, for example for oil-immersed gearbox parts, [17] H. Lin, G. N. Bennett, K.-Y. San, Biotechnol. Bioeng. 2005, 90,
pumps parts, and abrasion-resistant gear wheels. 775.
● Tearproof fibers with high water absorption, for example for [18] C. P. Davis, D. Cleven, J. Brown, Int. J. Syst. Bateriol. 1976,
blended fabrics for the use in outdoor clothes. 26.
● Hydrophilic, modifiable, mechanical resistant polymer [19] P. C. Lee et al., Enzym. Microbial. Technol. 1999, 24 (8–9),
membranes, for example for filtration techniques. 549.

© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim http://www.cet-journal.com

654 I. Bechthold et al. Chem. Eng. Technol. 2008, 31, No. 5, 647–654

[20] P. C. Lee, W. G. Lee, S. Y. Lee, H. N. Chang, Biotechnol Bioeng [53] R.G. Beaman et al., J. Polym. Sci. 1959, (XL), 329.
2001, 72 (1), 41. [54] P. Dreyfuss. J. Polym. Sci.: Polym. Phys. Ed. 1973, 11, 201.
[21] P. C. Lee et al., Biotechnol. Lett. 2003, 25, 111. [55] G. Pipper, E. M. Koch, US Patent 5,030,709, 1990.
[22] P. C. Lee et al., Biotechnol. Bioprocess. Eng. 2000, 5, 379. [56] R. J. Gaymans, V. S. Venkatraman, T. Schuijer, J. Polym. Sci:
[23] I. Meynial-Salles, S. Dorotyn, P. Soucaille, Biotechnol. Bioeng. Polym. Chem. Ed. 1984, 22, 1373.
2008, 99 (1), 129. [57] W. H. Carothers, US Patent 2,130,948, 1938.
[24] S. Kabasci et al., Schriftenreihe „Nachwachsende Rohstoffe“, [58] D. D. Coffman, G. J. Berchet, W. R. Peterson, E. W. Spanagel,
Verlag T. Mann, Gelsenkirchen 2007, 224. J. Polym. Sci. 1947, 2, 306.
[25] M. J. Van der Werf, M. V. Guettler, M. K. Jain, J. G. Zeikus, [59] R. D. Katsarava, D. P. Kharadze, L. M. Aualkhuili, Makromol.
Arch. Microbiol. 1997, 167, 332. Chem. 1986, 181, 2053.
[26] M. V. Guettler, M. K . Jain, D. Rumler, US Patent 5,573,931, [60] R. D. Katsarava et al., Acta Polym. 1988, 39, 523.
1996. [61] R. D. Katsarava, Macromol. Symp. 2003, 199, 419.
[27] M. V. Guettler, M. K. Jain, B. K. Soni, US Patent 5,504,004, [62] Q. Wang, Z. Shao, T. Yu, Polym. Bull. 1996, 36, 659.
1996. [63] B. D. Ahn, S. H. Kim, Y. H. Kim, J. S. Yang, J. Appl. Polym.
[28] S. J. Lee, H. Song, S. Y. Lee, Appl. Environ. Microbiol. 2006, Sci. 2001, 82, 2808.
72 (3), 1939. [64] B. Ke, A. W. Sisko, J. Polym. Sci. 1961, 50, 87.
[29] D. A. Glassner, R. Datta, US Patent 5,143,834, 1992. [65] R. J. Gaymans, T. E. C. van Utteren, J. W. A. van den Berg,
[30] R. Datta, D. A. Glassner, M. K. Jain, J. R. Vick Roy, US Patent J. Schuyer, J. Polym. Sci.: Polym. Chem. Ed. 1977, 15, 537.
5,168,055, 1992. [66] M. Baumann (Ed.), PolymerPlace Notes, 2007, 8, 5. http://
[31] Y.S. Huh et al., Process. Biochem. 2006, 41, 1461. www.polymerplace.com/newsletters/August%2007_newslet-
[32] C. Fumagalli, Succinic Acid and Succinic Anhydride, in Kirk ter.pdf
Othmer Encyclopedia of Chemical Technology, 5th ed., John [67] T. Fujimaki, Polym. Degrad. Stab. 1998, 59, 209.
Wiley & Sons, Hoboken 2006. [68] P. Drachman, Developments in Biodegradable Plastics for
[33] T. A. Werpy, J. Frye, J. Holladay, in Biorefineries – Industrial Packaging, Industry Insight, IntertechPira, 2007.
Processes and Products, Vol. 2 Status Quo and Future Direc- [69] W.S. Lyoo et al., Polymer, 2000, 41, 9055.
tions (Eds.: B. Kamm, P. R. Gruber, M. Kamm), Wiley-VCH, [70] X. Wang, J. Zhou, L. Li, Eur. Polym. J. 2007, 43, 3163.
Weinheim, Germany 2006, 367. [71] Y. Xu, J. Xu, B. Gou, X. Xie, J. Polym. Sci. Part B: Polym. Phys.
[34] T. A. Werpy, J. G. Frye, Y. Wang, A. H. Zacher, US Patent 2007, 45, 420.
6,632,951, 2004. [72] H. Shirahama, Y. Kawaguchi, M. S. Aludin, Y. Yasuda, J. Appl.
[35] T. A. Werpy, J. G. Frye, Y. Wang, A. H. Zacher, US Patent Polym. Sci. 2001, 80, 340.
6,603,021, 2004. [73] D. Jovanovic, M. S. Nikolic, J. Djonlagic, J. Serb. Chem. Soc.
[36] T. A. Werpy, J. G. Frye, Y. Wang, A. H. Zacher, US Patent 2004, 69, 1013.
6,706,893 2004. [74] M. S. Nikolic, J. Djonlagic, Polym. Degrad. Stab 2001, 74,
[37] T. A. Werpy, J. G. Frye, Y. Wang, A. H. Zacher, US Patent 263.
6,670,483, 2003. [75] S. Velmathi, R. Nagahata, J. Sugiyama, K. Takeuchi, Macro-
[38] T. A. Werpy, J. G. Frye, Y. Wang, A. H. Zacher, WO 02/ mol. Rapid Commun. 2005, 26, 1163.
102772 A1, 2002. [76] C. Zhu et al., J. Appl. Polym. Sci. 2003, 90, 982.
[39] T. A. Werpy, J. G. Frye, Y. Wang, A. H. Zacher, WO 02/ [77] D. N. Bikiaris, G. Z. Papageorgiou, D. S. Achilias, Polym. De-
102511 A1, 2002. grad. Stab. 2006, 91, 31.
[40] N. Nghiemet al., Chemicals and Materials from Renewable Re- [78] H.-J. Jin, B.-Y. Lee, M.-N. Kim, J.-S. Yoon, Eur. Polym. J.
sources (Ed: J. J. Borell), ACS, Washington 2001. 2000, 36, 2693.
[41] W. Fischer et al., WO 2006/066839 A2, 2006. [79] H.-J. Jin, B.-Y. Lee, M.-N. Kim, J.-S. Yoon, J. Polym. Sci. B:
[42] B. Wojcik, H. Adkins, J. Amer. Chem. Soc. 1933, 55, 4939. Polym. Phys. 2000, 38, 1504.
[43] S. Varadarjan, D. J. Miller, Biotechnol. Prog. 1999, 15, 845. [80] Y. Tokiwa, T. Suzuki, T. Ando, J. Appl. Polym. Sci. 1979, 24,
[44] C. Bauduin, W. Fischer, R. Pinkos, E. Scholten, EP 1,842,843, 1701.
2007. [81] E. Grigat, R. Koch, R. Timmermann, Polym. Degrad. Stab.
[45] A. Bhattacharyya, M. D. Manila, US Patent 2,006,004,212 A1, 1998, 59, 223.
2006. [82] H. Abe, Y. Dui, Macromol. Rapid. Commun. 2004, 25, 1303.
[46] M. Roesch et al., WO 2005058853 A2, 2005. [83] N. A. Jones, E. D. Atkins, M. J. Hill, Macromol. 2000, 33 (7),
[47] M. A. Wood, S. P. Crabtree, D. V. Tyers, WO 2,005,051,875 2642.
A1, 2005. [84] C. Koning, G. W. Buning, Macromol. Res. 1999, 4, 1.
[48] D. Campos, US Patent 2,004,122,242 A1, 2004. [85] G. Deerberg et al., 1st International Conference on Renewable
[49] D. Campos, G. M. Sisler, US Patent 6,670,490 B1, 2003. Resources And Biorefineries, Ghent, Belgium 2005.
[50] D. Ostgard, M. Berweiler, S. Roeder, WO 2002051779 A2, [86] X. Liu, C. Li, D. Zhang, Y. Xiao, Macromol. Chem. Phys.
2002. 2006, 207, 694.
[51] W. H. Carothers, Chem. Rev. 1908, 8, 353. [87] S.-W. Kim, J.-C. Lim, D.-J. Kim, K.-H. Seo, J. Appl. Polym.
[52] W. H. Carothers, G. J. Berchet, J. Amer. Chem. Soc. 1930, 52, Sci. 2004, 92, 3266.
5289.

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