Newsfront

Renewable Feedstocks:
TRADING Barrels for Bushels Starch based polymers Current bulk productions
Efforts to boost Polyhydroxyalkanoates Production on pilot scale
Research scale
conversion rates and CO2

Vinyl
yields and improve Starch C5 and
C6
Ethanol
Lactic acid
Ethylene chloride 1,3 Propanediol
1,2 Propanediol
separation efficiency sugars
3 HP Acrylic acid Acrylic acid

are helping, Wheat

maize
Sugar
beet, Succinic
PBS
THF
Poly lactic acid

potato sugarcane acid

but obstacles remain 1,4 Butanediol
Glycols
Sorbitol

W
Isosorbide Polymer
ith traditional petro- Isoprene Polyisoproprene
Cellulose/ C5 and
leum-derived feed- ligno C6
stocks facing relentless sugars Ethanol
cellulose
economic and environ- Levulinic acid MeMbl Cellulose ethers
mental pressures, it’s no surprise cellulose esters
and viscose
that stakeholders throughout Rapeseed, Vegetable Bio diesel Acrolein fibers
the chemical process industries soyseed oil
Glycerol Glycerol carbonate
(CPI) have been in hot pursuit of Natural oil 1,2 Propanediol
alternative routes for producing polyols (NOP)
Epichlorohydrin Epoxy resins
commodity and specialty chemi- Figure 1. Many platform
cals and polymers from cheap, and derivative chemicals and Polyurethanes 1,3 Propanediol
plentiful renewable feedstocks. polymers can be produced from
a handful of renewable agricultural and forest feedstocks Source: Frost & Sullivan
The most promising routes are
based on agriculturally derived,
starches, sugars, fats, oils, lignocellu- economic impact of using renewable acid, glutamic acid, itaconic acid, le-
lose, and proteins, and waste streams feedstocks, the integrated biorefiner- vulinic acid, 3-hydroxbutyrolactone,
from fruit and vegetable processing ies of the future will need to pursue glycerin, sorbitol and xylitol/arabi-
plants, pulp-and-paper mills, and a “one-to-many” concept — whereby nitol. According to Frost & Sullivan,
other biomass sources (Figure 1).1 each renewable feedstock will be con- efforts to produce the platform chemi-
Today, parallel efforts are beginning verted into any number of basic build- cals lactic acid, succinic acid, glycerin,
to bear fruit. According to market ana- ing block chemicals (so-called “plat- 1,3-propanediol (PDO), levulinic acid,
lyst Frost & Sullivan (London; www. form chemicals”), which would then and various cellulose and starch de-
chemicals.frost.com), the global mar- serve as the interim feedstocks for the rivatives are furthest along on the de-
ket for renewably sourced commodity production of countless downstream, velopmental continuum today.
chemicals earned revenues of $1.63 value-added chemicals, monomers and Still, challenges remain, because
billion in 2008, and this figure is pro- polymers, says Joseph J. Bozell, asso- “no two technologies reside within any
jected to reach $5.01 billion by 2015. ciate professor, Biomass Chemistry, single company — every company has
Many of the most mature processes Forest Products Center, University of perfected its own single technology for
to date tend to be focused on the con- Tennessee (Knoxville). producing single target products” says
version of a single renewable feed- In 2004, the U.S. Dept. of Energy Phani Raj Kumar Chinthapalli, senior
stock into a single biobased chemical (DOE; Washington, D.C.; www.doe.gov) research analyst for Frost & Sullivan,
or polymer (a “one-to-one” concept). identified 12 platform chemicals that who is based in Chennai, India.
However, to realize the full techno- can be produced from sugars via bio-
logical or chemical routes — 1,4-diac- Building blocks
1. A longer version of this article, which con-
tains additional process details and market in- ids (succinic, fumaric and malic acids), “After nearly two centuries, petroleum
formation, can be found online at www.che.com. 2,5-furan dicarboxylic acid, 3-hydroxy refineries are able to use proven, opti-
Browse the June 2009 issue or search the edito-
rial archives for this article title to access it. propionic acid, aspartic acid, glucaric mized technologies to produce a spec-
16 Chemical Engineering www.che.com June 2009
 Comparison of feedstock prices for the chemical industry
1,400 Maize Wheat
1,200 Sugar Crude brent
1,000
800
$/ton
600
400
200
0 lenge for any biorefinery. One classic
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Figure 2. Three of the most viable renewable feedstocks have enjoyed greater
price stability over the past few years than crude oil, the starting material for conven-
tional petrochemical feedstocks
trum of platform chemicals that serve
as chemical feedstocks for the down-
stream chemical industry,” says Luc
Moens, senior scientist, National Re-
newable Energy Laboratory’s National
Bioenergy Center (NREL; Golden,
Colo; www.nrel.gov). For developers
of renewable routes, efforts to take a
page from the petrochemical refinery’s
playbook have not been as straight-
forward as some might hope.
“Many of the classical unit opera-
tions from the petrochemical refiner-
ies, such as distillation, cracking and
conventional thermal processes such
as gasification and pyrolysis just
don’t work as well for renewable feed-
stocks,” says Bozell. “The high degree
of oxygenation associated with these
complex substrates hinders many
conventional chemical catalyst sys-
tems,” says Moens.
“This reduction either comes at the
cost of energy (for example, hydrogen
and natural gas) or through the loss of
carbon as CO2 and solid waste, all of
which increase capital requirements
and raw materials costs compared to
petroleum-based routes,” adds Bob
Maughon, Hydrocarbons & Energy
R&D director for Dow Chemical Co.
(Midland, Mich.; www.dow.com).
Instead of conventional catalysts,
many of the most well-developed,
biobased chemical production routes
in use today, such as fermentation,
rely on microbial or enzyme-driven
biochemical conversions, which are
challenging theselves, “Enzyme-based
processes have advantages [for renew-
able feedstocks], but they also have
some disadvantages,” says Maughon.
“They tend to be slower than chemi-
cal processes, they almost always re-
quire water to be present, and they
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Year
frequently suffer product inhibition.”
He adds: “Wresting products like alco-
hols and acids out of water often re-
quires massive amounts of energy, and
frequently requires steps to overcome
difficulties such as azeotropes.”
As a result, process developers have
been pursuing not only advanced en-
zymes to improve microbial and fer-
mentation processes, but advances
that will allow classical chemical pro-
cess and refinery techniques (such as
the use of thermal cracking, and acid
or base catalysis using homogeneous
and heterogeneous catalysts) to be
adapted for renewable feedstocks, as
well. “Once perfected, such techniques
are expected to offer advantages over
purely biological processing methods
of biomass,” says Bozell.
Looking at lignin
“Lignin is unique among its biomass
counterparts, in that it is the only
renewable source of aromatics — an
important, high-volume class of com-
pounds,” says Bozell. “The ability to
carry out direct, efficient conversion
of lignin to low-molecular-weight aro-
matics (including the BTX chemicals
benzene, toluene and xylenes) is an
attractive goal, but it is particularly
challenging due to the difficulties as-
sociated with separating lignin from
lignocellulosic feedstocks.”
According to DOE, process devel-
opers working with lignin have had
promising early success using gasifi-
cation to convert lignin into syngas
(carbon monoxide and hydrogen) and
eventually mixed alcohols, and pyrol-
ysis to convert lignin into gasoil and
other pyrolysis oils. These efforts have
fueled interest in the development of
other processes and improved cata-
Source: Frost & Sullivan
lysts to convert plentiful lignin into
downstream chemicals.
One key to using lignin is the sepa-
ration of biomass into its three main
components (lignin, cellulose and
hemicellulose). Today, effective up-
front separation remains a huge chal-
7-08
9-08
11-08
approach (dilute acid pretreatment)
removes a significant portion of the
hemicellulose, but leaves the remain-
ing two fractions (cellulose and lignin)
commingled, and “thus not available
in as useful a form,” says Bozell.
Advances in the use of acid or base
treatments, steam treatment and sol-
vent fractionation “appear to offer good
access to the components in biomass
and help to reduce the complexity of
the heterogeneous starting materials,
yielding simpler molecules, carbohy-
drates, lignins and plant-based hydro-
carbons,” says Bozell.
One solvent-based process devel-
oped by NREL, called Clean Frac-
tionation (CF), is able to isolate and
purify chemical-grade cellulose from
lignocellulosic materials. Designed
as a front-end pretreatment step for
biorefineries, the process separates
the previously commingled lignin/
hemicellulose streams, making both
available for chemical production.
First, the cellulosic feedstock is
treated with a ternary mixture of
methyl isobutyl ketone (MIBK), eth-
anol and water in the presence of a
dilute acid promoter such as sulfuric
acid, and the mixture is heated at
140°C for less than one hour. The sol-
vent mixture selectively dissolves the
lignin and hemicellulose components,
leaving the cellulose as an undissolved
solid material that can be washed, fi-
berized and further purified.
The soluble fraction containing both
lignin and hemicellulose is treated
with water, resulting in a phase sep-
aration into an organic phase con-
taining the lignin, and an aqueous
solution containing the hemicellulose-
derived sugars (pentosans). More than
95% of the components in the starting
feedstocks can be isolated, says Moen.
The process normally gives a cellulose
yield of about 47–48 wt.%, in compari-
son to maximum yields of about 40%
using conventional pulping processes.
The CF process also allows for 99%
Chemical Engineering www.che.com June 2009 17
 Source: Dr. Joseph Bozell,
Fuels (convergent) University of Tennessee (Knoxville)

Technology 1
Newsfront Technology 2 Single product Figure 3. While the ‘single-product’
Technology 3 (e.g., EtOH) approach has dominated the commercial-
etc. ization of many biobased chemicals and
plastics processes to date, many say that
recovery of the organic sol- Chemicals (divergent) the cost-effective biorefinery concept of
Product 1
vents, and produces no odorous Single technology tomorrow will be predicated on the ability
Product 2 to convert key renewable feedstocks into
emissions, says Bozell (who led (e.g., selective
oxidations) Product 3 intermediate ‘platform chemicals,’ which
the CF process development can be further processed to produce a
etc.
at NREL for 10 years before broad slate of value-added chemicals
moving to the University of
Tennessee). “This provides new op- feedstock propylene oxide, PG is used also reduces wastewater generation
portunities for the use of sugar cane in the manufacture of various plastics by over 90% and consumes 30% less
bagasse and other lignocellulosic and plasticizers, solvents, hydraulic energy compared to the conventional
feedstocks as chemical feedstocks,” fluids and lubricants, heat-transfer technology. Dow has had a GTE dem-
adds Moens. fluids, and more. onstration unit running at its Stade,
To take advantage of this sudden Germany, site since 2006, and in 2008
Levulinic acid availability of excess glycerin supply, announced plans for its first commer-
Levulinic acid (LA) is a diverse plat- at least a half dozen chemical compa- cial-scale GTE facility in China.
form chemical. This five-carbon com- nies (including Dow Chemical, Hunts- Similarly, in April 2007, Solvay
pound, traditionally produced from man Corp., ADM and others) are Chemicals (Brussels; www.solvay.
maleic anhydride and other petro- working in parallel to build grassroots com) started up a 10,000-m.t./yr plant
chemical feedstocks, has historically chemical plants to convert biodiesel- that produces epichlorohydrin at its
found use in the manufacture of ad- derived glycerin into PG. Tavaux, France, site, from biodiesel-
hesives, rubber, plastics, and synthetic However, “while near-term crude derived glycerin, using the company’s
fiber products. glycerin is in excess, the longterm patented Epicerol process (for more,
Today, it can be produced through view could change, as next-generation see CE, March 2006, p. 14, and April
the acid-catalyzed hydrolysis of cellu- biodiesel processes make no glycerin 2006, pp. 27–30). The company is now
lose (using, for instance, sulfuric acid). and renewable processes are already moving forward with a 100,000-metric
“Levulinic acid should receive much consuming this surplus,” says Maug- ton (m.t.)/yr Epicerol production facil-
more attention than it has, because it hon of Dow. He also notes that many ity in Map Ta Phut, Thailand, with
is such a versatile and reactive mol- of the technologies known today still startup slated for 2010.
ecule, from which numerous deriva- have competitive cost issues and prod-
tives can be synthesized,” says Moens. uct quality issues (especially around PDO and bioplastics
“When you consider how many chemi- pharmaceutical grades) that must be Two different renewable routes (based
cals can be made from levulinic acid — reconciled before they can be used on corn sugar and glycerin) have been
including levulinate esters, N-meth- more broadly on a commercial basis. commercialized for another widely
ylpyrrolidone, 1,4-butanediol, succinic used propanediol — 1,3-propanediol
acid, pyrrolidine, lactones, acrylic acid, Epichlorohydrin production (PDO), a premium-price intermediate
and furans, to name a few — you see Today, several major chemical compa- used in the production of polymers,
the versatile nature of this chemical. nies are also developing and commer- cosmetics, liquid detergents, anti-
And the ability to produce this cellu- cializing processes to produce epichlo- freeze, de-icing and heat transfer flu-
lose-derived platform chemical from rohydrin — a high-volume commodity ids and other products. Details about
waste materials, such as sugar cane chemical used largely in the synthesis the corn-sugar-based route from Du-
bagasse and other lignocellulosic feed- of epoxy resins — from biodiesel-de- Pont Tate & Lyle Bio Products LLC
stocks provides a compelling driver for rived glycerin. The conventional route (Wilmington, Del.; www.dupont.com),
process developers.” relies on propylene and chlorine as the and the glyerin-based route from
primary raw materials, but has par- Metabolic Explorer (Metex; Clermont-
Biodiesel’s downstream bounty ticularly low chlorine-atom efficiency, Ferrand, France; metabolic-explorer.
During the production of biodiesel, the so it produces unwanted byproducts com) and Institut Francais du Petrole
transesterification of feedstock veg- hydrogen chloride or waste chloride (IFP; Rueil-Malmaison) can be found
etable oils and animal fats produces anions that are expensive to dispose in the longer version of this article.1
one pound of glycerin for every nine of, says John Briggs, chemistry and Several facilities that are already pro-
pounds of diesel (or, stated another catalysis scientist for Dow. ducing plastics from ag-based starting
way, 1.25 lb of glycerin is produced for Dow’s two-step glycerin-to-epichl- materials are also discussed.
every gallon of biodiesel). Swift growth rohydrin (GTE) process provides a As interest in renewable feedstocks
in worldwide biodiesel capacity in re- variety of advantages over the multi- continues to grow, many stakeholders
cent years has created an abundant step incumbent process, including (but are channeling the spirit of the fairy
supply of byproduct glycerin, which not limited to) fewer unit operations, tale Rapunzel — spinning straw and
has fueled interest in processes to smaller environmental footprint and other low-cost, renewable agricultural
convert glycerin into propylene gly- overall cost, reduced equipment re- and forest products into value-added
col (1,2-propanediol; PG; see also CE, quirements, shorter residence times, chemicals that are worth their weight
Outlets for glycerin, Sept. 2007, pp. fewer reaction byproducts and a purer in gold. ■
31–37). Traditionally made from fossil final product, says Briggs. The process Suzanne Shelley
18 Chemical Engineering www.che.com June 2009