Bioethanol

from corn
and straw

Waste Management
& Valorization

Professors:

Inmaculada Sanz and

Carme Güell

Group 5:

Tùng Phạm
Paul Gustavino
Teresa
Introduction:

Catalonia, although is a very industrialized zone, also is a large agricultural and wine
producing region, that's why it is important to know how to manage the big quantity of
organic waste that generates the agricultural and winery sector. A very good
alternative is to produce bioethanol from these organic wastes.
Bioethanol, defined as ethyl alcohol originated from biological sources, is derived from
fermenting the sugar component of plant material. In this project we will use the
waste of winery production which is the grape pomace and lees.

Bioethanol is viewed as an alternative to fossil fuel because it is seen as a renewable

resource that may be exploited using more environmental friendly technologies.
Ethanol has the advantage of being a renewable fuel because it has a high miscibility
with the gasoline. Therefore, the use of ethanol in compression ignition engines has
received considerable attention in recent years because it can be used in unmodified
petrol engines with traditional fuelling infrastructure and is easily applicable as
additive for gasoline.

There are three main approaches to producing bioethanol from biomass materials:

1. Conventional fermentation of sugars obtained from sugar and starch crops.

2. Hydrolysis of cellulose to sugars using acid or enzymes followed by fermentation of

the sugars.

3. Gasification of any biomass to syngas followed by catalytic conversion to bio-

ethanol.

In this project we will use the hydrolysis of cellulose to sugars using acid or enzymes
followed by fermentation of the sugars obtained from the waste of winery production.
In the Hydrolysis process we broke the chain of cellulose in order to get the sugars.
In the fermentation process, which is a series of chemical reactions that convert sugars
into ethanol, the reaction is caused by yeast or bacteria. Ethanol and CO2 are
produced as the sugar is consumed. The simplified fermentation reaction equation for
the 6-carbon sugar, glucose, is:

Once we get the Ethanol we will separate it from the water using membrane process.
The viability of the process is good, obtaining for each ton of waste a yield of between
17-20%.
With the rest of the waste, it is sent to a composting plant where it is transformed as
fertilizer. Without this treatment it would not be good for the soil because of the
amount of pathogens it carries.
Process:

A Biochemical conversion uses enzymes

and microorganisms to convert biomass
into sugar and those sugars into,
(Bioethanol).
After Grapes Pomace is collected,
Grapes Pomace (GP) milled (to increase
the surface area) to enhance the break
down with enzymes in subsequent steps.
Steam or water, in the presence of acid is
used for pretreatment, to break down
the GP into cellulose, hemicellulose, and
lignin.
Enzymes can’t operate in highly acidic
conditions, so a base is used to balance the pH and the mixture is cooled before the
enzymes are added.
Enzymes perform a chemical reaction called hydrolysis. During this process the
enzymes break the cellulose chains into glucose and the hemicellulose chains into
xylose. Glucose and xylose are the sugars that can most readily be fermented into
ethanol.
During the fermentation process, the mixture is inoculated with yeast that digest the
sugars. Yeast break down complex carbohydrates (Glucose...) into simple sugars, and
used to ferment into ethanol and carbon dioxide.

Fermentation Equation:

C6H12O6 (aq) yeast Enzymes 2CH3CH2OH (aq)+2CO2(g) + Heat

Fermentation condition:

Fermentation takes place in an anaerobic condition reaction temperature at 37oC (the

optimum temperature for enzyme performance).
The reaction is exothermic, so we must ensure heat dose not build up and increased
the temperature above 37oC, the higher temperature will deactivate the enzyme.
Ethanol concentration can increase up to 15% before yeast dies so we need control the
concentration limit up to 12%.
This conversion process takes approximately three to five days.
The liquid can be separated by distillation, which is a method of separating mixtures
based on differences in their boiling points, but in this project we suggest to make the
separation by membranes.
The resulting ethanol is collected and purified for use in blending with fuel.
The solids and liquids remaining after the separation process undergo a series of steps
to remove water from the mixture.
Centrifugation is used to recover the insoluble lignin-rich residue. This residue can then
be sent to an onsite combustion system where it is burned to generate steam.
Separation of Water-ethanol mixture by ultrafiltration and pervaporation

The separation of ethanol-water mixtures is of great importance for the production of

ethanol from biomass. Both ultrafiltration and pervaporation processes can be used
for the continuous processing of fermentation and separation. The removal of ethanol
from the ultrafiltration permeate can be accomplished by pervaporation. Separation of
ethanol-water mixtures by the pervaporation process has been investigated. Results
are presented for membranes which are preferentially permeable for ethanol and for
others which are preferentially water permeable. Membrane types (homogeneous,
asymmetric and composite). The mixture of ethanol and water is passed through a
column containing pellets of a molecular sieve of 3 A (i.e. the pores have diameters of
3 angstroms, 3x10-10 m or 0.3 nm). [1]

Both ethanol and water are polar, only water molecules (diameter 0.28 nm) are able to
pass through the pores as the diameter of ethanol molecules is too large (0.44
nm). Thus the water molecules enter through the pores and are trapped in the cages
of the zeolite. The ethanol passes through the column and is collected.

Separation of Ethanol-Water mixture will happen using Zeolite catalyst or graphene

membrane which has 0.3 nm pour size, which is also ideal for the water-ethanol
separation.
Liquid solution of ethanol and water is passed through a column of the zeolite and the
pure ethanol is collected. Pure silicate membranes were prepared on porous supports
of sintered stainless steel or alumina discs is also used for water ethanol separation,
graphene membranes is also can be used since it has 0.3nm pore size. [2]
Mass balance, Reactions and Calculations:

Starting from the premise 100 l (1 hl) of wine are 160 kg for white grape, 130 kg for red
grape, and 140 kg for a mixture of red and white grape. [3]

The balanced equation of fermentation of sugar (glucose and fructose) to ethanol:

The conversion occur using Saccharomyces cerevisiae yeast. Fermentable sugars are:

- Glucose (also known as dextrose, blood sugar, or grape sugar), C6H12O6.

- Mannose, C6H12O6.
- Galactose, C6H12O6.
- Fructose (also known as laevulose), C6H12O6.

Yeast is a single celled fungus containing a number of enzymes useful during

fermentation. Brewer’s yeast and wine yeast, for example, contain zymase, an enzyme
that can convert glucose to ethanol [5].

The reaction conditions for fermentation are:

- Aqueous environment.
- Warm temperature (different enzymes will have different optimum
temperatures).
- Anaerobic environment (no oxygen present).
- Slightly acidic pH [5].

Fermentation will cease if:

- The ethanol concentration becomes too great (14% by volume ethanol for wine
yeast) [for more explanation below].
- The temperature is high enough to kill the yeast (>27 ºC for brewer’s yeast)
- The pH falls below ~6

Distillation of the aqueous mixture produced from fermentation can produce a

solution containing ~95% by volume ethanol [5].

Why does yeast stop working at certain levels of alcohol?

The ability of yeast cells to convert sugar into Carbon dioxide and Alcohol is down to
enzymes. Several enzymes are involved each does its step in the process. The final step
is Zymase reduction which takes the end product of the other enzymes
(acetaldehyde/glycerol), and turns this into good old ethyl alcohol. Sadly high
concentrations alcohol actually destroys enzymes and kills the yeast cell. Different
strains of yeast can tolerate different concentrations of alcohol. Brewer’s yeast cannot
withstand much beyond 5 or 6% Alcohol by volume. Wine yeast is more tolerant at a
range of 10-15% specially cultured strains of yeast with the correct environment can
withstand alcohol levels up to 21% alcohol [6].

Assume the waste that is generated to produce 1000 litres of wine:

Mass balance for Lees:

Since the volume percentage of the Lees produced with wine is 5%, so we have 50
litres of Lees. The ethanol content of the lees is as follows 61.9 g/l from grape pressing,
80.9 g/l and 74.5 g/l from white and red grape lees in the first decantation step
respectively, and from the second decantation step 55.9 g/l and 63.5 g/l from white
and red grape lees, so we use overall concentration of ethanol in the total amount of
lees produced of =61.9+ (80.9+55.9+74.5+63.5) /2 = 199.3 g/l .(Assuming we have a
mix of white & red grape waste with percentage 50% each).
So for 50 litre of lees we have a content of ethanol = 50 * (199.3+61.9) = 13060 g
=13,060 kg ethanol and, dividing by the density of ethanol 789 kg/m3 we get 0.01655
m3 which equals 16.55 litres of ethanol from the 50 litres of lees [3].

Calculating the amount of ethanol from glucose in the lees:

The glucose content of the waste mix = 0.4 + (1.4+.1)/2 = 1.15 g /l

So the mass of glucose that we get from 50 litres of lees = 50* 1.15 = 57.5 g = 0.0575
kg glucose. The number moles of glucose = , where
180 kg/kmole is the molecular weight of glucose..
So from the fermentation reaction the number of moles of ethanol = 0.00064 kmoles
And the mass of ethanol = no.moles * Mwt. = 0.00064 * 46 = 0.02938 kg
So volume of ethanol from glucose in the lees = 0.02938/789 = 0.000037 m3 ethanol =
0.0372 litres of ethanol.

Mass balance calculations for Pomace:

A wine production of 1000 litres which has a mass of 990 kg needs 1400 kg of mixed
white and red grapes, which means that the mass of pomace will be 410 kg pomace.
The pomace has fructose content of 8.91 g/100g, and a glucose content of 7.95
g/100g [4] so from the 410 kg of pomace we get 36.5kg fructose and 32.59 kg of
glucose.

The mass balance calculations of (glucose & fructose):

The molecular weight of the sugar C6H12O6 = 180 kg/ kmole.

The molecular weight of the ethanol C2H5OH = 46 kg/kmole.
Mass of glucose =0.0795*410=32.5 kg.
Mass of fructose =0.0891*410=36.5 kg
As from the balanced equation of the chemical reaction we can see that from 1 kmole
of sugar we get 2 kmole ethanol , the number of moles of sugar that we have in the
pomace ,

n= Mass of sugar= mass glucose + mass fructose =32.5+36.5= 69 kg sugar.

No.moles of sugar = kmole sugar.
So the No. of moles of ethanol = 2*0.38 = 0.766 kmole ethanol. And the mass of
ethanol = 0.766 kmole *46 kg /kmole = 35.3 kg ethanol, dividing by the density of
ethanol 789 kg/m3
So the Volume (Vethanol) = 35.3/789 = 0.04474 m3 = 44.74 litres of ethanol.

Mass balance calculations for cellulose in the fibres:

Now calculating the amount of ethanol that we can get from the cellulose in the fibres
of the grape pomace using an average value of the weight percentage of the cellulose
in grape pomace = 11.85 wt% (assuming we have a mix of white and red grape
waste),so from 410 kg of pomace we get a mass of cellulose = 0.1185*410 = 48.585 kg
cellulose.

The enzymatic hydrolysis reaction of the cellulose by which it's converted to glucose
monomers is as follows:

So from the reaction equation if the reaction was carried out for 1 mole then the mass
of species in the reaction equals the molecular weight, in other words from 162 kg
(cellulose) + 18 kg ( water )  180 kg (glucose), which means that the amount of
glucose that we can get from 48.58 kg cellulose = = 53.98 kg glucose .

-So the No. moles of glucose will be = 0.2999 kmole glucose.

-And the No. moles of ethanol = 0.2999*2 = 0.5998 kmole ethanol.

-Mass of ethanol =Mwt * No.moles = 46 * 0.5998 = 27.59 kg ethanol.

-Volume of ethanol = m3 = 34.96 litres of ethanol.

So the TOTAL amount of ethanol that we can get from 470 kg of winery waste (grape
pomace and lees) is 13.06 + 0.02938 + 35.3 + 27.59 = 75.98 kg of ethanol which is
96.28 litres.

That means that for each tone of Waste we get 161.77 kg of ethanol which is 205 litres
of Bioethanol.
Conclusions:

- This study was investigated to utilize the winery waste for ethanol production in
order to reduce the possible pollution generated for this kind of waste and take profit
of it making biofuel. The results of this study have revealed that this kind of waste can
efficiently be utilized for ethanol production with the help of Saccharomyces
cerevisiae in a process of fermentation, getting for each tone of waste 205 litres of
bioethanol, which means a yield of 19%.

Reference list:

[1] http://www.sciencedirect.com/science/article/pii/0376738894001200

[2] http://doc.utwente.nl/67225/

[3] UTILIZATION OF WINE WASTE FOR FERMENTATIVE PROCESSES -Page 12

http://library.iyte.edu.tr/tezler/master/gidamuh/T001100.pdf

[4] Chemical composition and bioactive compounds of grape pomace (Vitis vinifera L.),
Benitaka variety, grown in the semiarid region of Northeast Brazil- Page 138
http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0101-20612014000100020

[5] http://www.ausetute.com.au/thief.html

[6] http://www.yobrew.co.uk/fermentation.php