Index

[Xihua part]

1. Pretreatment and hydrolysis of rye shred

1.1. Mixing
1.2. Gelatinization
1.3. Liquefaction
1.4. Saccharification
2. Suggested process parameters
2.1. Optimum process variable for the mixing step
2.2. Optimum process variable for the Liquefaction step
2.3. Optimum process variable for the saccharification step
3. Literature
1. Pretreatment and hydrolysis of rye shred

The pretreatment and hydrolysis of rye shred is an important step in the production of
Bioethanol. The step contains the general upstream processes gelatinization, liquefaction
and saccharification.

1.1 Mixing

Rye shred containing starch in its native form is only slowly degradable. The Rye shred needs
to be mixed with water to make the starch susceptible to enzymatic breakdown [1]. The Rye
shred starts to absorb water of the suspension and swell to a limited extent. The ratio
between the Rye shred and the water is an impotent factor for the economy of the process.
A to high amount of dry matter in the dry matter suspension of Rye shred and water would
result in a high viscosity. This will cause several problems as for instance in the heat
exchange, the enzyme kinetics and the overall mixture of the suspension. The overall amount
of energy and therefore the cost will increase with the viscosity. In opposite, if the amount of
dry matter in the dry matter suspension of Rye shred is to low it results in poor economy of
the process. The most common dry mater content in the suspension is 30-40% [1].

1.2 Gelatinization

A further breakdown of the Rye shred structure is achieved by applying heat to the
suspension. The heat increases the breakdown of the hydrogen bondings and the adsorption
of water in the Rye shred. The Rye shred continues to swell till the gelatinization
temperature is reached. At this point the maximum viscosity will be reached will the Rye
shred structure breakdown, releasing the starch to the suspension as shown in fig1.
 Fig.1: gelatinization temperature

The gelatinization temperature varies with the source of the starch and the size of the
granules. Large granules tend to swell stronger as small granules because larger particles are
less affected by molecular bonding’s and have consequently a lower gelatinization
temperature. The different sources of starch vary in the content of amylose in the grain and
therefore in the amount of hydrogen bonds. A high amount in the starch source result in an
increased gelatinization temperature [2]. The usual range of the gelatinization temperature
for Rye grain is 57-70°C as shown in Table 1 [3].

Table1.: Gelatinization temperature ranges of various feedstock’s

1.3 Liquefaction

During the liquefaction step, starch is converted to oligosaccharides of varying length by

hydrolyzing the starch with the thermo tolerant form of the endo-acting enzyme α-amylase.
The enzyme hydrolyzes the (1-4)-glucosidic bonds of amylose (fig.2) and amylopectin (fig.3).
The oligosaccharides resulting from this process can’t be preceded by yeast. α-amylase can’t
hydrolyze (1-6)-glucosidic bonds of amylopectin [2].
The purpose of the liquefaction step is therefore mainly the reduction of the viscoses for the
saccharification step.

Fig.2: Struckture of Amylose

1.4 Saccharification

During saccharification the (1-6)-glucosidic bonds of amylopectin (fig.3) are hydrolyzed by the
enzyme glucoamylase, resulting in glucose that can be processed by yeast to ethanol.
The saccharification step can be carried out as a pre-step of the fermentation or
simultaneous with the fermentation in the fermenter. Both possibilities have their
advantages and disadvantages. A simultaneous saccharification together with the
fermentation reduces the amount of reactors and reduces the risk of substrate inhibition in
the fermentation step, resulting in higher yield. The disadvantages of the simultaneous
saccharification are mainly the process conditions. The temperature and the pH value need
to be adjusted to the fermentation process resulting in a lower yield and higher process
times.
Fig.3: Structure of amylopectin
2. Suggested process parameters
Several parameters influence the yield of the reactions. The optimal values vary in the
literature sources. The main source used to estimate the optimal conditions is article [4]. The
paper is used because of the same starch source used in the experiments and the
comparison given by the experiments and literature research in the paper. The data in the
experiments is in the range of literature date but more precise. An overall Yield of 96% can
be expected with the given data

2.1 Optimum process variable for the mixing step:

The optimum values are suggested to be 35% solids(w/w) and a temperature of 60°C, based
on the given literature data in Tab.2

Table.2: Literature values for pre-mixer

Article [2] Article [3] Article [1]

%Solids (w/w) 30 29-33 30-40
Temperature (°C) 55-65 60 -

2.2 Optimum process variable for the Liquefaction step:

Experimental results of the Institute of Agricultural Engineering Bornim [4] used as the
optimum process variables:
Particle size [4]: 2,72 mm
Temperature [4]: 83 °C
pH-value [4]: 5,85
duration [4]: 2 h

Table.2: Literature values for liquefaction

Article [2] Article [3]

pH-value 5,4-5,8 5,5-5,7
Temperature (°C) 89 85
Enzymes (kg/ton starch) - 0,4-0,6 (Termamyl 120L)
 Termamyl 120L has an activity of 120 U/Kg. An cheaper and less active enzyme with 80 U/Kg
is used in the process. Therefore 0,9 Kg/ton starch need to be used to achieve the same
results.
2.3 Optimum process variable for the saccharification step:

Experimental results of the Institute of Agricultural Engineering Bornim [4] used as the
optimum process variables:
temperature [4]: 52 °C
pH-value [4]: 4
duration [4]: 2 h

Table.3: Literature values for saccharification

Article [2] Article [3] Article [5]

pH-value 5,5 4-5,5 5
Temperature (°C) 58 60 60
Enzymes (kg/ton - - 1,2 (AMG 300L)
starch)

AMG 300L has an activity of 300 U/Kg. An cheaper and less active enzyme with 150 U/Kg is
used in the process. Therefore 2,4 Kg/ton starch need to be used to achieve the same results.
Literature

[1]

Handbook of Starch Hydrolysis Products and their Derivatives, Kearsley, W., Dziedzic, S.Z., ISBN
9780751402698, 1995, Springer US

[2]

Aldén, Anna. “Optimization of the Liquefaction Process in Bioethanol Production and Development of
Method for Quantification of Nonsolubilized Starch in Mash”. Master Thesis, University of Linköping,
2008

[3]

K. Jaques, T. Lyons, and D. Kelsall, The Alcohol Textbook, chap. 3, Nottingham

University press, , 4 ed., 2003, ISBN 1-897676-13-1.

[4]

K. Richter, C. Berthold, Biotechnological Conversion of Sugar and Starchy Crops into Lactic Acid,
Journal of Agricultural Engineering Research, Volume 71, Issue 2, October 1998, Pages 181-191, ISSN
0021-8634

[5]

“Efficient and quick saccharification”, ® Novozymes A/S · No. 2004-03816-03