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Biomass Chemicals 1

Biomass Chemicals
Barbara A. Tokay, Englewood, New Jersey 07631, United States

1. Introduction . . . . . . . . . . . . . . . . 1 4.5. Oilseed Chemicals . . . . . . .. . . . . 4


2. Raw Materials . . . . . . . . . . . . . . 1 4.6. Furfural and Its Derivatives . . . . . 4
3. Process Technology . . . . . . . . . . . 2 4.7. Cellulose Polymers . . . . . . .. . . . . 5
4. Biomass Chemicals . . . . . . . . . . . 3 4.8. Lignin Chemicals . . . . . . .. . . . . 5
4.1. Ethanol and Its Derivatives . . . . . . 3 4.9. Methanol . . . . . . . . . . . . .. . . . . 5
4.2. Other Fermentation Chemicals . . . 3 4.10. Methane . . . . . . . . . . . . .. . . . . 6
4.3. Sugar Chemicals . . . . . . . . . . . . . 4 5. Future Contributions . . . . .. . . . . 6
4.4. Starch Chemicals . . . . . . . . . . . . . 4 6. References . . . . . . . . . . . .. . . . . 6

1. Introduction United States, the biomass chemical receiving


the most attention was ethanol made by fermen-
Biomass chemicals are those chemicals made tation of grain (→ Ethanol). Ethanol was, at that
from renewable, organic materials. Most time, vigorously supported by the federal gov-
biomass materials are plant products or wastes, ernment as a gasoline extender and octane en-
but animal products, such as fats or manures, hancer. Other biomass-based commodity chem-
also are included. icals receiving attention at that time were meth-
Although this category enjoyed renewed in- anol, acetic acid, butanol/acetone, and ethanol
terest because of the oil crises during the derivatives.
1970s, biomass chemicals are not new in- Petroleum prices have stabilized and most
ventions. In fact, at one time, the chemi- United States’ chemicals producers have aban-
cal industry was largely based on chemical doned their interests in biomass commodity
products made from wood, sugars, starches, chemicals [3]. However, several manufacturers
and animal fats (→ Wood, → Sugar, → Starch, are developing new lines of biomass specialty
→ Polysaccharides, → Fats and Fatty Oils) [1]. chemicals, such as novel starch polymers [1],
Some biomass chemicals are still staples of [2, p. 147], [4], new lignin chemicals [4–6], and
chemical industry. Cellulose fibers, for example, polysaccharide gums [3].
command large markets even after years of com- The rapid rise and fall of interest in biomass
petition from petroleum-based materials. Many chemicals parallels, in part, the curve of
other biomass chemical processes were in oper- petroleum prices, but other characteristics of
ation until the 1960s, and some are still operat- biomass chemicals have contributed to the cau-
ing in developing nations or in countries with- tious attitude toward their redevelopment. These
out ready access to petroleum [2]. Among the characteristics and the potential for development
biomass chemicals that are, or were, important and manufacture of new and old biomass chem-
are ethanol, acetone/butanol, itaconic acid, lactic icals are detailed in the following sections.
acid, xanthan gum, sorbitol, industrial starches,
fatty acids and alcohols from vegetable and an-
imal sources, glycerol, soap, furfural and its 2. Raw Materials
derivatives, rayon, cellophane, carboxymethyl-
cellulose, lignosulfonates, tall oil, vanillin, and One major problem in organizing production of
methanol. biomass chemicals is the diversity of materi-
During the oil shocks of the 1970s, a num- als from which these chemicals may be made.
ber of chemical companies decided to take an- The biomass feedstock category is vast; it in-
other look at biomass chemicals [3]. In the cludes grains, sugar crops, oilseed crops, agri-

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim


10.1002/14356007.a04 099
2 Biomass Chemicals

cultural wastes, food processing wastes (liq- 3. Process Technology


uid and solid), wood, wood chips, bark, mill
residues, forest residues, pulping liquors, ani- Because biomass materials are complex in com-
mal fats, manures, algae, and exotic crops, such position, conversion of these substances to
as guayule, jojoba, and euphorbia. chemicals is often inefficient [1], [10]. Plant ma-
All biomass materials contain carbon, hydro- terials, for example, contain three major com-
gen, and oxygen, but the chemical composition ponents: cellulose, hemicellulose, and lignin
of each type of material is unique. Because most (→ Cellulose, → Lignin). If a chemical process
biomass materials contain considerable amounts uses only one component and the others be-
of oxygen (as much as 40 %), they are generally come wastes that must be disposed, the pro-
considered to be most useful as sources of oxy- cess often becomes uneconomic. In traditional
genated chemicals [7], [8]. wood pulping, for example, cellulose for cel-
The diversity of biomass materials means lulose fiber and chemical production is sepa-
that each biomass chemical process must be de- rated from lignin and hemicellulose fractions,
signed to use a specific type of material. Un- which are usually burned for their energy content
like petroleum, which is a much simpler, more or occasionally made into specialty chemicals.
homogeneous material, biomass from different New wood chemicals processes would almost
sources is not interchangeable. certainly have to include higher-value uses for
Production and collection of biomass feed- the lignin and hemicellulose. Some biomass ex-
stocks also present problems. If a process uses perts have suggested that a “biomass refinery”
a well-known biomass feedstock, for example, concept is necessary to any successful biomass
starch, then production and collection is simple chemicals plan in the future [4], [11].
because a starch-processing industry already ex- Separation of the components of lignocellu-
ists. However, use of starch for production of lose materials without intensive use of chemi-
new chemicals or for increased production of cals and energy, as is done in traditional wood
conventional starch-based chemicals may create pulping, is no easy matter. Development of
competition with existing starch markets. The new process technology that would convert the
same line of reasoning applies to the use of tim- six-carbon sugars of wood cellulose to ethanol
ber or pulp-grade wood as a feedstock for chem- has been slowed considerably by the separation
icals production. problem, although it was the subject of intensive
If a nonconventional biomass feedstock is se- research [10].
lected, agricultural residues, for example, then Biomass chemicals made from a purified
collection of this dispersed material poses lo- component of lignocellulose are often produced
gistical problems. In general, biomass wastes via fermentation. Feedstock for these chemicals,
are bulky, dispersed, and difficult to collect and which include ethanol, butanol/acetone, citric
transport economically for any appreciable dis- acid, and xanthan gum, is usually sugar or starch
tance. [2, pp. 5, 71]. Fermentation is a well-established
The biomass chemicals processes in opera- process, but there are some problems in its wider
tion today use conventional biomass feedstocks application to chemical production. A typical
(sugar, starch, wood) or biomass wastes (forest fermentation produces a dilute product stream
residues, pulping liquors, agricultural residues). containing 10 % or less of the desired prod-
Investigations are under way on new crops, such uct, which must then be concentrated. Ethanol
as guayule, jojoba, euphorbia, or crambe, that is usually separated from the fermentation beer
can be grown on currently uncultivated land and by energy-intensive distillation. There has been
used exclusively for chemicals production [9]. much research and development on ethanol sep-
Some of these projects, as well as creation of aration and progress has been made, but the
short-rotation forestry projects, still need fur- problem is by no means eliminated [8].
ther development of production and collection Biomass chemicals may also be made by
infrastructures, processing industries, and mar- chemical conversion routes. Chemically mod-
kets. ified industrial starches are produced by this
route, as are the starch-based polymers [1], [2,
pp. 137 – 154]. Vegetable-oil-based fatty acids
Biomass Chemicals 3

and alcohols are other products manufactured Ethanol may be converted to ethylene by pass-
via chemical process routes [2, pp. 155 – 223]. ing ethanol vapor over a heated fixed-bed alu-
Because separation of biomass components is mina catalyst. The ethylene – water mixture is
often difficult and costly, some biomass chem- quenched and the two components separated [2,
icals are made by thermochemical routes that pp. 40 –47]. Although this route would be pro-
use the entire material. The destructive distil- hibitively expensive in countries with a well-
lation of wood to methanol [67-56-1] is the developed petrochemical industry [1], [7], the
oldest and best known example of this type ethanol-to-ethylene method is used in Brazil,
of process(→ Methanol). The newer processes which has a large government-supported fer-
gasify biomass to synthesis gas, then reform it mentation ethanol program.
to methanol (→ Gas Production). Acetaldehyde, now made via a petrochem-
Biomass may also be gasified to methane or ical route, can also be produced from ethanol
pyrolyzed to tars and liquid hydrocarbon prod- (→ Acetaldehyde, Chap. 4.1.). Ethanol is va-
ucts. Most work on gasification and pyrolysis porized and passed over a heated, fixed-bed
for chemical production is in the laboratory or chromium-activated copper catalyst. Hydrogen
in early pilot plant development [12]. is separated from the acetaldehyde and untreated
Another whole material chemical conversion ethanol is recycled. Acetaldehyde may also be
route involves anaerobic digestion of biomass converted to n-butanol via acetaldol and croton-
solids or liquids. Developed as a method aldehyde, although this process is expensive [2,
for treating liquid sewage, methane-producing pp. 48 – 54].
anaerobic digestion was initially conceived as a Butadiene was once produced from ethanol in
less energy-intensive method of reducing chem- a single-step process in which acetaldehyde and
ical oxygen demand of wastes. The process was ethanol were passed over a tantalum oxide on sil-
also explored as a means of producing pipeline- ica gel catalyst. Energy intensive distillation op-
quality methane. erations necessary for product purification make
this process expensive [2, pp. 62 – 70].

4. Biomass Chemicals
4.2. Other Fermentation Chemicals
4.1. Ethanol and Its Derivatives Although ethanol production is the best known
chemical fermentation process, there are many
The biomass chemical that has attracted the most others. The butanol/acetone fermentation, still
interest in the early 1980s was ethanol [64-17-5] operated in South Africa, was once of great
(→ Ethanol) [1], [4], [13]. In the United States, industrial importance (→ Acetone, Chap. 4.6.;
production of fermentation ethanol for use as a → Butanols). Raw material for the process is
fuel extender was supported by a fuel tax ex- grain or molasses, and the anaerobic fermen-
emption that extended to the end of the 1980s. tation uses the bacterium Clostridium aceto-
The effect of this tax incentive has been a large butylicum. The fermentation process produces
growth in production of fuel and industrial-grade a 60 : 30 : 10 mixture of butanol/acetone/etha-
fermentation ethanol. Industrial grade fermenta- nol, which must be separated by distillation [2,
tion ethanol is displacing synthetic ethanol in the pp. 76 – 83].
chemicals market and some analysts predicted Submerged aerobic fermentations for an-
that the industrial ethanol market would be dom- tibiotic production, initially developed during
inated by fermentation ethanol by 1990 [13]. World War II, opened up new chemical pro-
Fuel ethanol is made by traditional batch fer- duction routes. Citric, gluconic, and itaconic
mentation of starches or sugars with the yeast acids are made by this route, as is xanthan
Saccharomyces cerevisiae. New continuous fer- gum, a polysaccharide with applications as
mentation processes are approaching commer- a thickener, emulsifier, and stabilizer of food
cialization [14]. products (→ Citric Acid, → Gluconic Acid,
Biomass-based ethanol may be converted → Polysaccharides) [15]. Xanthan gum and
to other large-volume commodity chemicals. other similar polysaccharides may have poten-
4 Biomass Chemicals

tial as oil recovery agents or in oil clean-up ap- Although biomass fatty acids have suffered
plications [16]. from competition from petrochemical equiva-
lents, they still retain sizable market shares in
surfactants, paint binders, and plasticizers.
4.3. Sugar Chemicals Natural fatty acids are made by hydrolyzing
fats or plant oils with high-pressure steam, which
Pure dextrose, usually obtained from starch, is requires investment in high-pressure equipment
the raw material for manufacture of sorbitol, a plus extensive vacuum distillation capacity to
well-established chemical used in foods, denti- fractionate the acid mixture. The products find
frices, and cosmetics, and as a chemical interme- big markets, however, in surfactants, plasticiz-
diate (→ Sugar Alcohols) [2, pp. 129 – 136]. Su- ers, greases, synthetic lubricants, cosmetics, toi-
crose polyols also have a role in urethane foam letries, textile chemicals, emulsifiers, secondary
manufacture. petroleum recovery products, and mineral ben-
eficiation [2, pp. 155 – 223]. Processes and mar-
kets are described in more detail under → Fatty
4.4. Starch Chemicals Acids.
Triglycerides also yield long-chain fatty al-
More than half the starch isolated from grains cohols, which have lubricant and surfactant ap-
and potato crops is converted into sugars. plications. Soap, another natural oil product, has
The remainder has many industrial applications lost ground to synthetic detergents, but glycerol,
(→ Starch). Industrial starch may be used as is which is a byproduct of soap or fatty acid manu-
or it may be modified by partial depolymeriza- facture, holds its own against synthetic glycerol.
tion to dextrins or by chemical reactions that Fatty acid derivatives, such as azelaic and
replace the hydroxyl groups of the dextrose unit pelargonic acids, formed by ozonolysis from
with other substituents. Among the many modi- oleic acid, find niches in specialty markets. Aze-
fied starches are oxidized starch, acetates, phos- laic and pelargonic acids are used in modified
phates, amino alkyl ethers, and other ethers. polyester fibers, elastomers, adhesives, plasti-
These large-volume, inexpensive materials are cizers, synthetic lubricants, and surface coat-
used as paper and textile sizes and as binders [2, ings. Nylon 11, made from ricinoleic acid de-
pp. 137 – 146]. rived from castor oil, is marketed as a plas-
Some more drastically modified starch chem- tic for molded parts in automobiles, conveying
icals have also been introduced. A starch- equipment, and other machinery. Other special-
acrylonitrile graft copolymer, developed and li- ized nylons may also be made from natural fatty
censed by the USDA, has specialty uses in per- acids. Nylon 9 is derived from soybean oil; ny-
sonal care products and in medical applications. lon 1313 is made from erucic acid from crambe
A starch slurry is treated with acrylonitrile in the oil.
presence of a ceric ammonium nitrate catalyst in Jojoba oil, extracted from the seed of the jo-
nitric acid. The product, called “Super Slurper,” joba plant, an exotic desert shrub, is used in cos-
absorbs hundreds of times its mass in water [2, metics. Its structure is very close to that of sperm
pp. 147 – 154]. oil, now on the proscribed list in many nations
Another starch-based chemical is α –methyl because of efforts to save the near extinct sperm
glucoside, a starch polyol used in production of whale. Jojoba oil producers are trying to intro-
rigid urethane foam (→ Polyurethanes) [7]. duce the oil, an ester of a long-chain fatty acid
and a long-chain alcohol, into the high-pressure
lubricant market and perhaps to the automobile
4.5. Oilseed Chemicals lubricant market [9].

Linseed, soybean, cottonseed, coconut, palm,


and other plant oils and animal fats have always 4.6. Furfural and Its Derivatives
been important raw materials for chemical man-
ufacture. These oils contain a mixture of triglyc- Furfural (2-furaldehyde) [98-01-1] and its-
erides of fatty acids in the 8 to 20 carbon range. derivatives, furfuryl alcohol [98-00-0], furan
Biomass Chemicals 5

resins, and tetrahydrofuran [109-99-9], are pro- streams, which contain chemicals from the pulp-
duced in many countries from corn cobs, wheat ing process, are usually burned for their energy
and oat hulls, and many other biomass materials value, but a small portion is converted to a vari-
(→ Furan and Derivatives, → Tetrahydrofuran). ety of chemicals.
Furfural, which is derived from the pentoses Neutral sulfite semichemical pulping yields a
(five-carbon sugars) present in hemicellulose, black liquor from which acetic and formic acids
one of the major components of lignocellulosic may be extracted. Kraft black pulping liquor
materials, is produced by steam treatment fol- may be a source of dimethyl sulfoxide, which is
lowed by dehydration. Furfural was often men- made by heating the liquor to convert the lignin
tioned in the early 1980s as a possible new methyl groups to methyl sulfide. Oxidation then
product for developing countries with plentiful produces dimethyl sulfide [2, pp. 295 – 302].
biomass resources, and several nations have suc- Sulfonated lignins, a major component of
cessfully established plants [13]. Kraft black liquor, can be recovered as lig-
One-third of the furfural produced is used as nosulfonates, which are used as dispersants,
a solvent; the other two-thirds is used as an in- sequestrants, emulsion stabilizers, and humec-
termediate in the manufacture of furfural deriva- tants. Crude calcium lignosulfonate can be ox-
tives. The most important furfuryl alcohol, used idized to vanillin, which competes with the ex-
to produce furan resins for foundry sand binders. tract from the vanilla bean [2, pp. 311 – 319].
Another derivative, tetrahydrofuran, can also be Tall oil is a byproduct of the Kraft process
produced via a petrochemical route. Other uses for pulping softwoods. Tall oil is a mixture of
for furfural, such as production of adiponitrile, rosin and a group of fatty acids (→ Tall Oil) [2,
might be found if furfural prices were reduced pp. 320 – 328].
by expanded production [13]. New lignocellulose separation processes,
such as steam explosion, have led to production
of an unmodified, low-molecular-mass lignin
4.7. Cellulose Polymers [5]. Although this material has yet to be widely
tested, it may be useful as a partial substitute for
Cellulose polymers, such as rayon, cellulose phenolic resoles in phenol – formaldehyde ad-
acetate, cellulose ester, cellophane, and mod- hesives. Other uses for this type of lignin have
ified cellulose, are still important in spite of also been suggested: binder for animal feeds, en-
heavy competition from petrochemical alter- capsulating agent, feed grain coating, road dust
natives. Markets and process technology for treatment chemicals, reinforcing fillers in rub-
these chemicals are described more fully under bers, and setting agent in Portland cement [5].
→ Cellulose, → Cellulose Esters. In addition use of lignin copolymers in drilling
Interest in cellulose stems from alternative muds has been discussed [17].
fuel research growing out of the oil crises of the Some proponents of “biomass refining” sug-
1970s. Cellulose is viewed as a possible source gest that lignin be hydrocracked and hydroalky-
of hexose sugars, which can be fermented to eth- lated to phenol and benzene [6], [11].
anol. New lignocellulose fractionation schemes
resulting from the cellulose-to-ethanol research
may contribute novel pulping technologies that 4.9. Methanol
will preserve the value of the hemicellulose and
lignin fractions of the lignocellulosic materials The old route to biomass methanol, often called
[4], [10]. wood alcohol, was destructive distillation. In this
method, 1 t of wood heated in steel ovens pro-
duces 0.25 t charcoal, 30 kg acetic acid, 10 kg
methanol, and 60 L tar and oil from low-energy
4.8. Lignin Chemicals
gas. This process is not economically feasible in
industrialized countries although it might be in
Paper pulp mills have long produced vast waste
less developed nations [2, pp. 339 –347].
streams containing the lignin (→ Lignin) and
New methods of methanol production require
hemicellulose fractions of wood. These waste
gasification of biomass, often in an oxygen-
6 Biomass Chemicals

blown gasifier, to produce synthesis gas, which is be necessary in development of new commodity
then reformed to give methanol. Several projects chemicals process technology [3].
are now in the pilot plant or demonstration stage Third, production of new biomass chemicals
(→ Methanol) [18]. will likely involve new collaborations between
producers of raw materials and chemical manu-
facturers. Such collaboration is now beginning
4.10. Methane between starch processing companies and a few
chemical manufacturers. Forest products com-
There are several ways to produce methane panies, which are likely suppliers of wood and
[74-82-8] from biomass. The most widely used wood wastes for chemical production, are much
is anaerobic digestion, a conversion process less interested at present in such collaboration
originally developed for clean up of low-strength [21].
organic liquid wastes. Anaerobic digestion is a
slow fermentation process in which a variety of
bacteria convert organic matter first to organic 6. References
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reactor designs and process research make this Processes that Use Biomass as a Raw
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5. Future Contributions Chemicals,” Chemical Business 1983 (August
22) 8 – 14.
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By-Product Lignins from Alcohol Fuel
must be met.
Processes,” Fourth Symposium on
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Biomass Chemicals 7

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International Conference on Microbial

Biopolymers → Cellulose
Biopolymers → Gelatin
Biopolymers → Lignin
Biopolymers → Nucleic Acids
Biopolymers → Proteins
Biopolymers → Starch
Biopolymers → Resins, Natural