Hydrolysis

Hydrolysis is the process by which water splits a larger molecule into two smaller molecules. In the case of the hydrolysis of polysaccharides to soluble sugars this is called “saccharifica­tion”. The goal of this process is the de-polymerization of cellulose and hemicelluloses into soluble monomer sugars (hexoses and pentoses). This can be accomplished by two different processes: (1) acid hydrolysis with a variety of low acid-high temperature or high acid-low temperature conditions being suitable to both the breakdown of the structure of the biomass and the release of free sugars, and (2) enzymatic hydrolysis after some sort of pretreat­ment which allows enzymatic attack of the polymers [22, 23]. The C6 dominated cellulose

Table 2.1

Overview pretreatment methods [9, 14-17].

Method

Technologies

Advantages

Disadvantages

Biological

Microbial

Good cellulose and lignin

Not very efficient

Fungal

degradation

Requires long treatment

Low energy requirements

times

No chemicals required

Physical

Freeze/thaw

No chemical or water

High energy input

Cycles

inputs

Limited effectiveness

Radiation

Mechanical

Sheering

No toxic residuals

Expensive

Thermal

Steam Explosion

Hydrolyzes significant

High energy input

Liquid Hot Water

fraction of hemicellulose

Often requires additional

Wet Oxidation

Prevents lignin

processing or the addition

re-precipitation

of a catalyst for maximum

Relatively well understood

yield

(Thermo-)

Acid Catalyzed

Hydrolyzes significant

Corrosion problems

Chemical

Nitric acid

fraction of hemicellulose

Some undesirable glucose

Sulfur Dioxide

Can reduce cost

degradation

Sulfuric acid

By-products can inhibit

Hydrochloric acid

fermentation

Phosphoric acid

(disadvantage less for diluted acids)

Base Catalyzed

More effective at

Not efficient when high

Ammonia (AFEX, ARP,

solubilizing a greater

lignin content

SAAa)

fraction of lignin

Environmental/safety

Lime (Ca(OH)2)

Can reduce cellulase

issues (except for lime)

Lye (NaOH, KOH)

requirement

Leaves much of the

Minimal formation of

hemicellulose in an

fermentation inhibitors

insoluble polymeric form

Solvent-Based

Very selective pretreatment

Significantly more

Organosolv

method yielding the 3

expensive

(Numerous organic or

separate fractions

High energy input

aqueous solvent mixtures

Very effective for

Solvents need to be

incl. methanol, ethanol,

high-lignin lignocellulose

drained and recycled

acetone, ethylene glycol

materials

Expensive

and tetrahydrofurfuryl

Recovery of relatively pure

Significant negative

alcohol)

lignin as a by-product

effects on cellulase

Ionic Liquids

Environmental friendly

activity possible

Minimal formation of degradation products

Further research needed

Other

Low environmental impact

High cost of equipment

CO2 Explosion

Increases accessible surface

Lignin and hemicelluloses

area

not affected

Cost effective

Very high pressure

No generation of toxic

requirements

compounds

Hydrolytic yield increases proportionately with the moisture content of the

unprocessed feedstock

1AFEX: Ammonia Fiber Expansion; ARP: Ammonia Recycled Percolation; SAA: Soaking Aqueous Ammonia.

can be enzymatically hydrolyzed by cellulases; for the C5 dominated hemicellulose the hemicellulases (such as xylanase) can be used.

Acid (sulfuric or hydrochloric) can serve both for disruption and hydrolysis of the cellulosic polymers and is currently seen as the most technologically mature method of sugar release from biomass. A major disadvantage of acid hydrolysis is the potential degradation of the released monosaccharides that leads to reduced sugar yields [13, 23]. Other drawbacks are the cost of acid, the requirement to neutralize the acid after treatment and the production of inhibitory by-products such as furfural and hydroxymetyl furfural [22, 24, 25].

Enzymatic degradation of lignocellulosic biomass on the other hand is very specific and side reactions, such as degeneration of sugars, do not occur. High yields are therefore possible. In addition, the mild conversion conditions lower the maintenance costs of the production plant [23]. High temperature and low pH tolerant enzymes are preferred for the hydrolysis due to the fact that most current pretreatment strategies rely on acid and heat [26]. In addition, thermostable enzymes have several advantages, including higher specific activity and higher stability, which improve the overall hydrolytic performance [27]. Ultimately, improvement in catalytic efficiencies of enzymes will reduce the cost of hydrolysis by enabling lower enzyme dosages [7].

Although acid hydrolysis methods have long industrial histories and are, therefore, more mature, enzymatic hydrolysis is seen as the most economically promising method for redu­cing costs while improving yields and a key to cost-effective production of monosaccha­rides [28]. Research is focusing on advanced screening processes of natural enzymes and developed man-made enzymes to increase the efficiency and improve enzymatic hydrolysis [29].