ACKNOWLEDMENT

Sense of acknowledgment are expressed to ALMIGHTY ALLAH, the creator of the

universe, the most merciful and beneficent for best owing us the will and ability to
undertake the study

Deep attributes are presented to Holy Prophet (PBUH) being a source and symbol of
knowledge and guidance to the entire mankind.

We would like to take this opportunity to thank everyone who contributed to the
successful completion of this thesis.

First of all, I would like to thank our project advisor Engr. Imran Swati, for his
invaluable advice, support, guidance and patience throughout our project.

We are thankful to Head of Chemical Engineering Department Dr. Saeed Gul and
also to Dr. Imran Ahmad, Lab Technician Tariq and other teachers of our
department for their support, guidance and sincere assistance during this course of our
study.

Furthermore, we would like to thank our friends for being there with their help and
support during the times we need it the most.

Lastly, we are very grateful to our parents, and to all our other family members,
whose patience, love, support and encouragement we could not have done without.

1
 ABSTRACT
The world is in energy crises today because of the accelerated sky touching prices of
conventional fuels which will last in 45 years, according to estimation. The world will
left no choice but to look for renewable energy sources like ethanol. This bio fuel will
not only overcome the energy shortages but will help in reduction of environmental
pollution by converted useless and pollution causing materials to use full product of
ethanol such wasted pine cone.

The study focus on controll of solid pine cone waste by fermentation process in which
solid pine cone is converted into energy. In this way not only bio waste is treated but
renewable energy can be generated. Fermentation process is carried out in a reactor
known as SSF (simulteneious and sacchrification fermentation).In fermentation all
types of bio waste can be considered as input. The proposed process will convert solid
pine cone waste into renewable energy. The process has the advantages of being
environment friendly as compared to the process of handling solid pine cone waste.
The input capacity is 244kg/day pine cone waste. Cost analysis indicates that
fermentation is feaseable.

2
 TABLE OF CONTENTS
Acknowledment..............................................................................................................i
Abstract..........................................................................................................................ii
Table of contents...........................................................................................................iii
List of Tables...............................................................................................................viii
List of FigureS..............................................................................................................ix
CHAPTER 1.................................................................................................................1
INTRODUCTION........................................................................................................1
1.1 Introduction.....................................................................................................1
1.2 History Of Ethanol..........................................................................................2
1.3 PHYSICAL PROPERTIES OF ETHANOL............................................................3
1.4 Chemical Properties Of Ethanol......................................................................4
1.4.1 Acid-base chemistry.................................................................................4
1.4.2 Halogenations...........................................................................................5
1.4.3 Halo form reaction...................................................................................5
1.4.4 Ester formation.........................................................................................6
1.4.5 Dehydration..............................................................................................6
1.4.6 Oxidation..................................................................................................6
1.4.7 Chlorination..............................................................................................7
1.4.8 Combustion..............................................................................................7
1.5 Grades Of Ethanol...........................................................................................7
1.5.1 On the basis of percentage of ethanol......................................................7
1.5.2 On the basis of purity of ethanol..............................................................8
1.6 Preparation Of Ethanol....................................................................................9
1.6.1 Reaction of ethane with steam.................................................................9
1.6.2 Alcoholic fermentation...........................................................................10
1.7 Raw Material For Production Of Ethanol......................................................11
1.7.1 Saccharides.............................................................................................11
1.7.2 Starches..................................................................................................11
1.7.3 Cellulose materials.................................................................................11
1.8 Uses Of Ethanol.............................................................................................12
1.8.1 As a fuel.................................................................................................12
1.8.2 Food versus fuel debate..........................................................................12
1.8.3 Ethanol fuel cells....................................................................................13
1.8.4 Rocket fuel.............................................................................................14
1.8.5 Alcoholic beverages...............................................................................14
1.8.6 Feedstock................................................................................................15
1.8.7 Antiseptic use.........................................................................................15
1.8.8 Antidote use...........................................................................................15
1.8.9 Other uses...............................................................................................16
1.8.10 Use in history.........................................................................................16
1.9 Problems Statement.......................................................................................16
1.9.1 Cost........................................................................................................16
1.9.2 Environmental issues.............................................................................16
1.9.3 World Demand.......................................................................................16
1.9.4 Natural Resources..................................................................................17
1.10 Objective Of Study........................................................................................17

3
 1.11 Scope Of Study..............................................................................................17
CHAPTER No 2.........................................................................................................19
LITERATURE REVIEW..........................................................................................19
2.1 Literature Review..........................................................................................19
2.1.1 Reference One:.......................................................................................19
2.1.2 Reference Two........................................................................................20
2.1.3 Reference Three.....................................................................................21
2.1.4 Reference four........................................................................................22
2.1.5 Reference five........................................................................................23
2.1.6 Reference six..........................................................................................24
2.1.7 Reference seven.....................................................................................24
2.1.8 Reference Eight......................................................................................25
CHAPTER 3...............................................................................................................26
MATERIAL AND MATHODOLOGY.....................................................................26
3.1 Raw Material.................................................................................................26
3.1.1 Peshawar Pine cone................................................................................26
3.1.2 Sulphuric Acid H2SO4............................................................................28
3.1.3 Distilled Water........................................................................................28
3.1.4 Sodium Hydroxide (NaOH)...................................................................29
3.1.5 Yeast.......................................................................................................29
3.2 Metholodogy..................................................................................................30
3.3 Equipments....................................................................................................30
3.3.1 Beakers...................................................................................................31
3.3.2 Test Tube................................................................................................31
3.3.3 Graduated cylinder.................................................................................32
3.3.4 Thermometer..........................................................................................33
3.3.5 Digital Weight Balance..........................................................................33
3.3.6 Magnetic Stirrers....................................................................................34
3.3.7 pH Paper and pH Meter..........................................................................34
3.3.8 Hydrometer............................................................................................35
3.3.9 Pipette.....................................................................................................36
3.3.10 Refractometer.........................................................................................36
3.3.11 Spectrophotometer.................................................................................36
3.3.12 Pine Cone Pretreatment..........................................................................38
3.3.13 Acid hydrolysis and Heating..................................................................38
3.3.14 Cooling...................................................................................................39
3.3.15 Brix determination.................................................................................39
3.3.16 Scarification and Fermentation Reactor (SSF)......................................39
3.3.17 Centrifuge...............................................................................................41
3.3.18 Distillation Column................................................................................41
CHAPTER # 04..........................................................................................................42
MATERIAL BALANCE............................................................................................42
4.1 Introduction...................................................................................................42
4.2 Overall Material Balance...............................................................................42
4.3 Component Material Balance:.......................................................................42
4.4 Pre Treatment Unit........................................................................................46
4.5 Hydrolyzer;....................................................................................................47
4.6 Cooler............................................................................................................47
4.7 SSF Unit........................................................................................................47
4.8 Centrifuge......................................................................................................48
4
 4.9 Distillation Coloumn.....................................................................................48
CHAPTER # 05..........................................................................................................49
ENERGY BLANCE...................................................................................................49
5.1 Introduction...................................................................................................49
5.2 Energy Balance Around Acid Hydrolyser.....................................................50
5.3 Energy Blance Around Ssf Reactor:..............................................................51
5.4 Energy Blance Around Cooler :.....................................................................51
CHAPTER #06...........................................................................................................53
PLANT DESIGN........................................................................................................53
6.1 Design of Fermenter (Ssf Reactor)................................................................53
6.1.1 Knowing Data:.......................................................................................53
6.1.2 Designing Steps:.....................................................................................53
6.1.3 Volume of SSF Reactor..........................................................................53
6.2 Design Of Distillation Column......................................................................54
6.2.1 Minimum numbers of stages..................................................................55
6.3.2 Minimum reflux ratio.............................................................................55
6.3.3 Actual Reflux Ratio:..............................................................................55
6.3.4 Actual number of theoretical stages.......................................................56
6.3.5 Location of feed:....................................................................................56
6.3.6 Diameter of the column..........................................................................57
6.3.7 Hight of Column....................................................................................58
6.3 Design Of Cooler...........................................................................................58
6.3.1 Area calculation:....................................................................................58
6.3.2 Number of Tubes....................................................................................59
6.3.3 Shell Diameter........................................................................................59
CHAPTER # 07..........................................................................................................60
COST ESTIMATION................................................................................................60
7.1 Introduction...................................................................................................60
7.2 Cost Estimation For Ssf Reactor...................................................................62
7.3 Cost Estimation For Cooler...........................................................................63
7.4 Cost Estimation For Distillation Column:.....................................................64
7.5 Total Purchased Equipment Cost ( Tpec)......................................................65
CHAPTER # 08..........................................................................................................69
PROCESS SAFETY AND HAZOPE STUDY.........................................................69
8.1 Chemical Process Safety...............................................................................69
8.2 Inherently Safer Processes.............................................................................69
8.3 Process Safety Analysis.................................................................................69
8.4 Safety Devices...............................................................................................70
8.4.1 Temperature Relief System....................................................................70
8.4.2 Pressure Relief System...........................................................................70
8.4.3 Spark Arresters.......................................................................................70
8.4.4 Emergency Assistance System...............................................................70
8.5 Hazardous Materials And Conditions............................................................71
8.5.1 Explosion................................................................................................71
8.5.2 Temperature Control..............................................................................71
8.5.3 Reactive Chemical.................................................................................71
8.6 Conducting The Safety Inspection................................................................71
8.7 Providing The Basis Of Analysis, Report And Control.................................72
8.7.1 Disabling injuries...................................................................................72
8.7.2 Severities................................................................................................72
5
 8.7.3 Exposure Hours......................................................................................72
8.8 Knowing The Hazards...................................................................................72
8.9 Record Keeping.............................................................................................72
8.10 Types Of Chemicals.......................................................................................72
8.10.1 Corrosive................................................................................................73
8.10.2 Flammable and combustible..................................................................73
CHAPTER # 09..........................................................................................................74
INSTRUMENTATION AND PROCESS CONTROL............................................74
9.1 Introduction...................................................................................................74
9.2 Objective Of Instrumentation & Control System..........................................75
9.3 Components Of Control System....................................................................75
9.3.1 Process....................................................................................................75
9.3.2 Measurement Mean................................................................................75
9.3.3 Process Variables....................................................................................75
9.4 Temperature Measurement & Control...........................................................77
9.5 Pressure Measurement & Control.................................................................77
9.6 Flow Measurement & Control.......................................................................78
9.7 Instrumentation & Control On Ssf Reactor...................................................78
9.8 Components Of Feedback Control Loop.......................................................78
9.9 Process Requirments.....................................................................................78
9.10 Thermocouples..............................................................................................79
9.11 Resistance Thermometer...............................................................................79
9.12 Bimetallic Thermometer................................................................................79
9.13 Radiation Pyrometery....................................................................................80
9.14 Controller & Pneumatic Valves.....................................................................80
CHAPTER # 10..........................................................................................................81
MAINTENANCE OF EQUIPMENT.......................................................................81
10.1 Maintenance Of Ssf Reactor..........................................................................81
10.1.1 Reactor Geometry..................................................................................81
10.1.2 Pressure Check.......................................................................................81
10.1.3 Reactor Cleaning....................................................................................82
10.2 Maintenance for heat transfer equipment’s...................................................82
10.2.1 Cooler (Heat exchanger- Shell and tube plate)......................................82
10.2.2 Plate heat exchangers- Gasket................................................................83
10.2.3 Shut down to heat exchangers................................................................83
10.3 Maintenance Safety.......................................................................................84
10.4 Maintenanace Of Distillation Column...........................................................84
10.4.1 Inspection and Repair.............................................................................84
10.4.2 Corrosion on column intervals...............................................................84
10.4.3 Leak Test................................................................................................85
10.4.4 Angle of repose for tower......................................................................85
CHAPTER # 11..........................................................................................................86
EXPERIMENTS AND RESULTS............................................................................86
11.1 Results...........................................................................................................86
11.1.1 Mesh No 65 Hydrolysis.........................................................................86
11.2.2 Mesh No 28 Hydrolysis.........................................................................86
11.2.3 Fermentation of Mesh no 65..................................................................88
11.2.4 Fermentation of Mesh no 28..................................................................89
11.2.5 Ethanol and pH Relation........................................................................90

6
CHAPTER # 12..........................................................................................................92
CONCLUSION AND FUTURE WORK..................................................................92
12.1 Conclusion.....................................................................................................92
12.2 Future Work...................................................................................................93
12.2.1 Mesh No.................................................................................................93
12.2.2 Agitation.................................................................................................93
12.2.3 Temperature............................................................................................93
12.2.4 Yeast.......................................................................................................94
12.2.5 Nutrients.................................................................................................94
References...................................................................................................................95

7
 LIST OF TABLES
Table 2.1 Initial Enzyme Loading................................................................................19

Table 2.2 Initial enzyme loading..................................................................................23

Table 4.1:Typical Composition of Pinecone................................................................45

Table 4.2:For 100% conversion...................................................................................45

Table 4.3: Component Material Balance according to Glucose and Ethanol yield.....46

Table 7.1:Typical average equipment materials of construction capital cost factors. .60

table 7.2:Typical materials of construction capital cost factor for pressure vessel and 
Distillation column .................................................................................................61

table 7.3: Typical materials of construction capital cost factor for shell and tube heat 
exchange ..................................................................................................61

table 7.4: Typical equipment pressure capital cost factors..........................................62

table 7.5: Capital equipment pressure capital cost factors ..........................................62

Table No 11.1 Mesh No 65 Hydrolysis.......................................................................86

Table No 11.2 Mesh No 28 Hydrolysis.......................................................................87

Table No 11.3 Fermentation of Mesh no 65................................................................88

Table No 11.4 Fermentation of Mesh no 28................................................................89

Table No 11.5 Ethanol and pH Relation......................................................................90

8
 LIST OF FIGURES
Figure No 1.1 Ethanol molecular arrangement...................................................1
Figure No 1.2 Ethanol molecular structure.........................................................1
Figure No 1.3 world demand of ethanol...........................................................17
Figure No 3.1 Peshawar Pine cone...................................................................27
Figure No 3.2 Beakers.......................................................................................31
Figure No 3.3 Test tubes...................................................................................32
Figure No 3.4 Graduated cylinder.....................................................................32
Figure No 3.5 Thermometer..............................................................................33
Figure No 3.6 Digital Weight Balance..............................................................33
Figure No 3.7 Magnetic Stirrers........................................................................34
Figure No 3.8 pH paper.....................................................................................35
Figure No 3.9 pH Meter....................................................................................35
Figure No 3.10 Hydrometer..............................................................................35
Figure No 3.11 Pipette......................................................................................36
Figure No 3.12 Refractometer...........................................................................36
Figure No 3.13 Spectrophotometer...................................................................37
Figure No 3.14 process flow sheet....................................................................38
Figure 4.1: Pretreatment...................................................................................46
Figure 4.2: Hydroloyzer...................................................................................47
Figure 4.3: Cooler.............................................................................................47
Figure 4.5: Centrifuge......................................................................................48
Figure 4.6: Distillation column........................................................................48
Figure No 11.1 Time Vs Brix............................................................................87
Figure No 11.2Time Vs Specific Gravity..........................................................88
Figure No 11.3. Brix Vs Ethanol ml/ 20 ml Solution........................................89
Figure No 11.2Ethanol ml / 20 ml solution Vs pH...........................................91

9
 CHAPTER 1

INTRODUCTION

1.1 INTRODUCTION

Ethanol is also called ethyl alcohol, pure alcohol, grain alcohol, or drinking alcohol. It
is a volatile, flammable, colorless liquid. Ethanol is a 2-carbon alcohol with the
empirical formula CH3O. Its molecular formula is CH3CH2OH.

An alternative notation is CH3-CH2-OH, which indicates that the carbon of a methyl

group (CH3–) is attached to the carbon of a ethylene group (–CH2–), which is attached
to the oxygen of a hydroxyl group (–OH). It is a constitutional isomer of diethyl ether.
Ethanol is often abbreviated as EtOH, using the common organic chemistry notation
of representing the ethyl group (C2H5) with Et.

Ethanol is the systematic name defined by the IUPAC nomenclature of organic

chemistry for a molecule with two carbon atoms, having a single bond between them
and an attached -OH group. Fig 1.1 and 1.2 shows the molecular arrangement and
molecular structure of ethanol.

Figure No 1.1 Ethanol molecular arrangement

1
 Figure No 1.2 Ethanol molecular structure

1.2 HISTORY OF ETHANOL

The fermentation of sugar into ethanol is one of the earliest biotechnologies employed
by humans. The intoxicating effects of ethanol consumption have been known since
ancient times. Ethanol has been used by humans since prehistory as the intoxicating
ingredient of alcoholic beverages. Dried residues on 9,000-year-old pottery found in
China imply that pre-historic people consumed alcoholic beverages. Although
distillation was well known by the early Greeks and Arabs, the first recorded
production of alcohol from distilled wine was by the School of Salerno alchemists in
the 12th century.

In 1796, Johann Tobias Levitz obtained pure ethanol by mixing partially purified
ethanol (the alcohol-water a zoetrope) with an excess of anhydrous alkali and then
distilling the mixture over low heat. Antoine Lavoisier described ethanol as a
compound of carbon, hydrogen, and oxygen, and in 1807 Nicolas-Theodore de
Saussure determined ethanol's chemical formula. Fifty years later, Archibald Scott
Couper published the structural formula of ethanol. It was one of the first structural
formulas determined.

Ethanol was first prepared synthetically in 1825 by Michael Faraday. He found that
sulfuric acid could absorb large volumes of coal gas. He gave the resulting solution to
Henry Hornell, a British chemist, who found in 1826 that it contained "sulphovinic
acid" (ethyl hydrogen sulfate). In 1828, Hornell and the French chemist Georges-
Simon Sérullas independently discovered that sulphovinic acid could be decomposed
into ethanol. Thus, in 1825 Faraday had unwittingly discovered that ethanol could be
produced from ethylene (a component of coal gas) by acid-catalyzed hydration, a
process similar to current industrial ethanol synthesis.

Ethanol‘s first use was to power an engine in 1826, and in 1876, Nicolas Otto, the
inventor of the modern four-cycle internal combustion engine, used ethanol to power
an early engine. Ethanol also was used as a lighting fuel in the 1850s, but its use
curtailed when it was taxed as liquor to help pay for the Civil War. Ethanol is not a
new fuel. In the 1850s, ethanol was a major lighting fuel. During the Civil War, a

2
liquor tax was placed on ethanol to raise money for the war. The tax increased the
price of ethanol so much that it could no longer compete with other fuels such as
kerosene in lighting devices. Ethanol production declined sharply because of this tax
and production levels did not begin to recover until the tax was repealed in 1906.

In 1908, Henry Ford designed his Model T to run on a mixture of gasoline and
alcohol, calling it the fuel of the future. In 1919, when Prohibition began, ethanol was
banned because it was considered a liquor. It could only be sold when it was mixed
with petroleum. With the end of Prohibition in 1933, ethanol was used as a fuel again.
Ethanol use increased temporarily during World War II when oil and other resources
were scarce. In the 1970s, interest in ethanol as a transportation fuel was revived
when embargoes by major oil producing countries cut gasoline supplies. Since that
time ethanol use has been encouraged by offering tax benefits for producing ethanol
and for blending ethanol into gasoline. In 1988, ethanol began to be added to gasoline
for the purpose of reducing carbon monoxide emissions.

Ethanol use as a fuel continued after the tax was repealed, and fueled Henry Ford‘s
Model T in 1908. The first ethanol blended with gasoline for use as an octane booster
occurred in the 1920s and 1930s, and was in high demand during World War II
because of fuel shortages.

Today‘s ethanol industry began in the 1970s when petroleum-based fuel became
expensive and environmental concerns involving leaded gasoline created a need for
an octane. Corn became the predominant feedstock for ethanol production because of
its abundance and ease of transformation into alcohol. Federal and state subsidies for
ethanol helped keep the fuel in production when ethanol prices fell with crude oil and
gasoline prices in the early 1980s.

1.3 PHYSICAL PROPERTIES OF ETHANOL

The physical properties of ethanol stem primarily from the presence of its hydroxyl
group and the shortness of its carbon chain. Ethanol's hydroxyl group is able to
participate in hydrogen bonding, rendering it more viscous and less volatile than less
polar organic compounds of similar molecular weight, such as propane. Some of the
main physical properties of ethanol are given below.

3
Ethanol is a volatile liquid. One must observe this property of ethanol in the form of
spirit which escapes if the bottle lid is kept open even for very short interval of time.

1. Ethanol is a colorless liquid just like water.

2. It has a slight odor, having a pleasant smell that is why often used in perfumes.
3. It has a boiling point of 78.37 °C and melting point is −114 °C.
4. Its density is 0.789 g/cm3 at 20°C.
5. Its molar mass is 46.07 g/mol
6. It burns with a smokeless blue flame that is not always visible in normal light.
7. Ethanol is slightly more refractive than water, having a refractive index of
1.36242
8. Ethanol is a versatile solvent, miscible with water and with many organic
solvents, including acetic acid, acetone, benzene, carbon tetrachloride,
chloroform, diethyl ether, ethylene glycol, glycerol, nitro methane, pyridine,
and toluene It is also miscible with light aliphatic hydrocarbons, such as
pentane and hexane, and with aliphatic chlorides such as trichloroethane and
tetrachloroethylene.
9. Mixtures of ethanol and water form an azeotrope at approx. 89 mole-%
ethanol and 11 mole-% water or a mixture of about 96 volume percent ethanol
and 4 % water at normal pressure and T=351 K. This azeotropic composition
is strongly temperature and pressure-dependent and vanishes at temperatures
below 303 K.
10. Ethanol is not an acid or a base but it is neutral and its PH is almost 7.
11. The addition of even a few percent of ethanol to water sharply reduces the
surface tension of water. This property partially explains the tears of wine
phenomenon. When wine is swirled in a glass, ethanol evaporates quickly
from the thin film of wine on the wall of the glass. As the wine‘s ethanol
content decreases, its surface tension increases and the thin film heads up and
runs down the glass in channels rather than as a smooth sheet.

1.4 CHEMICAL PROPERTIES OF ETHANOL

Ethanol is classified as a primary alcohol, meaning that the carbon to which its
hydroxyl group is attached has at least two hydrogen atoms attached to it as well. The
chemistry of ethanol is largely that of its hydroxyl group.

4
1.4.1 Acid-base chemistry

Ethanol's hydroxyl group causes the molecule to be slightly basic. It is almost neutral
like water. The pH of 100% ethanol is 7.33, compared to 7.00 for pure water. Ethanol
can be quantitatively converted to its conjugate base, the ethnocide ion (CH3CH2O−),
by reaction with an alkali metal such as sodium:

2CH3CH2OH + 2Na → 2CH3CH2ONa + H2

or a very strong base such as sodium hydride:

CH3CH2OH + NaH → CH3CH2ONa + H2

This reaction is not possible in an aqueous solution, as water is more acidic, so that
hydroxide is preferred over ethoxide formation.

1.4.2 Halogenations

Ethanol reacts with hydrogen halides to produce ethyl halides such as ethyl chloride
and ethyl bromide:

CH3CH2OH + HCl → CH3CH2Cl + H2O

HCl reaction requires a catalyst such as zinc chloride. Hydrogen chloride in the
presence of their respective zinc chloride is known as Lucas reagent.

CH3CH2OH + HBr → CH3CH2Br + H2O

HBr requires refluxing with a sulfuric acid catalyst.

Ethyl halides can also be produced by reacting ethanol with more specialized
halogenating agents, such as thionyl chloride for preparing ethyl chloride, or
phosphorus tribromide for preparing ethyl bromide.

CH3CH2OH + SOCl2 → CH3CH2Cl + SO2 + HCl.

1.4.3 Halo form reaction

"The haloform reaction is a chemical reaction where a haloform (CHX 3, where X is a

halogen) is produced by the exhaustive halogenations of a methyl ketone (a molecule
containing the R-CO-CH3 group) in the presence of a base"

5
1.4.4 Ester formation

Under acid-catalyzed conditions, ethanol reacts with carboxylic acids to produce ethyl
esters and water:

RCOOH + HOCH2CH3 → RCOOCH2CH3 + H2O.

For this reaction to produce useful yields it is necessary to remove water from the
reaction mixture as it is formed.

Ethanol can also form esters with inorganic acids. Diethyl sulfate and triethyl
phosphate, prepared by reacting ethanol with sulfuric and phosphoric acid
respectively, are both useful ethylating agents in organic synthesis. Ethyl nitrite,
prepared from the reaction of ethanol with sodium nitrite and sulfuric acid, was
formerly a widely-used diuretic.

1.4.5 Dehydration

Strong acid desiccants, such as sulfuric acid, cause ethanol's dehydration to form
either diethyl ether or ethylene:

2CH3CH2OH → CH3CH2OCH2CH3 + H2O (on 120 Co)

CH3CH2OH → H2C=CH2 + H2O (on 180Co)

Which product, diethyl ether or ethylene, predominates depends on the precise

reaction conditions.

1.4.6 Oxidation

Ethanol can be oxidized to acetaldehyde, and further oxidized to acetic acid. In the
human body, these oxidation reactions are catalyzed by enzymes. In the laboratory,
aqueous solutions of strong oxidizing agents, such as chromic acid or potassium
permanganate, oxidize ethanol to acetic acid, and it is difficult to stop the reaction at
acetaldehyde at high yield. Ethanol can be oxidized to acetaldehyde, without over

6
oxidation to acetic acid, by reacting it with pyridinium chromic chloride. The direct
oxidation of ethanol to acetic acid using chromic acid is given below.

C2H5OH + 2[O] → CH3COOH + H2O

The oxidation product of ethanol, acetic acid, is spent as nutrient by the human body
as acetyl, where the acetyl group can be spent as energy or used for biosynthesis.

1.4.7 Chlorination

When exposed to chlorine, ethanol is both oxidized and its alpha carbon chlorinated to
form the compound, chloral.

4Cl2 + C2H5OH → CCl3CHO + 5HCl

1.4.8 Combustion

Combustion of ethanol forms carbon dioxide and water.

C2H5OH(g) + 3O2 (g) → 2CO2 (g) + 3H2O (l); (ΔHr = −1409 kJ/mol).

1.5 GRADES OF ETHANOL

Ethanol is available in a range of purities that result from its production or, in the
case of denatured alcohol, are introduced intentionally. It can be divided into grades
by two bases.

1.5.1 On the basis of percentage of ethanol

Alcohol can be categorized on the basis of percentage of ethanol in solution with

water.

1.5.1.1 Denatured alcohol

Pure ethanol and alcoholic beverages are heavily taxed, but ethanol has many uses
that do not involve consumption by humans. To relieve the tax burden on these uses,
most jurisdictions waive the tax when an agent has been added to the ethanol to
render it unfit to drink. These include bettering agents such as denatonium benzoate
and toxins such as methanol, naphtha, and pyridine. Products of this kind are called
denatured alcohol.

7
1.5.1.2 Absolute ethanol

Absolute or anhydrous alcohol generally refers to purified ethanol, containing no

more than one percent water. Absolute alcohol not intended for human consumption
often contains trace amounts of toxic benzene (used to remove water by azeotropic
distillation). Consumption of this form of ethanol can be fatal over a short time
period. Generally this kind of ethanol is used as solvents for lab and industrial settings
where water will disrupt a desired reaction.

1.5.1.3 Rectified ethanol

A rectified spirit, rectified alcohol, or neutral spirit is highly concentrated ethanol

which has been purified by means of repeated distillation, a process that is called
rectification. It typically contains 95% alcohol by volume .Rectified spirits are used in
mixed drinks, in the production of liqueurs, for medicinal purposes, and as a
household solvent. The purity of rectified spirit has a practical limit of 95.6% when
produced using conventional distillation processes, because a mixture of ethanol and
water becomes an azeotrope at this concentration.

1.5.2 On the basis of purity of ethanol

Several grades of ethyl alcohol are available on the basis of the amount of impurities
present. Generally, as you move down the chain to a lower quality ethanol, higher
amounts of impurities are present.

1.5.2.1 The Purest

The highest level of ethanol purity is GNS or grain neutral spirits, beverage quality.
This is only domestically produced from fermentation grain sources, typically corn or
wheat. Based on the type of grain processed and the enzymes used to break starch
down to sugar, different quantities and types of impurities are produced. In addition to
meeting all of the quality requirements for FCC grade materials, GPC beverage
alcohol must pass stringent organoleptic analysis. Even in this day of modern
technology and sophisticated analytical equipment and techniques, the human senses
are able to detect impurity levels beyond the detection limits of the equipment. Since
GNS is intended for human consumption, this test is the most important screening
tool. Organoleptics are normally run at 40 proofs (20% by volume).

8
1.5.2.2 Purer

FCC Grade‖ ethanol (Food Chemical Codex) adds heavy metal specification limits to
the grades below since most FCC grade materials are used in food applications. This
can be either of fermentation or synthetic origin.

1.5.2.3 Pure

Industrial Grade ethanol can be of either fermentation or synthetic origin. It has most
of the impurities removed. USP Grade ethanol (U.S. Pharmacopoeia) has specific
tests that measure impurities present, setting limits on each type. NF Grade ethanol
(National Formulary) lowers the amount of impurities further to the 20 to 25 ppm
levels.

1.6 PREPARATION OF ETHANOL

Ethanol can be prepared as 95% alcohol which is also called rectified spirit (a solution
of ethanol and water having 95% ethanol and 5% water) by distillation of the solution
which results from the fermentation of sugars.

There are two major pathways to ethanol production. Ethanol which is intended for
industrial use is made by first method, while ethanol intended for food use tends to be
made by second method. Both the methods are described below.

1.6.1 Reaction of ethane with steam

Most of ethanol used in industry is made, not by alcoholic fermentation, but by an

addition reaction between ethane and steam. The reaction is reversible, and the
formation of the ethanol is exothermic.

Only 5% of the ethane is converted into ethanol at each pass through the reactor. By
removing the ethanol from the equilibrium mixture and recycling the ethane, it is
possible to achieve an overall 95% conversion.

9
1.6.2 Alcoholic fermentation

Alcohol fermentation is the conversion of sugar into carbon dioxide gas and ethyl
alcohol. This process is carried out by yeast enzymes. This in fact a complex series of
conversions that brings about the conversion of sugar to CO2 and alcohol. Yeast is a
member of the plant family and in fermentation we use the sugar fungi form of yeast.
These cells gain energy from the breakdown of the sugar. The by product, CO2,
bubbles through the liquid and dissipates into the air. The other product, alcohol,
remains in the liquid which is great for us but not for the yeast, as the yeast dies when
concentration of alcohol exceeds 12% of ethanol produced.

Saccharomyces cerevisiae (baker's yeast) are the most commonly used

microorganisms for ethanol production due to its excellent characteristics of growing
at high sugar concentrations and producing high yields of ethanol. The yeast tolerates
up to 5% alcohol. Beyond this level, the yeast cannot continue fermentation. Wine
yeast on the other hand tolerates up to about 12% alcohol. The level of alcohol
tolerance by yeast varies from 5% to 12% depending on yeast strain. The ability of
yeast cells to convert sugar to carbon dioxide and alcohol is down to enzymes. The
final step is zymase reduction which takes the end product of the other enzymes
(acetaldehyde/glycerol), thus reduce ethanol production. Alcohol actually destroys
enzymes and kills the yeast cells if concentration is high. This happens at different
levels for different strains of yeast. The fermentation process has other limits such as
temperature. Greater than 40 degree Celsius and less than 20 degree Celsius kills the
yeast. The amount of sugar in solution can be too much which must be lowered
through dilution to the minimum of 15% to 25%.Some recepies suggest adding the
sugar in parts throughout fermentation rather all at the beginning. This is especially
true if the fermentation is aimed at producing a high level of alcohol. Some yeast
strains have evolved to handle high sugar levels. E.g yeast such as Tokay and
sauterne.

A solution of sucrose, to which yeast is added, is heated. An enzyme, invertase, which

is present in yeast, is added and this acts as a catalyst to convert into glucose and
fructose.

C12H 22O11 + H2O------------------------------›C6H12O6+C6H12O6

Sucrose glucose fructose

10
The glucose, C6H12O6, and fructose, C6H12O6, formed are then converted into ethanol
and carbon dioxide by another enzyme, zymase, which is also present in yeast.

C12H22O11 + H2O------------------------------›2C2H5OH+ 2CO2

The fermentation process takes two days. The ethanol is then obtained by fractional
distillation.

1.7 RAW MATERIAL FOR PRODUCTION OF ETHANOL

Ethyl alcohol may be obtained by the fermentation process from three basic types of
raw materials, called feedstock.

The three basic types of feed stocks are;

1. Saccharides
2. Starches
3. Cellulose

1.7.1 Saccharides

These are sugar containing materials in which the carbohydrate (The actual substance
from which alcohol is produced) is present in form of simple, directly fermentable six
and twelve carbon sugar molecules such as glucose, fructose and maltose. Such
materials include sugarcane, sugar beets, fruit (both fresh and dried), citrus molasses,
cane sorghum, whey and skim milk.

1.7.2 Starches

Starch materials contain more complex carbohydrates such as starch and insulin that
can be broken down into the simpler six and twelve carbon sugars by hydrolysis with
acid or in the action of enzymes in a process called malting. Such materials include
corn, grain sorghum, bareley, wheat, potatoes, sweet potatoes, Jerusalem artichokes,
cacti, manioc, and arrowroot etc.

1.7.3 Cellulose materials

These are materials such as woods, wastes, paper, straw, cornstalks, corncobs, cotton
etc, which contain materials that can be hydrolyzed with acid, enzymes or otherwise
converted to fermentable sugars called glucose.

11
1.8 USES OF ETHANOL

Ethanol has the following uses.

1.8.1 As a fuel

The largest single use of ethanol is as a motor fuel and fuel additive. The largest
national fuel ethanol industries exist in Brazil (gasoline sold in Brazil contains at least
25% ethanol and anhydrous ethanol is also used as fuel in more than 90% of new cars
sold in the country). The Brazilian production of ethanol is praised for the high carbon
sequestration capabilities of the sugar cane plantations, thus making it a real option to
combat climate change.

Henry Ford designed the first mass-produced automobile, the famed Model T Ford, to
run on pure anhydrous (ethanol) alcohol—he said it was "the fuel of the future".
Today, however, 100% pure ethanol is not approved as a motor vehicle fuel in the
U.S. Added to gasoline, ethanol reduces ground-level ozone formation by lowering
volatile organic compound and hydrocarbon emissions, decreasing carcinogenic
benzene, and butadiene, emissions, and particulate matter emissions from gasoline
combustion. Ethanol is also used as a cooking and lighting fuel. In India ethanol stove
and lanterns have been developed which can run on 50% by weight ethanol/water
mixture. This mixture (hooch or illicit liquor) is easy to distill, safer to handle and use
than 100% ethanol, can be produced by small local producers and uses less energy in
its production.

1.8.2 Food versus fuel debate

It is disputed whether corn ethanol as an automotive fuel results in a net energy gain
or loss. As reported in "The Energy Balance of Corn Ethanol: an Update," the energy
returned on energy invested for ethanol made from corn in the U.S. is 1.34 (it yields
34% more energy than it takes to produce it). Input energy includes natural gas based
fertilizers, farm equipment, transformation from corn or other materials, and
transportation. However, other researchers report that the production of ethanol
consumes more energy than it yields. In comparison, sugar cane ethanol is at around 8
(it yields 8 joules for each joule used to produce it). Recent research suggests that
cellulosic crops such as switch grass provide a much better net energy production than
corn, producing over five times as much energy as the total used to produce the crop
12
and convert it to fuel. If this research is confirmed, cellulosic crops will most likely
displace corn as the main fuel crop for producing bioethanol.

Michael Grunewald reports that one person could be fed for 1 year "on the corn
needed to fill an ethanol-fueled SUV". He further reports that though "hyped as an
eco-friendly fuel, ethanol increases global warming, destroys forests and inflates food
prices." Environmentalists, livestock farmers, and opponents of subsidies say that
increased ethanol production won't meet energy goals and may damage the
environment, while at the same time causing worldwide food prices to soar. Some of
the controversial subsidies in the past have included more than $10 billion to Archer-
Daniels-Midland since 1980. Critics also speculate that as ethanol is more widely
used; changing irrigation practices could greatly increase pressure on water resources.

A February 7, 2008 Associated Press article stated, "The widespread use of ethanol
from corn could result in nearly twice the greenhouse gas emissions as the gasoline it
would replace because of expected land-use changes, researchers concluded Thursday.
The study challenges the rush to biofuels as a response to global warming." he article
does not take into account that even when grown in an industrial, soil-depleting
manner, corn still sequesters carbon through its unharvested root and stalk tissues,
which form soils, while gasoline production does not have a carbon-sequestration
component in its production cycle.

One acre of land can yield about 7,110 pounds (3,225 kg) of corn, which can be
processed into 328 gallons (1240.61 liters) of ethanol. That is about 26.1 pounds
(11.84 kg) of corn per gallon.

1.8.3 Ethanol fuel cells

Ethanol may be used as a fuel to power Direct-ethanol fuel cells in order to produce
electricity and the by-products of water (H 2O) and carbon dioxide (CO2). Platinum is
commonly used as an anode in such fuel cells in order to achieve a power density that
is comparable to competing technologies. Until recently the high price of platinum
has been cost prohibitive. A company called Acta Nanotech has created platinum free
nano structured anodes using more common and therefore less expensive metals. A
vehicle using non-platinum nanostructures anodes was used in the Shell Eco-

13
Marathon 2007 by a team from Offenburg Germany which achieved an efficiency of
2716 kilometers per liter (6388 miles per gallon).

1.8.4 Rocket fuel

Ethanol was commonly used as fuel in early bipropellant rocket vehicles, in

conjunction with an oxidizer such as liquid oxygen. The German V-2 rocket of World
War II, credited with beginning the space age, used ethanol, mixed with water to
reduce the combustion chamber temperature. The V-2's design team helped develop
U.S. rockets following World War II, including the ethanol-fueled Redstone rocket,
which launched the first U.S. satellite. Alcohols fell into general disuse as more
efficient rocket fuels were developed.

1.8.5 Alcoholic beverages

Alcoholic beverages vary considerably in their ethanol content and in the foodstuffs
from which they are produced. Most alcoholic beverages can be broadly classified as
fermented beverages, beverages made by the action of yeast on sugary foodstuffs, or
as distilled beverages, beverages whose preparation involves concentrating the
ethanol in fermented beverages by distillation. The ethanol content of a beverage is
usually measured in terms of the volume fraction of ethanol in the beverage,
expressed either as a percentage or in alcoholic proof units.

Fermented beverages can be broadly classified by the foodstuff from which they are
fermented. Beers are made from cereal grains or other starchy materials, wines and
ciders from fruit juices, and meads from honey. Cultures around the world have made
fermented beverages from numerous other foodstuffs, and local and national names
for various fermented beverages abound.

Distilled beverages are made by distilling fermented beverages. Broad categories of

distilled beverages include whiskeys, distilled from fermented cereal grains; brandies,
distilled from fermented fruit juices, and rum, distilled from fermented molasses or
sugarcane juice. Vodka and similar neutral grain spirits can be distilled from any
fermented material (grain or potatoes are most common); these spirits are so
thoroughly distilled that no tastes from the particular starting material remain.
Numerous other spirits and liqueurs are prepared by infusing flavors from fruits,

14
herbs, and spices into distilled spirits. A traditional example is gin, which is created by
infusing juniper berries into a neutral grain alcohol.

In a few beverages, ethanol is concentrated by means other than distillation.

Applejack is traditionally made by freeze distillation, by which water is frozen out of
fermented apple cider, leaving a more ethanol-rich liquid behind. Eisbier is also
freeze-distilled, with beer as the base beverage. Fortified wines are prepared by
adding brandy or some other distilled spirit to partially-fermented wine. This kills the
yeast and conserves some of the sugar in grape juice; such beverages are not only
more ethanol-rich, but are often sweeter than other wines.

Alcoholic beverages are sometimes used in cooking, not only for their inherent
flavors, but also because the alcohol dissolves hydrophobic flavor compounds which
water cannot.

Just as industrial ethanol is used as feedstock for the production of industrial acetic
acid, alcoholic beverages are made into culinary/household vinegar.

1.8.6 Feedstock

Ethanol is an important industrial ingredient and has widespread use as a base

chemical for other organic compounds. These include ethyl halides, ethyl esters,
diethyl ether, acetic acid, butadiene, and ethyl amines.

1.8.7 Antiseptic use

Ethanol is used in medical wipes and in most common antibacterial hand sanitizer
gels at a concentration of about 62% (percentage by volume, not weight) as an
antiseptic. Ethanol kills organisms by denaturing their proteins and dissolving their
lipids and is effective against most bacteria and fungi, and many viruses (including
SARS 2), but is ineffective against bacterial spores.

1.8.8 Antidote use

Ethanol can be used as an antidote for poisoning by other toxic alcohols, in particular
methanol and ethylene glycol. Ethanol competes with other alcohols for the alcohol
dehydrogenate enzyme, preventing metabolism into toxic aldehyde and carboxylic
acid derivatives.

15
1.8.9 Other uses

Ethanol is easily miscible in water and is a good solvent. Ethanol is less polar than
water and is used in perfumes, paints and tinctures .Ethanol is also used in design and
sketch art markers, such as Copic, and Tria. Alcohol is also found in certain kinds of
deodorants.

1.8.10 Use in history

Before the development of modern medicines, ethanol was used for a variety of
medical purposes. It has been known to be used as a truth drug, as medicine for
depression and as an anesthetic.

1.9 PROBLEMS STATEMENT

1. Cost
2. Environmental Issue
3. World Demand
4. Natural Recourses

1.9.1 Cost

The main purpose of production of ethanol is that the price of ethanol per barrel is less
then petrol barrel.

The price of petrol= $100/ barrel

The price of ethanol= $45/ barrel

1.9.2 Environmental issues

The use of petrol causes the emission of NOX, SOX and CO which are the major air
pollutants. On the hand ethanol is environmental friendly.

1.9.3 World Demand

Due to higher price of liquid fuels and environmental issues, the world deviate to the
production of ethanol. Ethanol is high energy efficient and highly economical. For the
production of ethanol, raw materials are easily available.

16
 Figure No 1.3 world demand of ethanol

1.9.4 Natural Resources

The purpose of production of ethanol is to maintain the natural resources of energy

because the consumption of fuels rises day by day and our natural resources of fuel
levels down day by day. The use of ethanol has major effect on the economy of any
country.

1.10 OBJECTIVE OF STUDY

There are many processes for production of ethanol but production from pine cone is
newest and easiest way.

1. To maximize the production of ethanol from wastes material

2. To minimize operation cost
3. To assess efficient process parameters
4. To Reduce the solid waste

1.11 SCOPE OF STUDY

1. To meet the energy crises.

2. To improve the economics condition.
3. To maintain the level of natural resources.
4. To protect environment from global warming.
5. To reduce the explosion in spills and accident.
6. To meet the ISO and global standard.
17
7. To reduce the in-combustion problems.
8. To reduce the knocking in vehicles.

18
 CHAPTER NO 2

LITERATURE REVIEW

2.1 LITERATURE REVIEW

To satisfy the desire to make life better for man through science and technology and
having in view the potentials ethanol has in this regard, there have been some
concerted efforts directed at perfecting the fermentation techniques and feedstock
used. The following are some literature which has been studied for the purpose of the
project.

2.1.1 Reference One:

M. Ballesteros et al. worked on ethanol production from paper material using

simultaneous Scarification and fermentation . For this purpose temp is maintained at
42c standard SSF assays were performed in 250 ml flask that containing 100 ml of
fermentation medium in which yeast extract 5, Peptone 5, NH4Cl 2, KH2PO4 1,
MgSO4.7H2O, 0.3flask were inoculated with 5% (v/v) of yeast suspension. The
process was performed at 42C and 150 rev/min agitation and enzymes loading (15
and 45 FPU/g substrate) For SSF in fed batch assays were initiated at 5% w/v
substrate concentration and enzymes loading of 15 Fpu/g substrate. At 24 hr from the
onset of SSF 3% w/v of fresh substrate were added and mixture incubbed for 24 hr.
then new addition of 2% w/v of substrate incubbed for 24 hr. to maintain the initial
enzyme loading of 15 Fpu/g substrate was performed at same time and following
results are gotten.

Table 2.1 Initial Enzyme Loading

Substrate loading Enzymes loading Ethanol %age of

substrate w/v Fpu/g substance Theoretical Yield

5 15 8.2 74.2

7.5 15 8.9 80.3

10 15 12.6 78.6

19
2.1.2 Reference Two

J. N. Nwakaire*, S. L. Ezeoha, B. O. Ugwuishiwu

(Department of Agricultural & Bio-resources, University of Nigeria, Nsukka, Enugu

State, Nigeria)

Energy from fossil fuels has played a very important role in our lives, but such an
important role has been clouded out due to the environment hazards caused from
fossil emissions.

This work thus was carried out to utilize a local available biomass waste as an
alternative source of ethanol which is currently used for spark ignition engines as a
renewable energy fuel. It also determined the yield of ethanol from the sawdust used.
The sawdust sample was collected from the Nsukka Sawmill (Timber shade).
Materials used included 18 m (78% concentration) of sulphuric acid, 6 m of sodium
hydroxide for hydrolysis, and fermentation process. The hydrolysis involves the
extraction of fermentable sugar from a cellulosic biomass. The sawdust of sulfuric
acid mixture was allowed to sit for 48 hours, and then the distilled water was used to
dilute in order to bring its pH between 5.0 - 6.0. 10 kg of sawdust gave 500 cm3 of
ethanol using Beer-Lambert plot of ethanol water mixture. The success of the
extraction of ethanol shows there are possibilities for improvement.

2.1.2.1 Methodology

The materials used in the experiment to produce bio-ethanol were from Food and
Bioprocess laboratory, in the Department of Agricultural and Bioresources
engineering, University of Nigeria, Nsukka. The materials were 30 kg of wood
sawdust collected from the Nsukka Sawmill which were divided into 10 kg each, 18
moles (78% concentration) of Tetra-oxo-sulphate (6) acid, 6 M of sodium hydroxide,
packages of commercial yeast (EBY 100 strain), distilled water, test tubes, 600 mL
beakers, measuring cylinders, glass bioreactor, and electronic balance. 18 M of 100
cm3 of sulphuric acid was used to hydrolyze 10 kg of wood sawdust, after
pretreatment to remove impurities, and was allowed to sit for 48 h. After hydrolysis,
the pH was reduced to a proper level of within 5.0-6.0 using distilled water. Then the

20
products from the pH normalization were inoculated with yeast for fermentation to
proceed. The mixture was allowed to stand for 72 h, after which the products were
separated with fractional distillation.

2.1.3 Reference Three

Z.J. Wang a,b, J.Y. Zhu b, Ronald S. Zalesny Jr. c, K.F. Chen a State Key Laboratory
Pulp and Paper Engineering, South China University of Technology, Guangzhou,
China.

They work on the production of ethanol from wood. Cellulosic ethanol i.e. ethanol
from forestry or agricultural waste is considered a way to prevent displacement of
crops to feed humans. Corn-based ethanol has been blamed by some for higher food
prices and shortages because food producers are at times forced to compete with
energy companies for grain.

Before 1914, in France, alcohol manufacture from sawdust was studied and
implemented industrially in a distillery in the Ardeche region. Due to the need for
alcohol for national defense during the World War. Wood alcohol was reconsidered
during the 1914-1918 war, production of wood alcohol was achieved in Germany with
either the classen or the Windesheim-ten-Doornkaat process. The latter involved
heating sawdust with dilute hydrochloric acid in the presence of catalysts (metallic
salt), in rotator autoclaves, at 7 to 8 atmospheres for 20 to 30 minutes. Yield is 6 liters
of alcohol per 100 kilograms of dry matter, but it is surely possible to improve this.

In saccharifying sawdust with 2 parts of sulphuric acid (90-95% H2SO4) per 100
parts of dry sawdust, maximum yield is obtained with a pressure of 7.5 atmospheres;
yield decreases above or below this pressure. With wood, yields of 22 to 23% sugar
are obtained, giving on average 100 to 115 liters of 95% alcohol per ton of wood
treated.

Hydrolysis is the conversion of cellulose to glucose also known as

SACCHARIFICATION. In 1965, P.M Sinclair, in his book reported that the
concentration of glucose in starch digests is 30-40 percent and highest glucose
concentration in cellulose digest is 5 percent. Selby however obtained 17 percent
glucose from cellulose. However, presently, using specific techniques 30 percent
glucose can be obtained from cellulose.

21
22
2.1.3.1 Methodology

They collect 20 kg of wood and reduce it size by milling. They divide into 10 kg of
each. They take 100ml distilled water and 20 ml sulphuric acid in 600 ml beaker for
hydrolysis. Heating the sample for two hours up 110 0C.the maximum yield of 23%
sugar is obtained from acid hydrolysis. Then the sample is transfer for fermentation.
Where yeast is added and pH is 5-6 maintained. The time for fermentation is 72
hours. Each 10 kg of sample give 700 cm3 of ethanol after separated by distillation.

2.1.4 Reference four

P.Alvira, E. Tomas-Prjo, M. Ballesteros and M>J Negro. They worked on

pretreatment technologies for an efficient bio ethanol production based on enzymatic
hydrolysis. Bio fuel produced from rigno calluses materials, so called generation
bioethanol describe energetic economic and friendly environmental advantages in
others methods of production of ethanol such as form starch or sugar of molasses. So
chemical and physical barriers caused by the close association of the main
components of lignocelluloses biomass hinder the hydrolysis of cellulose and
hemicelluloses to fermentable sugars. The main goal of pretreatment has a specific
effect on the cellulose hemicelluloses and lignin fraction so different pretreatment
methods and condition should be chosen according to the process configuration
selected for the production from lignocelluloses and it points out several key
properties that should be targeted for low cost advanced pretreatment process.

2.1.4.1 Methodology

High hydrolysis have been achieved when pre-treating lignocelluloses components

with diluted H2SO4 that is most studied acids such as Hcl phosphoric acid and nitric
acid also have been treated. Scarification yield as high as 74% was shown when
wheat straw was subjected to 0.7% v/v of H2SO4 for 1 hour at 121 C. olive tree
biomass was pretreated with 1.4% H2SO4 at 210 C give 76.55 hydrolysis yields. But
now a days ethanol production is high as 0.47 g/g glucose was obtained in
fermentation test with cashew apple bagass pretreated with dilute sulphuric acid at
121C for 15 minutes.

23
Table 2.2 Initial enzyme loading

Acid Ethanol Production Total fixed Capital

dollar$/gallon annual
basis

Diluted H2SO4 56.1 mm gallon/year $3.72

2.1.5 Reference five

Ye Sun, Liaoyang Cheng. Department of biological and Agricultural Engineering

North Carolina State University USA they worked on hydrolysis of lignocelluloses
Materials for Ethanol Production. Lignocelluloses are a biomass which can be used to
produce ethanol. It is a good source alternative energy source of limited crude oil.
Two processes involve in the conversion. One process in compressed hydrolysis of
cellulose in the lignocelluloses biomass to producing reducing sugars and then
fermentation the sugar to ethanol. The cost of this process is to high based on current
technologies and the main disadvantages is low yield and high cost by hydrolysis
process several research have been made to enhance the hydrolysis of lignocelluloses
materials. First fermentation of lignocelluloses material occurs to remove lignin and
semi cellulose which will enhance the hydrolysis of cellulose. The optimization of the
process can also be done on by the optimization of cellulose enzymes and enzymes
leading can also improve the hydrolysis and due to fermentation effectively removes
glucose which is an inhibitor to cellulose activity. This will increase the production of
cellulose hydrolysis.

2.1.5.1 Methodology

Waste material was cutting down and grinding into pieces such as in size 0.2-2 mm
for grinding the vibratory mill was used. The main purpose of grinding of waste
material was increase the degradability of waste materials. After process the materials
was treated at 300 0C and cellulose rapidly decomposes to produce gaseous products
and residual char by the addition of H2SO4 in steam explosion to improve enzymatic
hydrolysis and to complete removal of hemicellulose. The decomposition is much
slower and less volatile products are produced at lower temperature. Mild acidic
hydrolysis pretreatment (in H2SO4 97 0c, 2.5 hr) of the residues from paralysis
pretreatment has resulted in 80-85 conversion of cellulose to reducing sugar with
24
more than 50% glucose. The process can be enhanced eighth presence of oxygen.
When sodium carbonate is added as catalyst the decomposition of pure cellulose can
occur at lower temperature.

2.1.6 Reference six

Chantraporn Wong son, Taiwan Kangsadan and Sasisthorn Kongruang. The

Sirindhorn International Thai-German Graduate School of Engineering, King
Mongkut’s University of Technology North Bangkok, Thailand.

Vorakan Burapatana and Pichiti Pripanapong. PTT Research and Technology Institute
PTT public community limited, Ayutthaya, Thailand.

They worked on ultra sonic pretreatment enhanced the enzymatic hydrolysis of rice
straw. Abstract rice straw can be utilized to use as a raw material for production of
biofuel due to its content with high amount of sugar in a form of 35-40% w/w
cellulose and 25-30% w/w hemicelluloses. The effect of ultra sonic treatment to
enhanced the asccharification process of the enzymatic hydrolysis from rice straw was
investigated. To frequencies at 20 and 24 kHz of ultrasonic treatment were used for 80
min on rice straw before the enzymatic hydrolysis was applied by using commercially
available enzyme cocktail: Accelerate 1000, cellic Ctec and NS 50013 at 50C for 48
h. the result was found that the glucose concentration of pretreatment rice straw was
significantly higher than that of all enzymes significantly greater than that of enzymes
at frequency of 20 kHz (p 0.0001). When treating the rice straw with the Accellerase
1000 was yield significantly the highest glucose concentration among the other
enzymes (p 0.0001). These results reviewed that the ultrasonic pretreatment could
enhance the scarification process resulting in the acceleration of enzymatic
hydrolysis.

2.1.7 Reference seven

Rangasamy Parthiban. Sri Venkateswara College of engineering, Sriperumbudur,

Tamilnadu, India Meenakshisundarm Sivarajan. Scientist, Leather Research Institute,
Chenna, Tamilnadu, India Muthusamy Sukumar. Department of Biotechnology, Anna
University, Chennai. Tamilnadu, India.

25
They worked on ethanol production from banana peel waste using Saccharomyces
cerevisiae.

This paper analysis the production of ethanol from waste banana peel using
Saccharomyces cerevisiae at optimal growth conditions. The objective is to identify
and isolate the elite strains of yeast suitable for fermentation of banana peel, optimize
the fermentation condition for maximum production of the product, standardize the
concentration of acid for the maximum recovery of alcohol and assess the production
potential from banana peel and study the parameters associated with it. High ethanol
concentration was achieved with acid saccharification than enzymatic saccharification
and it is concluded that ethanol production from banana peel waste is the best
renewable natural resources or developing country like India.

2.1.8 Reference Eight

Qin ZHANG, Yanbin LI, XINJIANG production and construction corps key
laboratory of protection and utilization of biological resources in tarim basin, Tarim
University. College of live science, Tarim University.

They worked on dilute acid hydrolysis of cotton stalks and ethanol production from
hydrolytic liquids.

Dilute and hydrolytic condition of cotton stalks and ethanol production from
hydrolytic liquids were studied in this paper. Single factors experiments and
orthogonal experiment were designed to explore effects of sulfuric acid concentration,
hydrolysis time, solid-liquid ratio and hydrolysis temperature on the yield rates of
cotton stalks and condition was optimized, the acid hydrolysis liquids are collected
under the optimum condition and used in ethanol fermentation after detoxification, dis
coloration and condensation process. the ethanol fermentation parameters
(concentration of reducing sugar, strain mixture proportion, original pH value,
fermentation time) were examined results showed that the optimal dilute acid
hydolytic condition was determined as follows: sulfuric acid concentration 4.0 %,
hydrolysis time 30 min, solid solution ratio 1:5 and hydrolysis temperature 121 C and
the optimized parameters for ethanol were identifies as reducing sugar 7.0%,
including Saccharamyces cerevisiae and pashysolen tannophilus with proportion 1:1,
original pH value 5.0 and fermentation time between 36h to 48h .

26
 CHAPTER 3

MATERIAL AND MATHODOLOGY

3.1 RAW MATERIAL

Raw materials used in this process are given bellow.

1. Peshawar Pine cone

2. Sulphuric Acid (H2SO4)
3. Sodium Hydroxide (NaOH)
4. Distilled Water (H2O)
5. Yeast

3.1.1 Pine cone

The name "cone" derives from the fact that the shape in some species resembles a
geometric cone. The individual plates of a cone are known as scales. It is the fruit of
pines tree. Pine cone is cellulosic material. There are two types of pine cone.

 Male pine cone

 Female pine cone

3.1.1.1 Peshawar Pine cone

In Peshawar pine cone trees are planted is a green trees of Peshawar. Numbers of pine
trees in Peshawar city are twenty to thirty thousands according to the 2014 survey of
forest department Peshawar, per year plantation of cone trees are one to two thousand.
The survival rate of cone trees is 40 percent after plantation. They produce cone twice
a year, one cone fruit is prepared in six months. In Malakand division there are also a
lot of pine cone trees. It is a waste material in Peshawar city. Sometime it is used for
burning or heating process.

27
 Figure No 3.1 Peshawar Pine cone

3.1.1.2 Cellulose

Cellulose in lengthy chain of attaches sugar molecules that give wood its good
strengths. It is the major component of plant cell walls. It is used mainly in textile and
paper pulp industries. Cotton is pure form cellulose.

Cellulose is complex nature polymer a long chain made by the attachment of smaller
molecules. The cellulose contains long chain of sugar molecules that are called B.D
Glucose. The two unlike molecules of B.D Glucose are,

1. The sugar units are attached when water is removed by combining OH and H
highlighted in gray. Attachment of these two sugar molecules give
disaccharides which is also known as cellbiose.
2. Cellulose is polysaccharide made by sugar molecule combining in the same
way.

The cellulose contain mostly polar OH group. They are usually hydrogen bonds
contain OH group on adjacent chain, building the chain together. Cellulose is
important component of wood. Cellulose fiber normally in wood are bound in lignin a
complex polymer.

28
The formula of cellulose is (C6H10O5)n . Polysaccharide consists of hundred to over
thousand linked -D -glucose molecule.

Some sources of cellulose are given bellow:

1. Cellulose is mainly obtained from wood pulp and cotton.

2. Cellulose is found in plant as microfiber.

3. Cellulose is also produced in a hydrated form by some bacteria such as,

Acetobacter xylinum.

4. Aerobic bacteria give actinomycetes.

5. An aerobic bacterium gives clostridium.

6. Fungi give trichoderma cellulose.

3.1.2 Sulphuric Acid H2SO4

Sulfuric acid is a highly corrosive strong mineral acid with the molecular formula
H2SO4. It is a pungent, colorless to slightly yellow viscous liquid which is soluble in
water at all concentrations. Sometimes, it is dyed dark brown during production to
alert people to its hazards. The historical name of this acid is oil of vitriol.

Sulfuric acid has a wide range of applications including domestic acidic drain cleaner,
electrolyte in lead-acid batteries and various cleaning agents. It is also a central
substance in the chemical industry. Principal uses include mineral processing,
fertilizer manufacturing, oil refining, wastewater processing, and chemical synthesis.
It is widely produced with different methods, such as contact process, wet sulfuric
acid process and some other methods.

In this process Sulphuric acid (1N sol) is used for hydrolysis process.

3.1.3 Distilled Water

Distilled water is water that has many of its impurities removed through distillation.
Distillation involves boiling the water and then condensing the steam into a clean
container. In chemical and biological laboratories, as well as industry, cheaper
alternatives such as de-ionized water are preferred over distilled water. However, if
these alternatives are not sufficiently pure, distilled water is used. Where

29
exceptionally high purity water is required, double distilled water is used. Distilled
water is mineral free.

3.1.4 Sodium Hydroxide (NaOH)

Sodium hydroxide, also known as caustic soda, It is an inorganic compound with

the chemical formula NaOH.

It is a white solid and highly caustic metallic base and alkali salt which is available in
pellets, flakes, granules, and as prepared solutions at a number of different
concentrations. Sodium hydroxide forms an approximately 50% (by weight) saturated

solution with water. Sodium hydroxide is soluble in water, ethanol and methanol.

Sodium hydroxide is used in many industries, mostly as a strong chemical in the

manufacture of pulp and paper, textiles, drinking water, soaps and detergents and as

a drain cleaner.

In this Process sodium hydroxide is used to maintain the desired pH of solution.

3.1.5 Yeast

Yeast is unicellular fungi. The precise classification uses the characteristics of the cell,
ascosporic and colony. Physiological characteristics are also used to identify species.
One of the more well known characteristics is the ability to ferment sugars for the
production of ethanol. Budding yeasts are true fungi of the phylum Ascomycetes,
class Hemiascomycetes. The true yeasts are separated into one main order
Saccharomyce tales. Yeasts are characterized by a wide dispersion of natural habitats.
Common on plant leaves and flowers, soil and salt water. Yeasts are also found on the
skin surfaces and in the intestinal tracts of warm-blooded animals, where they may
live symbiotically or as parasites. Yeasts multiply as single cells that divide by
budding (e.g. Saccharomyces) or direct division (fission, e.g. Schizosaccharomyces),
or they may grow as simple irregular filaments (mycelium). In sexual reproduction
most yeasts form asci, which contain up to eight haploid ascospores. These ascospores
may fuse with adjoining nuclei and multiply through vegetative division or, as with
certain yeasts, fuse with other ascospores. The awesome power of yeast genetics is
partially due to the ability to quickly map a phenotype-producing gene to a region of

30
the S. cerevisiae genome. For the past two decades S. cerevisiae has been the model
system for much of molecular genetics research because the basic cellular mechanics
of replication, recombination, cell division and metabolism are generally conserved
between yeast and larger eukaryotes, including mammals. The most well-known and
commercially significant yeasts are the related species and strains of Saccharomyces
cerevisiae. These organisms have long been utilized to ferment the sugars of rice,
wheat, barley, and corn to produce alcoholic beverages and in the baking industry to
expand, or raise, dough etc.

3.2 METHOLODOGY

In this project we produce ethanol from Peshawar pine cone by hydrolysis method. In
which cut down the pine cone into small pieces and passed them through different
mesh screen. After that we put the H2SO4 in test tube the purity of H2SO4 (1 Nol Sol )
and we put 5ml H2SO4 in test tube after and as well as we put 15ml distilled water in
test tube after that we shake the test tube for 2 minutes. After shaking we put waste
pine cone 0.4g into the test tube and heat them at 90 oC temperature for 2 hours.
During heat process we continuously shake the test tube after 2 hours the waste cone
is converted into sugar brix because in which cellulose is also present that are
converted into sugar brix. After that process fermentation is done that convert the
sugar brix into ethanol by maintaining the pH 4-5. To maintain the pH, we neutralize
the solution and the sugar brix are converted into ethanol.

3.3 EQUIPMENTS

The equipments used in the process of ethanol production from pine cone are given
below:

1. Beaker
2. Test Tubes
3. Graduated Cylinder
4. Thermometer
5. Digital weight balance
6. Magnetic Agitator
7. pH paper and pH meter
8. Hydrometer
9. Pipette
10. Refractrometer
11. 11.Spectrophotometer

31
3.3.1 Beakers

A Beaker is a simple container for stirring, mixing and heating liquids commonly used
in many laboratories first designed in 1453. Beakers are generally cylindrical in
shape, with a flat bottom. Most also have a spout or (beak) to aid pouring as shown in
picture. Beakers are available in a wide range of size, from one milliliter up to several
liters.

In this process we used three beakers of different sizes given below:

1. 150 ml
2. 250 ml
3. 800 ml

Figure No 3.2 Beakers

3.3.2 Test Tube

A test tube, also known as a culture tube, is a common piece of laboratory glassware
consisting of a finger-like length of glass or clear plastic tubing, open at the top,
usually with a rounded U-shaped bottom. The tubes are available in a multitude of
lengths and widths, typically from 10 to 20 mm wide long. The top often features a
flared lip to aid pouring out the contents; some sources consider that the presence of a
lip is what distinguishes a test tube from a culture tube. A test tube has either a flat
bottom, a round bottom, or a conical bottom. Some test tubes are made to accept a

32
ground glass stopper or a screw cap. They are often provided with a small ground or
white glaze area near the top for labeling with a pencil.

Figure No 3.3 Test tubes

3.3.3 Graduated cylinder

Graduated cylinders are used to measure the volume of liquid samples and are
available in many different sizes. The measurement accuracy of a graduated cylinder
is rather poor (may be as much as 10% off) so you must consider the desired accuracy
before choosing to use a graduated cylinder. Generally, graduated cylinders are not
appropriate for the preparation of analytical solutions - pipettes, volumetric flasks,
and burettes should be used instead.

Figure No 3.4 Graduated cylinder

33
3.3.4 Thermometer

A thermometer is a device that measures temperature or temperature gradient using a

variety of different principles. A thermometer has two important elements: the
temperature sensor (e.g. the bulb on a mercury thermometer) in which some physical
change occurs with temperature, plus some means of converting this physical change
into a numerical value (e.g. the scale on a mercury thermometer).

Figure No 3.5 Thermometer

3.3.5 Digital Weight Balance

It is a device to calculate the weight of the material. It is a digital measuring device.

To calculate the weight first balance is standardized at 0.00 gram. By the help of this
device we can calculate up to 80 gram.

Figure No 3.6 Digital Weight Balance

34
3.3.6 Magnetic Stirrers

This a device formed by a little metallic bar (called the agitation bar) which is
normally covered by a plastic layer, and by a sheet has underneath it a rotatory
magnet or a series of electromagnets arranged in a circle form to create a magnetic
rotator field. It is a very common that the sheet has an arrangement of electric
resistance that can heat some chemical solutions.

Thus, during the operation of a typical magnetic agitator, the magnetic agitator bar is
moved inside a container that can be a flask or a glass with some liquid inside that can
be agitated. The container must be placed on the sheet, so that the magnetic field
influences the agitation bar and makes it rotate. This allows it to mix different
substances at high speeds. Its abbreviation is “Agg”.

Figure No 3.7 Magnetic Stirrers

3.3.7 pH Paper and pH Meter

1. pH Paper

pH paper (sometimes called litmus paper) is used to test the pH level in certain things.
The paper is specially coated, and when dipped in a liquid it will turn a certain color
depending on if the solution is a base (ammonia) or an acid like (vinegar).

35
 Figure No 3.8 pH paper
2. pH Meter:

A pH meter represents the hydrogen ion concentration in pH units. A pH meter

consists of a glass electrode and a read out screen. The glass electrode is made of very
thin glass that establishes and measures the electrical potential difference between the
analytic solution (the solution to be measured) and an internal reference. The
electrical potential is then converted into a pH reading for the sample.

Figure No 3.9 pH Meter

3.3.8 Hydrometer

A hydrometer is an instrument used to measure the specific gravity (or relative

density) of liquids; that is, the ratio of the density of the liquid to the density of water.

Figure No 3.10 Hydrometer

36
3.3.9 Pipette

A pipette is laboratory tool used to transport a measured volume of liquid.

Figure No 3.11 Pipette

3.3.10 Refractometer

It is used for measuring the amount of sugar bricks in a sample. Usually it measure up
to 30 bricks.

Figure No 3.12 Refractometer

3.3.11 Spectrophotometer

A spectrophotometer is commonly used for the measurement of transmittance or

reflectance of solutions, transparent or opaque solids, such as polished glass, or gases.
However they can also be designed to measure the diffusivity on any of the listed
light ranges that usually cover around 200 nm -2500 nm using different controls
and calibrations. Within these ranges of light, calibrations are needed on the machine

using standards that vary in type depending on the wavelength of the photometric
determination.

37
Figure No 3.13 Spectrophotometer

38
 Process Flowsheet

NaOH & WATER

Pine Cone Pretreatment Hydrolyzer and Heater Cooler

Unreacted

Ethanol Cellouse

Enzyme

SSF REACTOR
Distillation
Centrifuge

Enzyme solution

Figure No 3.14 process flow sheet

3.3.12 Pine Cone Pretreatment

Pine cone is the source of cellulose, In this operation we crush down the pine cone
into small pieces in jaw crusher. Reduce the size to the powder form it will help in
acid hydrolysis process.

3.3.13 Acid hydrolysis and Heating

Acid hydrolysis is important chemical process in which rapture of chemical bonds by

the action of water take place. Generally acid hydrolysis is degradation of a substance.

Acid hydrolysis is the process in which we convert the cellulose into sugar bricks. In
this process we take 5ml of Sulphuric acid (1 N ) solution, 15 ml of distilled water and
0.4 grams of pine cone in test tube. Then we take water in a beaker and put the test

39
tube in the beaker and heat the samples up to 90 C o with constant shaking while
maintain the temperature for different time.

After different time pine cone cellulose is converted into sugar brix.

3.3.14 Cooling

After acid hydrolysis we cool the solution below 20 C o. for this purpose we take the
water in 1000 ml beaker and put the test tube in it. After two hours the sample
becomes cool down. The temperature of the solution is determined by thermometer.

3.3.15 Brix determination

The sugar brix is determined by brix meter or refractrometer. Put the drop on the
screen of brix meter and it will give reading in sunlight. We find the brix by help of
this formula:

Brix = (((182.4601 * SG -775.6821) * SG +1262.7794) * SG -669.5622)

Specific gravity (SG) is determined with the help of hydrometer.

3.3.16 Scarification and Fermentation Reactor (SSF)

Fermentation typically refers to the conversion of sugar to acid, gases and or alcohol
using yeast or bacteria. In its strictest sense, fermentation is the absence of the
electron transport chain and takes a reduced carbon source, such as glucose, and
makes products like lactic acid or acetate. No oxidative phosphorylation is used, only
substrate level phosphorylation, which yields a much lower amount of ATP.
Fermentation is also used much more broadly to refer to the bulk growth of
microorganisms on a growth medium. The science of fermentation is known as
zymology.

The process is often used to produce wine and beer, but fermentation is also employed
in preservation to create lactic acid in sour foods such as pickled cucumbers, and
yogurt.

The chemical equation below shows the alcoholic fermentation of glucose, whose
chemical formula is C6H12O6. One glucose molecule is converted into two ethanol
molecules and two carbon dioxide molecules:

40
 C6H12O6 → 2C2H5OH + 2CO2

C2H5OH is the chemical formula for ethanol.

Before fermentation takes place, one glucose molecule is broken down into two
pyruvate molecules. This is known as glycolysis.

The fermentation process is affected with the following variables.

1. Concentration of sugar
2. Time of fermentation
3. Temperature of fermentation
4. PH of Pine cone solution

The samples made by above process are carried out into the fermentation process. The
following steps are involved:

1. Now the sample of 20 ml is passing through filter paper.

2. In this process of fermentation we will control these parameter
a. pH= 4-5
b. temperature= 20-30 Co

These are the important parameter for the fermentation process.

1. Now we will check the pH of solution by pH paper or by pH meter, if ph is

high more than 5 then we will add some acid H 2SO4 , HCl drop wise, and with
constant shaking and properly examining of pH with the help of pH meter.
2. Then we add 0.4 grams of yeast into the samples and the temperature of
solution in between 20-30 co.
3. When pH is below then 4 then we put some drops of NaoH solution slowly
drop wise and with constant shaking and examining of pH with pH meter, then
add 0.1 to 0.2 grams of yeast and prepare the solution for fermentation .
4. Leave the sample for 24 hours and periodically shake the sample after fix
interval of time.
5. Leave a hole in the test tube so that oxygen can enter and bacteria can grow.
6. Then after 24 hours check the percentage of alcohol by spectrophotometer.

41
3.3.17 Centrifuge

The stream out from the SSF reactor pass to the centrifuge to separate ethanol ,
unconverted raw material on the basis of density.

3.3.18 Distillation Column

Ethanol and enzyme solution out from the centifuge is passed through distillation
column to separate the ethanol and enzyme solution on the basis of boiling point.

42
 CHAPTER # 04

MATERIAL BALANCE

4.1 INTRODUCTION

A material balance also known as mass balance, is an application of conservation of

mass to the analysis of physical systems.

By accounting for material entering and leaving a system, mass flows can be
identified which might have been unknown, or difficult to measure without this
technique. The exact conservation law used in the analysis of the system depends on
the context of the problem, but all revolve around mass conservation, i.e. that matter
cannot disappear or be created spontaneously.

4.2 OVERALL MATERIAL BALANCE

An overall material balance is the application of the conservation of mass to the whole
process. It is simple and is concerned with the input and output streams i.e. the raw
material used and the product obtained. Overall material balance for the process flow
diagram is given as calculated from the Fermentation reaction that takes place.

Overall Fermentation reaction:

2C 6 H 10 O 5 +2 H 2 O → 4 C2 H 5 OH +4 C O2

A general required production of 100 Kg( ≈ 126.7 Liters) of Ethanol is considered.

Knowing the required amount of product, the amount of raw material required can be
calculated from the reaction equation given above, using stoichiometric amounts as
shown

4.3 COMPONENT MATERIAL BALANCE:

The same principles apply as in overall mass balance except that individual
components are considered. The Fermentation reaction given in the previous section
can be split into three separate reactions as under:

1. Liquefaction

43
 2C 6 H 10 O 6 + H 2 O−−−→ C12 H 22 O11

2. Saccharification

C12 H 22 O11 + H 2 O−−−→ 2C 6 H 12 O6

3. Fermentation

2C 6 H 12 O 6−−−→ 4 C2 H 5 OH +4 C O2

Since only the amount of Ethanol required is known, stoichiometric will provide the
amounts produced from which it will be scaled up or down as required and will
consequently be used to calculate the amount of the different components.

Calculations are shown as under.

2C6H10O5+H2O −−−→ C12H22O11 -------------------------------- equation 1

2moles of starch+1mole of water −−−→ 1 mole of sucrose

C12H22O11 +H2O −−−→ 2C6H12O6 --------------------------------- equation 2

1mole sucrose + 1 mole water −−−→ 2moles of glucose

2C6H12O6 −−−→ 4C2H5OH+4CO2 -------------------------------- equation 3

2moles glucose −−−→ 4 molesof ethanol+4molesof carbon dioxide

MAIN REACTION

2C6H10O5 +2H2O −−−→ 4C2H5OH+4CO2

2molesof starch+2 molesof water −−−→ 4 molesof ethanol+4moles carbon

dioxide

Basis is100kg ethanol, but from stoichiometry we have,

From equation 1

324 kg starch + 18 kg water −−−→ 324 kg sucrose

From equation 2

324 kgsucrose+18 kg water −−−→ 360kg glucose

From equation 3

360 kg glucose −−−→ 184 kg ethanol+176 kg CO2

44
Main Reaction:

324 kg starch+36 kg water −−−→ 184 kg ethanol+176 kg CO2

Calculations, for 100 % efficient process are as follows;

From equation 3

184 Kg of Ethanol −requires−−→ 360 Kg of Glucose

360∗100
100 Kg of Ethanol −requires−−→ = 196 Kg of Glucose ----------------
184
1

360 Kg of Glucose −requires−−→ 176 Kg of Carbon Dioxide

176∗196
196 Kg of Glucose −requires−−→ = 95.8 Kg of Carbon Dioxide
360
--------- 2

From equation 2

360 Kg Glucose −requires−−→ 324 Kg of Sucrose

324∗196
196 Kg of Glucose −requires−−→ = 177 Kgof Sucrose ------------- 3
360

360 kg Glucose −requires−−→ 18 Kg of Water

18∗196
196 Kg Glucose −requires−−→ = 9.8 Kg ofWater ------------- 4
360

From equation 1

342 Kg of Sucrose −requires−−→ 324 Kg of Starch

177∗324
177 Kg of Sucrose −requires−−→ = 162 Kg of Starch --------------- 5
342

342 Kg of Sucrose −requires−−→ 18 Kg of Water

177∗18
177 Kg of Sucrose −requires−−→ = 9.31 Kg of Water --------------- 6
342

A 100 Kg of Pine cone contain 65.40% by weight Starch as shown in the table below.

45
Now, amount of Pine cone t o produce100 Kg of Ethanol required −→ 65.40
Kg of starch

100kg of pine cone required = 65.40 Starch

? = 162kg of Starch

= 162×100÷65.49

=244kg

Table 4.1: Typical Composition of Pinecone

Parameters % dry weight

Moisture 14.66
Nitrogen 1.3
Protein 8.0
Total Soluble Sugars 1.0
Total Carbohydrates 65.49
Reducing Sugars 0.61
Fat 2.6
Ash 6.34

Table 4.2: For 100% conversion

Components Moles Mass Mass (Process

(stoichiometric) Requirement)

Starch 2 324 162Kg

Disaccharide(sucrose) 1 342 177 Kg
Total Water 2 36 9.87Kg
Glucose 2 360 196 Kg
Carbon Dioxide 4 176 95.8 Kg
Ethanol 4 184 100Kg
pine cone - - 244 Kg

46
SSF process has a typical efficiency of 90 %. Applying a conversion factor of
(100/90), the new amounts are

Table 4.3: Component Material Balance according to Glucose

and Ethanol yield

Actual Yield Components Actual Process

- Starch 145.80kg
- Disaccharide(sucrose) 159.30
- Total Water 8.883 Kg
- Glucose 176.40 Kg
- Carbon Dioxide 86.22Kg
90% Ethanol 100 Kg
- Pine cone 219.60Kg

Equipment Material Balance

A material balance applied around each equipment of the process to specify each inlet
and outlet stream along with their masses. In this case, the equipment material balance
will be done on the:

4.4 PRE TREATMENT UNIT

Inlet stream outlet stream

PRE TREATMENT

219.60g pine cone 219.60 kg pine cone

Figure 4.1: Pretreatment

47
4.5 HYDROLYZER;

219.60*1.O5=230.58Kg while 1.05 is conversion factor

H2SO4(CONC) Hot H2O

HYDROLYZER
219.60 kg pine cone 230.58 kg gelatinized pine
NaOH

Figure 4.2: Hydroloyzer

4.6 COOLER

COOLER
230.58 KG PINE CONE

At 90CO 230.58 KG Pine cone at 45C0

Figure 4.3: Cooler

4.7 SSF UNIT

enzyme
SSF UNIT
Gelatenized pine cone3.83 kgenzymes

230.58Kg pine cone

90 kg of ethanol + 3.83 kg enzymes solution

48
4.8 CENTRIFUGE

90 kg ethanol + 3.83 enzyme sol.90 kg ethanol + 3.83 enzyme sol +unconverted raw
material(55.8kg)

Centrifuge

ethanol + 3.83 enzyme To distillation coloumn

Unconverted raw material (55.5kg)

Figure 4.5: Centrifuge

4.9 DISTILLATION COLOUMN

Distillation
column

90 kg ethanol + 3.83 enzyme sol Purified ethanol

Storage tank

(96%) pure

Residue

Figure 4.6: Distillation column

49
 CHAPTER # 05

ENERGY BLANCE

5.1 INTRODUCTION

Alcoholic fermentation also referred to as ethanol fermentation is a cellular energy

and produce ethanol & carbon dioxide as a metabolic waste products. Because yeast
performs this conversation in absence of oxygen, so it is also called anaerobic
process.

Energy is required for conversation of sucrose into glucose so this energy is supplied
to hydrolyser in form of heat. In hydrolyses heat is supplied at 90c 0 for two hour. In
chemical process, energy should be in or out. Energy is key factor for chemical
process while designing a process must be balanced; energy balance is very useful for
chemical process. By the help of energy balance we can find total energy required
for chemical process. As we know there are two types of chemical process, one is
endothermic process and other one is exothermic process. Endothermic process is a
process in which heat is required and exothermic process is a process in which heat is
evolved.

Energy balance tells about how much energy will be evolved. If incorrect energy
balance is carried over a process, then process will move in wrong direction and left
the process will collapse. There are several types of energy balance carried over a
chemical process i.e. integral energy balance and other one is differential energy
balance should be taken over all relative and non-relative process. In relative process
the breakdown of native molecules in formation new molecules and compounds .The
process of separation, drying and evaporation is non-reactive.

In formation process hydrolyser, SSF reactor and cooler are used, so energy balance
must be carried out each reactor individually. Energy balances help us in designing a
process because maintenance, safety and instrumentation greatly depend on energy
balance. Also some amount of catalyst used in chemical process. These catalysts
deactivate at low and high temperature, so energy balance is necessary for a process
design.

50
Energy balance has some bases, first law of thermodynamics, and law of conversation
of energy.

5.2 ENERGY BALANCE AROUND ACID HYDROLYSER

It is a unit in while sucrose is treated with what concentrated Hydrogen sulphuric acid
(H2SO4) with constant is heating at 90C0 for two hours. So energy is given to system
in form of heating so energy balance will be

REACTION:

C12H22O11+H2O (T,P),90 C0 , 1 atm 2C6H12O6

(Sucrose) (Glucose)

Applying energy balance equation

Q - WS = ΔHr + ΔK.E + ΔP.E ………………….. ( 1 )

Q = ΔHr

∆ Hr = Hreactant– Hproduct (at 25 C0 , 1atm )

= (1194.618 KJ / mol) …………………( from literature )

Now at 90C0 use the formula,

∆HT = ∆ Hr + ʃ Cp ∆T

∆HT = ∆Hr + Cpʃ ∆T

∆HT = ∆Hr + CP (T2 – T1). . . . . . . . (2)

Cp = 1.607 kj/kg.k ( from literature)

∆T = (T2 – T1) = ( 90 – 25 )

= 65 C0 = 338 K

Putting the Value in equation (1)

=1194.68 KJ / mol+ (1.607) (338) KJ.K/ Kg.K

= 1194.68KJ/mol +543.16KJ/kg

= 1194.68 KJ/mol + 543.16 kj/kg × 342 kg/ K mol × 1Kg/ 1000 gm

51
 ∆H = 1380.4407KJ/mol

Putting in equation ( 1 ) ,

Q = 1380. 4407 KJ / mol

Since it has positive sign ,So it is endothermic process .

5.3 ENERGY BLANCE AROUND SSF REACTOR:

It is performed at room temperature, So taking value from literature

REACTION

2C6H12O6 Yeast 4C2H5OH + 4CO2 ( T,P) = 25Co& 1atm ,

Applying energy balance equation ,

Q - WS = ΔHr + ΔK.E + ΔP.E ……… ( 3)

Q = Δ Hr …………………… ( 4)

From literature heat of reaction of the above reaction ,

Δ H r = - 137 . 7 KJ / mol

Putting values in equqtion ( 4),

Q = - 137 . 7 kj /mol

Since it is negative sign, so it is exothermic process .

5.4 ENERGY BLANCE AROUND COOLER :

The purpose of the cooler is to evaloved extra amount of heat from the product.

Applying energy balance equation,

Q - WS = ΔHr + ΔK.E + ΔP.E ………… ( 5)

H = ʃ n c mdT . . . . . . . . (6)

n = 2 (from material balance)

molar heat capacity of ethanol = cml = -1.2KJ/mol

put in equation ( 5 )

52
 Q = - 2.4 KJ/mol

Since negative sign, so it is exothermic process.

53
 CHAPTER #06

PLANT DESIGN

6.1 DESIGN OF FERMENTER (SSF REACTOR)

It is necessary to calculate the volume of SSF reactor.

6.1.1 Knowing Data:

Conversion = 90 %

Density = 120 Kg / m3

Temperature = 25 C®

6.1.2 Designing Steps:

REACTION: 2C6H12O6 4C2H5OH + 4CO2

To calculate holding time ,

-ln (1 - xA ) = Kt . . . . . . . . . (1)

XA = 90%

The reaction is first order reaction so the rate constant value from
literature,

K = 0.0052 min-1

So,

= -ln ( 1 - 0.90 ) = 0.0052min-1 t

t = 4 hr

6.1.3 Volume of SSF Reactor

V = m/ƿ . . . . . . . . . . . . . (2)

Mass of pine cone = 219.6 Kg (from material balance)

(from literature) ,the pine cone density

54
 Density = 120 Kg/m3

So, put in equation

V = 219Kg/ 120 Kg / m 3

V = 1.83m3 = 1830 liters

t = 7.5 hours (holding time)

6.2 DESIGN OF DISTILLATION COLUMN

Objective

To separate ethanol / enzyme solution.

Assumption

The feed to the column is completely vapour at temperature of 78C 0at pressure of 1
atm.

Tray spacing is 0.61 m.

Desired

To obtain product (ethanol) of 96% purity.

Steps

Material balance around the column

F = B + D. . . . . . (3)

Fxeth = Bxeth + Dyeth. . . . . . (4)

Fxenz = Bxenz + Dyenz . . . . . .(5)

Putting value in equation (3)

0.93 x 0.90 = 0.04 ( 0.03 - D ) + 0.96 D

D = 0.86 kmol

S0,

F = B + D

0.93 = B + 0.86

55
 B = 0.07 kmol

(Xeth)B = ? , ( xenz) B = ?

Fxeth = B ( xeth)B + D ( xeth) D . . . . . . . (6)

0.93 x 0.90 = 0.07 ( xeth )B + 0.86 x 0.96

Xeth = 0.171 kmol

So,

Fxenz = B ( xenz ) B + Dyenz . . . . . . . . . (7)

0.93 x 0.03 = 0.07 xenz + 0.86 x 0.04

Xenz = 0.336 kmol

6.2.1 Minimum numbers of stages.

Nmin = ln[ (XLK / XHK )D ( XHK / XLK )B] . . . . . . (8)

LnαLK / HK

Heavy Key component =HK = enzyme

Light key component =LK = Ethanol

Nmin = ln[ ( 0.996 / 0.004 ) ( o.336 / 0.171 ) ]

ln 1.136

Nmin = 51.58

6.3.2 Minimum reflux ratio

Rm = 1/α - 1 [ Xd / Xf - α ( 1 - Xd / 1 - Xf) ] . . . . (7)

Rm = 1 / 1.136 – 1 [0.96 / 0.90 - 1.136 (1-0.96/1-0.90)]

Rm= 4.48

6.3.3 Actual Reflux Ratio:

We know that

R = 1.2 Rmin

56
 R = 1.2 x 4.48

R = 5.38

6.3.4 Actual number of theoretical stages.

N-Nmin/N+1 = 0.75 ( 1 - R- Rmin/R+1) 0.566……………….. (9)

N– 51.58/ N + 1 = 0.75 (1 – 5.38 - 4.48 / 5.38 + 1)

N = 145 Theoretical stages

6.3.5 Location of feed:

log ND/NB = 0.206 log [( B/D) ( XHK / X LK ) F [ ( XLK ) B / (XHK)D ]2]……(8)

log ND/NB = 0.206 log [ ( 0.07 /0.86) ( 0.03 / 0.90) [ 0.171 / 0.004 )2 ]

log ND/NBB= - 0.28

ND = 0.75 NB ……………………………………… (9)

So,

N = ND +NB………………………………………………(11)

145 = 0.75 NB + NB

Solving the equation

NB = 83 , ND= 62

The feed enters the column 83 theoretical stages above the bottom stages.

To obtain the net vapour velocity at flood condition .The net vapour velocity should
be obtain at bottom ends of the column, which is required for column diameter.

So,

Equation from plant design book ,

Vnf = C sb ( α / 20 )0.2 ( ƿ L - ƿ V / ƿ V ) 0.5 …………………………………(12)

Liquid ethanol density =ƿL = 789 kg/m3 ( from literature )

Vapour ethanol density = ƿ v = 1.5 kg/m3 ( from literature )

57
 Surface tension = α = 17.6 dyne /cm ( from literature )

So,

First calculate Csb from fig 15.5 (PD book)

(L /V) ( ƿV / ƿ L ) 0.5

L = 15. 58 , V = 16.58 ( from literature)

(15.58 / 16.58) (1.5 / 789) 0.5

0.04

C sb= 10 -1 = 0.1 m/sec

Put Csbin eq (12)

Vnf= 0.1 (17.6 / 20) (789 – 1.5 / 1.5) 0.5

Vnf = 2.01 m /sec

Assume 80% flooding velocity.

Vn = 0.8 Vnf …………………………………………………………………. (13)

Vn = 0.8 × 2.01

Vn =1.6 m / sec

From equation (15.8) PD book

An =m v / Vn…………………………………………………………………. (14)

An = 16. 58 m3 / sec / 1.6 m / sec

An =10.3 m2

Assume the down comer area occupies 15% of cross sectional area of column

So,

Ac =An / 0.85 ………………………………………………………………. (15)

Ac =13.4 m2

6.3.6 Diameter of the column

D = (4 A c / π) 0.5………………………………………………………….(16)
58
 D = (4 × 13.4 / 3.14)0.5

D = 4.13 m

6.3.7 Hight of Column

HC = ( N act - 1 ) H S + ∆ H………………………………………(17)

∆H =0 (Because no additional height required for column)

H S = Tray Spacing

So,

H C = (N act - 1) H S……………………… (18)

HC = = (145 – 1) (0.61)

H C = 87m

6.3 DESIGN OF COOLER

Cooler is actually a heat exchanger .Considering one shell pass and two tubes passes
heat exchanger

6.3.1 Area calculation:

Q = U A ∆ T lm ……………………………………… ( 19)

A = Q / U ∆Tlm……………………………………………………………….. (20)

Q = 3276000 × 10 3 KJ/ hr

U = 100 Btu / hr.ft2.K (taking from table)

T lm = ( T2 - T 1 ) - ( t2 - t1 ) / ln[ ( T 2 - T1 ) /( t2 - t1 )] ……………….. (21)

ΔTlm= ( 194 – 113 ) - (104 – 77) / ln (194 -113)/ ( 104 – 77)

ΔTlm = 94.54 K

Putting in equation (20) ,

A = 3276000 × 10 3 / 26063829

A = 125 ft2 = 11.67 m2

Now for,

59
6.3.2 Number of Tubes

Choosing 20 mm OD and 16mm ID and taking 4.83 m long tube

Area of the tube =π L D0............................. (21)

= 3.14× 4.83 × 20 / 1000

= 0.303 m2

Number of tubes = A / A t ……………….. ( 22)

= 125 ft2 ×1 m 2/ 0.303 m2× (3.2 ft) 2

Number of tubes = 40 tubes

Number of shell = 40 / 2

Number of shell = 20

6.3.3 Shell Diameter

The mixture is relatively clean using 1. 25 triangular pitch

Bundle Diameter , D b = D 0 ( Nt / K ) 1 / n …..……………. (23)

For one shell pass and two tubes passes

K = 0.249

N = 2.207

D b = 20 (40 / 0.249) 1 / 2.207

Db = 196 .6 mm

Using split ring floating head type,

Bundle Diametrical clearance = 68 mm

Shell diameter = 196.6 + 68

= 264.6 mm

60
 CHAPTER # 07

COST ESTIMATION

7.1 INTRODUCTION

Cost is the worth of money to have been utilized up to build somewhat and therefore
it is not objectionable for utilize anymore .In business the cost can be one of gaining
in which case the quantity of money obtaining it is calculate as cost .In this case,
money is the output that is vanished in position to obtain the project .This gaining cost
may be the amount of the cost of manufacture as gain by the original procedure and
additional cost of contract as gained by acquirer of excess of as and higher than the
value paid to the manufacture. Generally ,the worth also comprises a gain for earning
over the cost of construction.

When raising a business plan for fresh or obtainable company or project cost
estimation is made and also look its feasibility report ,also look that hoe much it is
profitable .Also through benefit cost analysis calculation and comparison of cost and
project is take place that how much it is profitable .

It is used for calculation of positive and negative task

Table 7.1: Typical average equipment materials of

construction capital cost factors

Materials Correction factor (fM)

Carbon steel 1
Aluminum 1.3
Stainless steel (Low grade) 2.4
Stainless steel (High grade) 3.4
Hastelloy C 3.6
Monel 4.1
Nickel and Inconel 4.4
Titanium 5.8

61
TABLE # 7.2: Typical materials of construction capital cost
factor for pressure vessel and Distillation column

Materials Correction factor (fM)

Carbon steel 1

Stainless steel (Low grade) 2.1

Stainless steel (High grade) 3.2

Mantel 3.6

Inconel 3.9

Nickel 5.4

Titanium 7.7

TABLE #7.3: Typical materials of construction capital cost

factor for shell and tube heat exchange

Materials Correction factor (fM)

Cs shell and tube 1

Cs shell, Aluminum tubes 1.3

Cs shell, ss (low grades) tubes 2.1

Ss ( low grades ) shell & tubes 2.9

62
TABLE # 7.4: Typical equipment pressure capital cost
factors

Design Pressure ( Bar Absolute ) Correction factor (fP)

0.01 2

0.1 1.3

0.5___7 1

50 1.5

100 1.9

TABLE # 7.5: Capital equipment pressure capital cost

factors .

Design Temperature ( C0) Correction factor (fT)

0_________100 1

300 1.6

500 2.1

7.2 COST ESTIMATION FOR SSF REACTOR

Material of construction, carbon steel

Cost found by formula

CE = CB (Q /QB) M …………………… ( 24)

CE = Equipment cost with capacity Q

CB = Know BASE cost of equipment for QB

QB= Base size

M= Constant depend on equipment type

Now to design the SSF reactor of volume ,Q = 1.83m3

So,

63
 CE = 1.15 × 104 ( 1.83 m 3 / 1 m3 )

CE = $ 15093.8

NOW,

CE1 /CE2= index1(2000) / index2(2005)…………(25)

CE2 = index2(2005) × CE1 / index1(2000)……… (26)

SO,

CE2 = 15093.8 × 441.9 / 435.8

CE2 = $ 15305

Now including correction factors,

Temperature correction factor

Ft = 1.0(for 0_100)

Pressure correction factor

Fp = 1.0 (0.5 – 7)

And

Material of construction of equipment

Fm = 1.0(for carbon steel)

Now,

Total cost =CE × Ft ×Fp×FM

= 15305×1.0×1.0×1.O

=$15305

7.3 COST ESTIMATION FOR COOLER

The material of construction for shell and tube heat exchanger is carbon steel.

SO,

CE = C B (Q / QB )M…………………………(27)

CB = 3.2 × 104

64
 QB = 80 m2 , M= 0.68

To design cooler of area, Q = 11.67m2

Put values in equation (27)

CE = 3.2 × 104 (11.67 m / 80 m )0.67

CE= $ 8644

To update the capital cost

CE1 / CE2 = Index1 / Index2 ……………….(28)

CE2 = CE1 × Index2 / Index1 ………… ……(29)

CE2= 8644 × 441.9 / 435.8

CE2= $ 8765

Including correction factors

Ft = 1.0

Fp = 1.0

FM =1.0

So,

Total cost = $ 8765×1×1×1

=$ 8765

7.4 COST ESTIMATION FOR DISTILLATION COLUMN:

Material of construction is stainless steel

CE = CB ( Q / QB)M …………………. (30)

Height = h = 87 m

CB = 1.8 × 10 4

QB = 0.5 m , M = 1.7

To design distillation of diameter, Q= 4.13m

Put in equation (30),

65
 CE = 1.8 × 104 (4.13 / 0.5)1.7 × 87/ 5

CE = $ 9.4 × 10 6

Now to update the capital cost,

CE2 = CE1 × index1 / index2 …………….. (2)

CE2 = 9.4 × 10 4 (441.9 / 435.8 )

CE2 = $ 9.53 × 10 6

Including correction factors

Ft = 1.0

Fp =1.0

FM =2.1

Now,

Total cost = $ 9.53 × 10 6 ×1.0×1.0×2.1

= $2001300

7.5 TOTAL PURCHASED EQUIPMENT COST ( TPEC)

Total purchased equipment cost = SSF reactor + cooler + distillation column

= $15305 + $8765 +$2001300

= $2025370

Now ,

Estimating total fixed cost;

Total fixed cost,cf =

From cost index,

For, erection of equipment =0.4

Fpip, piping =0.7

Fins, instrumentation =0.2

Felect =0.1

66
 F utility = 0.5

F off side = 0.2

F build = 0.1

F design = 1.0

F contingency =0.4

F working capital =0.7

F side preparation = 0.1

So,

Cf=$2025370[1+0.7]+$2025370[0.4+0.2+0.1+0.5+0.2+0.1+0.1+1.0+0.4+0.7]

= $10936998

Now other cost

Maintenance cost

The range of maintenance cost is 5 _ 10 %

Maintenance cost = 8%( CF )

CM =$10936998 ×0.08

= $874959.84

Labour cost = 15% ( CF )

= $10936998×0.15

=$1640549.7

Capital charges =15% ( CF )

=$10936998×0.15

==$1640549.7

Insurance =1% ( CF)

=$109369.98

Local taxes =2%( CF)

67
 =$218739.96

Royalities = 1%(CF)

=$109369.98

Miscellaneous materials = 10%( CF)

= $1093699.8

Plant overhead = 50%(labour cost)

=$820274

Supervision = 20%( labour cost)

=$328109

Labortary cost = 20%( labour cost)

=$328109

Raw materials cost = $1.1/Kg

= 220×$1.1/Kg

=$242

Total cost =

=874959+1640549+1640549+109369+218739+109369+1093699+8220274+328109
+328109+242

= $13579637

Sales+overhead+research = 25% 0f ( production cost + raw materials cost)

=$ 3394969.8

Annual production cost = $13579637 +$1.25×(raw materials cost)

=$13579637 +$1.25( 242)

= $13579940

So,

Annual production cost = $13579637+$ 3394969.8+$13579940

68
 = $30554546

Now,

Sales price of bio ethanol= $0.357/Kg

Total profit = (sale price of bio ethanol × SSF reactor)

=$0.357/Kg × 100 Kg × 100 Rs / $1

Total profit =3000 Rs/day

69
 CHAPTER # 08

PROCESS SAFETY AND HAZOPE STUDY

The number of accident has been increase as the world got industrialization. So the
chemical process has been priority .These accident include the releasing of poisonous
gases, explosion and environmental problems. The national and international rules are
composed to bring safety in industries particularly in chemical process industries. No
one can think about a chemical industry without safety which is explained here in
production or generation of ethanol from pinecone. Toxic and corrosive agent
generating from the process are dangerous.

8.1 CHEMICAL PROCESS SAFETY

* In chemical process safety we deal with the accident which are caused by
machine only.

* Increase awareness of potential chemical hazards associated with chemical

manufacture in batch and Sami batch process.

* Provide a systematic approach for the design operation and control of

chemical reaction in batch and semi batch process.

8.2 INHERENTLY SAFER PROCESSES

However, o preferred philosophy is being used increasingly within industry. This is to

eliminate hazard completely or to reduce its magnitude sufficiently to avoid the need
for elaborate safety system and procedures. This hazard elimination or reduction can
be done by means that are inherent in the process .It is easier to consider inherently
safer processes or plant at the earliest stages of process development.

Changing the materials, chemistry or process condition can reduce or eliminate

hazards .Reduction of hazards in process this way are inherently safer processes.

70
8.3 PROCESS SAFETY ANALYSIS

In process analysis, we analyses the process from point of view of hazards, risk and
methods for loss evaluation and process assessment and audit. It will also be useful in
administration in risks in a process. It includes:

 Hazards examination.
 Risk analysis.
 Estimating loss.
 Process calculation.
 Process procedure.

8.4 SAFETY DEVICES

There are many chances of occurring accidents in many positions. An accident can
rise in pressure relief system, spark arresters and technique of controlling sewage.
Techniques of controlling sewage also control the unwanted products. In ethanol
generation from pine cone some highly unwanted gases are also obtained .Particular
equipment should be used for controlling highly poisonous chemicals.

The following problem are considered

8.4.1 Temperature Relief System

This system maintains the temperature of the process. Any inequality of temperature
will be adjusted by the temperature system.

8.4.2 Pressure Relief System

This system can maintain the pressure at a desired value. If the pressure of process
increases from the desired, this system brings back the pressure to the desired value.

8.4.3 Spark Arresters

Spark arresters can cause fire to burn. It should be handled gently otherwise serious
problem can take place.

8.4.4 Emergency Assistance System

Initiating emergency procedures at the earliest stage of an incident significantly

reduce the impact of an incident on people and premises. In case of fire, spills or
leaks.
71
It should cover:

 Raising the alarm.

 Calling the emergency services.
 Evacuating the area and providing safe havens.

8.5 HAZARDOUS MATERIALS AND CONDITIONS

The chemical and physical properties of hazardous material that are to be handled
should be aware of gently.

In our plant, we will deal with the following hazardous materials and precarious
functions. These are:

8.5.1 Explosion

Explosion take place as a result of high pressure .In SSF reactor the reaction take
place normally high pressure and a high temperature is used .The pressure inside SSF
reactor can be reduce by the help of relief valves. We will first measure the pressure
of SSF reactor .The explosion that will take place will be most dangerous, because
reactive chemical, corrosive agent, toxic agent and other catalyst will deeply hurt the
environment.

8.5.2 Temperature Control

The temperature of the SSF reactor should be notice gently. Any incorrect reading can
damage the process and also the entire plant.

8.5.3 Reactive Chemical

Reactive chemicals are also dangerous they consist of all harmful agents. They should
be handled gently.

8.6 CONDUCTING THE SAFETY INSPECTION

To make the process safe and sound, there should be regular inspection of the process.
This inspection should be after a fix interval of time .If any maintenance required, and
then it should be done. Inspection also helps in minimizing the causality because it
will be treated before it convert into any giant problem. Safety inspection can increase
the cost of process.

72
8.7 PROVIDING THE BASIS OF ANALYSIS, REPORT AND
CONTROL

8.7.1 Disabling injuries

By disabling injuries, we mean reducing injuries. It provide basis for investigation and
safety of the process.

8.7.2 Severities

The severities of the process should be completely eliminated; otherwise the

performance of the process and plant will be affected.

8.7.3 Exposure Hours

The exposure time of hazards should be kept at maintain. The exposure cannot be
completely eliminated. If the exposure hour become large, then serious health and fire
problems takes place .It will directly affect lungs and can create cancer and breath
problems.

8.8 KNOWING THE HAZARDS

The knowledge of the hazards is most important. There are many hazards which are to
be faced during the process. They should be treated according to the situation .Any
improper treatment can cause dangerous problems .These hazards can cause death.

8.9 RECORD KEEPING

The efforts and inspection done for making the process safe should be recorded .This
record will show the when the inspection was done and how it was treated. The date
and time of inspection and treatment should also be recorded .This record will helps
in future inspection, treatment, designing and planning.

8.10 TYPES OF CHEMICALS

There are several chemical which are associated with SSF reaction process. They
affect animals and environment equally.

73
8.10.1 Corrosive

The corrosive agent can create skin problems, irritation and corrosion of the process
equipment and non process equipment .IT can be very dangerous when humidity of
air is high especially when contact time is more.

8.10.2 Flammable and combustible

The flammable and combustible product is also dangerous. When there is high
amount of the combustible, the of fire is high.

There is some also reactive agent. These reactive can create skin problems and can
generate irritation.

74
 CHAPTER # 09

INSTRUMENTATION AND PROCESS CONTROL

9.1 INTRODUCTION

Due to the advancement of technology instrumentation has grown up from a series of

devices developed to fill specific needs of measurements and control, to a science
itself where economics of entire plant and processes are based on suitable control
strategies and instrumentation systems. Control system technologies are developed for
rapid expansions in chemical and petroleum industries.

So this topic is easily organized in terms of

1. The variables that require measurement.

2. The means used to control these variables automatically, semi automatically

or manually.

As a process is designed for a particular output and is then found, sometimes by trial
and error and sometimes by inference from previous experience that control of a
particular variable associated with some stages of the process is necessary to achieve
the desired efficiency. Instrumentation generally and process control specially are
directed responsible for processes which are complex, integrated and large, both
physically and in terms of through put faster more critical and more hazardous
operation can be carried out because of suitable control equipment.

In manual control an operator may periodically read the process variable and adjust
the input up or down in such a direction as to derive the temperature to its desired
value. Manual control is used in non-critical applications, where any process
conditions occur slowly and in small increments and where a minimum of operator
attention is required.

While in automatic control, measurements and adjustments are made automatically on

a continuous basis. Today automatic control is used in industry due to following
benefits.

1. Improvement in product quality.

75
2. Increase in process yield or production rate.

3. Increase safety for personnel and equipment.

4. Economics saving in materials, energy or time.

5. Improvement of working conditions.

6. Achievement of operation not possible by manual control.

9.2 OBJECTIVE OF INSTRUMENTATION & CONTROL

SYSTEM

1. Suppressing or killing the external disturbances.

2. Operate the process in a stable manner.

3. Optimize the process operation.

9.3 COMPONENTS OF CONTROL SYSTEM

9.3.1 Process

Any operation or series of operations that produces a desired final result is a process.

9.3.2 Measurement Mean

Measurement is a fundamental requisite to process control whether that control is

affected automatically, semi automatically or manually. Therefore of all the parts of
the control system, the measuring element perhaps the most important. If
measurement is not made properly, the remainder of the system cannot operate
satisfactory.

9.3.3 Process Variables

The even operation of a process is dependent upon the control of the process
variables. These are defined as conditions in the process materials or apparatuses,
which are subject to change. Temperature, pressure, flow and liquid level are the
major variable, followed by perhaps a dozen less frequently encountered variables
such as chemical composition, viscosity, density, humidity, moisture content and so
forth.

76
Measurement is a fundamental requisite to process control either the control can be
affected automatically, semi automatically or manually. The quality of control
obtainable also bears a relationship to the accuracy, reproducibility and reliability of
the measurement methods, which are employed. Therefore, selection of the most
effective means of measurements is an important first step in the design and
formulation of any process control system.

An automatic control is used to measure, correct and modify changes of the four
principle types of process variations.

1. Temperature measurements
2. Pressure measurements.
3. Flow rate measurements.
4. Level measurements

Various type of measuring instruments for temperature, pressure, flow, and level are:

Measured Process Measuring Devices Comments

Variable

TEMPERATURE Thermocouples Most common for

relatively low temp.
Resistance thermometers Thermistor

Filled system thermometers Bimetallic

thermometers Radiation pyrometers Used for high temp.
Oscillating quartz Crystal

PRESSURE Manometers With float or

displacers based on
Bourdon Tube elements Bellows
the elastic
elements
deformation of
Diaphragm elements
materials
Strain gauges
Used to convert
Piezo-resistivity elements Piezo- pressure to Electrical
electric element signal

For Measurement of
vacuum
Capsule gauges

77
 Thermal conductivity gauge McLeod
gauge

Flow Orifice plates Measuring pressure

drop across a flow
Venture flow nozzle
constriction
Dall flow tube

Pitot tube

Kennison flow nozzle

Turbine flow meter

For high precision
Hot wire anemometry
quantity flow meter
Positive displacement & mass flow
meter.

9.4 TEMPERATURE MEASUREMENT & CONTROL

The temperature measurement is used to control the temperature of outlet & inlet
streams in heat exchangers, reactors etc. most temperature measurement in the
industry are made by means of thermocouples to facilitate bringing the measurements
to centralized location, for local measurements at the equipment bi-metallic or filled
system thermometers are used to a lesser extent .usually, high measurement accuracy
resistance thermometers are used. All these meters are installed with thermo-walls
when used locally. This provides protection against atmosphere and other physical
elements.

9.5 PRESSURE MEASUREMENT & CONTROL

Like temperature, pressure is a variable indicating material state & composition. In

fact, these two measurements considered together are the primary evaluating devices
of industrial materials.

In the reactor, pressure measurement is of primary importance. Pumps, compressors

and other process equipment associated with pressure changes in the process material
are furnished with pressure measuring devices. Thus pressure measurement becomes
an indication of energy increase or decrease.

78
Most pressure measurement in industry is elastic element devices, either directly
connected for local use at transmission type to centralized location. Most extensively
used industrial pressure element is the bourdon tube or a diaphragm bellows.

9.6 FLOW MEASUREMENT & CONTROL

Flow indicator-controllers are used to control the amount of liquid. Also all manually
set streams require some flow indication or some easy means for occasional sample
measurement, for accounting purpose; feed and product streams are metered. In
addition utilities to individual and group equipment are also metered. Most flow
measurements in industry are variable head devices. To a lesser extent Variable area is
used, as are the many available types as special metering situations arise.

9.7 INSTRUMENTATION & CONTROL ON SSF REACTOR

Amongst the two types of control loops i.e. Feed forward control loop and Feed
backward control loop, we have selected Feed backward control loop to be efficiently
installed on our heat exchanger which is an ancillary equipment for the reactor in our
process.

9.8 COMPONENTS OF FEEDBACK CONTROL LOOP

The basic Feedback control loop consists of a sensor to detect the process variable; a
transmitter to convert the sensor signals into an equivalent air pressure or electrical
signal; a controller that compares this process signal with a set point and produces an
appropriate control signal; and a final control element that changes the manipulated
variable. Usually the final control element is an air operated control valve that opens
and closes to change the flow rate of the manipulated stream. Here in our system, the
manipulated stream is the cold water entering the Reactor and we applied control over
it.

9.9 PROCESS REQUIRMENTS

In our process, the reaction which is going on in the reactor is exothermic and to
maintain the temperature in the reactor we have to remove excess heat from the
reactor. For that purpose cold water is allowed to circulate through the vertical coil in
the reactor. So for that purpose we are using a thermocouple, which tells us the

79
temperature in the reactor. We want to maintain the temperature at 81C. So if there are
some fluctuations in the reactor temperature then through the thermocouple wires, the
signals enter the Transmitter. The Transmitter converts the EMF signals coming from
the thermocouple into the process signals. The signals after the transmitter are also
called Process Signals. Then these process signals go into the Feedback Controller.
The controller has already been given as Set Point of 81 C. Now the controller
compares the measured value coming from the thermocouple with the set point given
and estimates the Error. This error, in the form of Control Signals, is passed to the
Pneumatic Control Valve. The error estimated in the controller actuates the control
valve to take the necessary action. This pneumatic control valve is installed on the
inlet of the cold water which is entering into the vertical coils of the reactor. This
valve controls the flow rate of the water entering the reactor by which a constant
temperature can be maintained of the required stream. If the thermocouple measures
the exit temperature more than 81 C then the controller actuates the control valve and
it opens more so that more water can pass through the reactor. So in this way control
works.

9.10 THERMOCOUPLES

Thermocouples are the most commonly used temperature sensing devices. The two
dissimilar wires produce a milli-volt EMF that varies with the “Hot junction”
temperature. The thermocouples therefore give the output signals in the form of
electronic senses which are undoubtedly more accurate and the biggest advantage is
that they have least Time Lag or Delay.

9.11 RESISTANCE THERMOMETER

Are not used in this system because they use the principle that the electrical resistance
of a wire changes with temperature. This involves the material properties of wires and
complex equations which are applied to get the temperature readings from the
resistance measured. Here we used copper – constantan thermocouple which has a
range of -200C to 381C. The other types of thermocouples are expensive than copper
type and also their ranges are not feasible here.

80
9.12 BIMETALLIC THERMOMETER

Are not used because they have lower ranges than thermocouples. As the temperature
increases, the metal begin to expand but not with the same rate and their differential
expansion causes the helices to uncoil.

9.13 RADIATION PYROMETERY

Radiation pyrometers do not need to be in direct contact with the object whose
temperature is sought, since they are based on the measurement of the radiant energy
emitted by the body. The ranges involved are usually above the freezing point of gold
(1063C the gold point). As brine is not radioactive in nature nor it is brought to
temperatures of 1063C that why we are not using this technique of measuring
temperature.

9.14 CONTROLLER & PNEUMATIC VALVES

The controller is the heart of control system and its job is to compare the process
signal from the transmitter with the set point and to send an appropriate actuating
signal to the control valve. The controller is usually located on a panel in the control
room that is some distance from the process equipment.

Electronic control devices are used when the control room is located a long distance
from the process equipment and when rapid transmission of signals is required. In
pneumatic systems the transmitter is connected with controller and controller to the
valve this represents a dynamic lag in the control loop. Pneumatic systems are most
widely used by chemical engineers due to their ease of usage. Here we used a
pneumatic control valve which is connected to the controller with a feedback control
system as the manipulated variable is changed after the disturbance has been sensed.

81
 CHAPTER # 10

MAINTENANCE OF EQUIPMENT
Maintenance is a combination of actions carried out in order of repair, replace of
service the components a manufacturing plant, so that it will continue to operate for a
specified availability, for a specified time. Maintenance is to done to raise the level of
performance and increase the profit.

The principle purpose of maintenance in a typical industrial environment is;

 To efficiently, effectively and rapidly respond to the need for corrective action
in the event of equipment failure.
 To preserve the value of a plant by minimizing wear and deterioration.
 To maximize the availability of the equipment for production.
 To maximize the probity that the equipment is fully capable of performing its
intended service.
 To assist in minimizing unit capital cost of production in the long run.

10.1 MAINTENANCE OF SSF REACTOR

10.1.1 Reactor Geometry

Reactor geometry can limit of potential temperature excursions in a chemical process.

For example , malefic anhydride is manufactured by partial oxidation of benzene In a
fixed catalyst bed tubular reactor .There is a potential for extremely high temperature
due to thermal runway if feeds ratios are not maintained within the safe limit .
Catalyst geometry, heat capacity, and partial catalyst deactivation to create a self –
regulatory mechanism to prevent excessive temperature.

10.1.2 Pressure Check

The loss of feed water meant that the reactor’s heat had nowhere to go, so temperature
and pressure started to climb .Sensing, the control system tripped the reactor, within a
few second, all control rods were fully inserted. A reactor core doesn’t cool down
instantly the rods are driven in. In fact the residual “decay heat “ of a shutdown
core can account for a few megawatts thermal power .So , three emergency feed water

82
pumps , two electric and one stream – operated for redundancy ,were automatically
started to provide feed water to the rapidly emptying steam generator.

10.1.3 Reactor Cleaning

Disassemble reactor. When removing cooling water hoses, do not get water into
reactor. Remove gas outlet ( but not the inlet) .Remove very bottom screw in the outer
ring .Lessen all six on screw on inner ring ,alternating to not put more pressure on one
side . Use lift to lift up reactor and pick outer ring .Removing both halves of inner
ring .Shift mixer to one side and put out thermocouple. Pull out inside of reactor and
place on stand.

1. Recover all of the catalyst as is possible and store in used catalyst bottle. Dry
it eighth nitrogen to remove solvent.
2. Clean inside of reactor with cyclohexene. Scrub with green scotch pads gently.
3. Clean catalyst filter with cyclohexene and wash filtering container.
4. Clean all of screws and other parts for reactor by putting in THF in the
solicitor for 1 hour.

10.2 MAINTENANCE FOR HEAT TRANSFER EQUIPMENT’S.

10.2.1 Cooler (Heat exchanger- Shell and tube plate)

Both the primary side water loop and the secondary side recirculation systems are
treated systems. Under normal operation, this unit doesn’t required frequent
inspection and cleaning. If a unit experience continuous leakage, however it will be
necessary to open the unit and do a through a cleaning job as recommended by
equipment manufacture.

The need to open the heat exchanger can be detected by the following:

1. Leaks cannot be stop by tightening the bolts according to the manufacture’s

specifications.
2. An increase in pressure drop across the heat exchanger.
3. Lake of heat transfer causing inadequate heat to the building.

10.2.2 Plate heat exchangers- Gasket

Different plate heat exchanger manufacture supplies their heat exchangers with
different types of selling material between the plates. The most common type of

83
gasket material we have on our district heating system and nitrile and ethylene
propylene rubber (EPR and EPDM).

Based on published data for different type of elastomers for seals. The gasket material
has the following temperature ranges;

Nitrile: -40 F to 225 F for the low temperature

Nitrile; -40 F to 225 F for the high temperature

EPR and EPDM: -80 F to 300 F

10.2.3 Shut down to heat exchangers

If it becomes necessary to shut down the building’s heating plate heat exchangers, the
following suggested steps should be taken.

If the building is served by two plate heat exchangers, one unit can be isolated
completely without affecting the operation of the heating system.

Each of the plate heat exchanger is sized for 100 percent standby and or 66 percent of
the total heating load of the building. Therefore one unit can serve the building
temporary until repair or maintenance is completed on the other unit without lake of
adequate heat in the building.

As soon as maintenance work is completed, the unit can be put back in the service as
needed.

It is essential that plate heat exchangers be started up and shut down be according to
the recommendations in the manufacture’s instruction manual.

If the plate heat exchangers must be shut down during the heating season, the
following requirements should be observed:

Ventilation equipment should be put into the “off” position.

Hot water heating pumps should be put into the “off” position. No equipment should
be calling for heat at this time.

The primary supply and return water valves on the heat exchangers can be should off.

Plate heat exchangers should not be heated and cool quickly. The unit should be left
alone for 24 hour cool naturally and allow the stainless steel plate to contract

84
normally. Quick cooling of the unit will start leaks at the gasket and will force scaling,
dirt, and ventilation system and heating pump remain running, the heat exchangers
will be force to cool quickly, the metal will contract and the secondary side treated hot
water will leak to the floor.

To bring the plate heat exchanger back on the system, the secondary hot water heating
isolation valves on the heat exchangers should be opened; the hot water heating
pumps should be stared; and the primary side isolation valve should be opened slowly.
The unit should not be open slowly. The unit should not be heated and cool quickly.
Some plate manufacturer recommended that the units be heated up to the operated
temperature over a 24 hour period. When the secondary hot water heating system is
stabilized, the ventilation equipment can be stated.

Under normal condition, do not isolate the unit completely. Keep on hand valve in the
“open” position on both sides of the heat exchanger.

10.3 MAINTENANCE SAFETY

1) Always lockup power.

2) Ensure pump is isolated from the system and pressure is relieved before
disassembling pump, removing plug, or disconnecting piping.

3) Use proper lifting and supporting equipment to prevent serious injury.

4) Observe proper decontamination procedure.

5) Know and follow company safety regulation.

6) Never apply heat to remove impeller.

10.4 MAINTENANACE OF DISTILLATION COLUMN

10.4.1 Inspection and Repair

10.4.2 Corrosion on column intervals.

* Effect of corrosion on caps, Rings and Trays.

* Corrosion inhibition initiatives.

* Down comer inspection and repair.

85
 *Alternative action when maintenance becomes too costly.

10.4.3 Leak Test

10.4.4 Angle of repose for tower

86
 CHAPTER # 11

EXPERIMENTS AND RESULTS

11.1 RESULTS

11.1.1 Mesh No 65 Hydrolysis

20 ml solution consists of:

15 ml distilled water

5 ml H2SO4 1 N solution

0.4 gm pine cone

Temperature is 90 Co constant in hydrolysis.

Table No 11.1 Mesh No 65 Hydrolysis

Experiment No Time of Heating Specific gravity Brix

1 45 min 1.1011 24
2 60 min 1.1057 25
3 90 min 1.1197 28
4 120 min 1.1292 30
5 135 min 1.1306 30.3

11.2.2 Mesh No 28 Hydrolysis

20 ml solution consists of:

15 ml distill water

5 ml H2SO4 1 N solution

0.4 gm pine cone

Temperature is 90 Co constant in hydrolysis.

87
Table No 11.2 Mesh No 28 Hydrolysis

Experiment No Time of Heating Specific gravity Brix

1 45 min 1.0997 23.7

2 60 min 1.1011 24
3 90 min 1.1057 25
4 120 min 1.1150 27
5 135 min 1.1173 27.4

Time vs Brix
32

30

28

Mesh No 65
26
Brix

Mesh No 28

24

22

20
30 45 60 75 90 105 120 135 150
Time of Heating(mins)

Figure No 11.1 Time Vs Brix

88
 Time vs Specific gravity
1.14

1.13

1.12
Specific Gravity

Sp.g of Mesh No 28
1.11
Sp.g of Mesh No 65

1.1

1.09

1.08
30 45 60 75 90 105 120 135 150
Time of Heating(minutes)

Figure No 11.2Time Vs Specific Gravity

11.2.3 Fermentation of Mesh no 65

Table No 11.3 Fermentation of Mesh no 65

Experiment No Brix Ethanol by

volume(%) / 20 ml
Solution

1 24 14.4
2 25 15.1
3 28 17.5
4 30 19.2
5 30.3 19.4

Following fermentation parameter are same for each experiment:

pH= 4-5

Temperature= 25-30 Co

Time= 24 hours

Yeast = 0.4 gm

89
The maximum production of ethanol is 19.4% by volume which is equal to 3.84 ml in
20 ml solution.

Brix vs Ethanol ml / 20 ml sol

4.1
3.9
Ethanol ml / 20 ml solution

3.7
3.5
3.3
3.1
2.9
2.7
2.5
20 22 24 26 28 30 32
brix

Figure No 11.3. Brix Vs Ethanol ml/ 20 ml Solution

11.2.4 Fermentation of Mesh no 28

Table No 11.4 Fermentation of Mesh no 28

Experiment No Brix Ethanol by volume(%) /

20 ml Solution

1 23.7 14.1
2 24 14.4
3 25 15.1
4 27 16.7
5 27.4 17.1

Following fermentation parameter are same for each experiment:

pH= 4-5

Temperature= 25-30 Co

Time= 24 hours

90
Yeast = 0.4 gm

The maximum production of ethanol is 17.1% by volume which is equal to 3.4 ml in

20 ml solution.

Brix vs Ethanol ml / 20 ml sol

3.5
3.4
3.3
Ethanol ml/ 20 ml solution

3.2
3.1
3
2.9
2.8
2.7
2.6
2.5
22 23 24 25 26 27 28
Brix

Figure No 11.4 Brix Vs Ethanol ml/ 20 ml solution

11.2.5 Ethanol and pH Relation

Table No 11.5 Ethanol and pH Relation

Experiment No Ph Ethanol ml/ 20 ml

solution

1 4 3
2 4.5 3.8
3 5 3.4
4 5.5 3
5 6 2.8

For each experiment we use following parameter:

Brix= 30 solution

Fermentation Time= 24 hours

Temperature= 25-30 Co

91
 Ethanol ml/ 20 ml solution vs pH
3.9

3.7

3.5
Ethanol ml/ 20 ml sol

3.3

3.1

2.9

2.7

2.5
3 3.5 4 4.5 5 5.5 6 6.5
pH

Figure No 11.2Ethanol ml / 20 ml solution Vs pH

92
 CHAPTER # 12

CONCLUSION AND FUTURE WORK

12.1 CONCLUSION

The world is in energy crises today because of the accelerated sky touching prices of
conventional fuels which will last in 45 years, according to estimation. The world will
left no choice but to look for renewable energy sources like ethanol. This bio fuel will
not only overcome the energy shortages but will help in reduction of environmental
pollution by converted useless and pollution causing materials to use full product of
ethanol such wasted pine cone.

Pakistan is specially affected by energy crisis which have stopped foreign investors to
invest here but also we are paying huge amount of money on oil import which has
really disturbed our economy. This problem can be solved if the track of the country is
changed from conventional fuels to bio fuels, using its natural gift of being agriculture
country. Allot of resources are available in our country, presenting solution of the
energy crisis but just need little attention.

Ethanol offers a valuable energy alternative of common fuels, which are non
renewable. Ethanol is often referred to as a Biofuel since it can be manufactured by
fermenting Grains, plant biomass, and other organic materials using micro organisms,
such as yeast cells. Ethanol is renewable because it is primarily the result of
conversion of the sun energy into usable energy. Ethanol is most commonly used to
power automobiles such as ethanol-based engines, ethanol fuel cells, and rocket fuels.
Similarly using ethanol as fuel in the auto mobiles, it has minute effect on the
environment.

The maximum amount of ethanol can be produced when time of hydrolysis is two
hours; Mesh No is 65 by keeping the temperature and PH within the range of 20-30
degree Celsius and 4-5 respectively. The time required for fermentation to get
maximum ethanol product at given conditions is 24 hours.

93
12.2 FUTURE WORK

So far we limited the process to these variables which can effect the overall process
and on the basis of these variables and we found the maximum ethanol production
these variables are;

1. Mesh No 65 & 28
2. Time of Heating for Hydrolysis: 45-135 mins
3. Temperature for hydrolysis: 90 degree Celsius
4. Temperature for fermentation: 20 – 30 degrees Celsius
5. PH: 4-5
6. Time 24 hours

We proceed the process by limiting the above variables in their specified ranges. Now
there are still allot of other variables which can effect the process, including those
whose effect can be seen by introducing them in the process of ethanol production
from pine cone. These variables may be:

12.2.1 Mesh No

It was concluded by the experiment that when Mesh No increase the reduce and the
productivity of ethanol also increase.

12.2.2 Agitation

By using an agitator, whose speed can be varied easily, we can find its effect on the
process and will know its effect, whether its results in increase or decrease of
production of ethanol.

12.2.3 Temperature

We just proceed by limiting our process between the range of temperature in which
Saccharomyces cerevesiae growth in fermentation is secured but we don’t know the
effect s of fixed temperature and its effects on the variables. So one can easily
transform this idea in to practical work by finding the effect of ethanol production at
fixed temperature within the specified range.

12.2.4 Yeast

The yeast selection is of major importance because it determines the allowance in

other variables and the whole process of fermentation. There are allot of choices

94
available in the selection of yeast depending upon our choice of selection between
qualitative process or economical process. Other yeasts will lead to different process
paths and different process variables e.g. turbo yeast, zygo saccharomyces etc.

12.2.5 Nutrients

Nutrients are added to the solution of pine cone having yeast .The nutrients acts as a
food for yeast, helping them to bloom and guarantee their survival. It faster the
growth rate of yeast the lesser will be the time taken by fermentation. So one can
easily perform experiments on the amount and type of nutrients used, which are
commonly nitro phosphate and urea etc.

95
 REFERENCES
1. R. M. Ethanol, Production from hydrol using Saccharomyces cerevisiae and
optimization of temperature, pH and substrate concentration. M.Phil Thesis,
University of Agriculture, Faisalabad, Pakistan (2003) 23.

2. www.directindustry.com

3. www.hannainst.com/usa/subcat.cfm id=040

4. M.L. Cazetta, M.A.P.C. Celligoi.2006, Fermentation of molasses by

zymomonas mobilis: Effect of temperature and sugar concentration on ethanol
production, Bio resources technology, 8, 3367-3374.

5. Kunkee, Ralph E. and Amerine, Maynard A. (1968). "Sugar and Alcohol

Stabilization of Yeast in Sweet Wine". Appl Microbiol. 16 (7): 1067–75. PMC
547590. PMID 5664123

6. Harijan, K. Modeling and analysis of the potential demand for renewable

sources of energy in Pakistan. MPhil report. Jamshoro, Pakistan: Mehran
University of Engineering and technology;2006.

7. Nwakaire J. N., S. L. Ezeoha, and B. O. Ugwuishiwu. 2013. Production of

cellulosic ethane from wood sawdust. Agric Eng Int: CIGR Journal, 15(3): 136
－140.

8. Alvira P1, Tomás-Pejó E, Ballesteros M, Negro MJ. Efficent bioethanol

production process base on enzymatic hydrolysis. Renewable Energy
Division, Biomass Unit, Avda. Complutense 22, Madrid 28040, Spain.

9. Aluira. P, Parjo. E.T, Ballesteros. M Negro. M.J. Efficient Bioethanol

Production Process Based On Enzymatic Hydrolysis.

10. Sun. Y, Cheng. J. Hydrolysis of Lignocellosic Materials For Ethanol

Production. Department Of Biological And Agriculture Engineering. North
Carolina State University. USA October 2001.

96
11. Son. C.W, Kangsadant, T, Kangruang. S . Pretreatment Of Enzymatic
Hydrolysis Of Rice Straw: The Sirindhor International Thai- Garman Graduate
School Of Engineering Thailand.

12. Parthiban. R, Venkateswara. S, Sukimar, M.Production From Waste Banana

Pell Using Yeast.

13. Department of Biotechnology, Anna University, chennai, tanilnadu, India.

(2014).

14. Zhang. Q, LI.Y, Xinjiang. Acid Hydrolysis of Cotton Stalks And Ethanol
Production From Hydrolylic Liquids. College And Live Science, Tarim
University( 2014).

15. Anderson. P, Baumberg, B. Report On Alcohol In Europe. Institute Of Alcohol

Studies.UK, (June 2006)

16. "Ethanol – Compound Summary". The PubChem Project. USA: National

Center for Biotechnology Information.

17. Ballinger, P., Long, F.A.; Long (1960). "Acid Ionization Constants of
Alcohols. II. Acidities of Some Substituted Methanols and Related
Compounds1,2". Journal of the American Chemical Society 82 (4): 795–798.

18. Stogner, John M.; Eassey, John M.; Baldwin, Julie Marie; Miller, Bryan Lee
(September 2014). "Innovative alcohol use: Assessing the prevalence of
alcohol without liquid and other non-oral routes of alcohol administration".
Drug and Alcohol Dependence 142: 74–78. doi:10.1016j.drugalcdep.2014.

19. Gilman, Jodi M; Ramchandani, Vijay A; Crouss, Tess; Hommer, Daniel W (28
September 2011). "Subjective and Neural Responses to Intravenous Alcohol in
Young Adults with Light and Heavy Drinking Patterns". Neuro
psychopharmacology 37 (2): 467–477.

20. González, Begoña; Calvar, Noelia; Gómez, Elena; Domínguez, Ángeles

(2007). "Density, dynamic viscosity, and derived properties of binary mixtures
of methanol or ethanol with water, ethyl acetate, and methyl acetate at T =
(293.15, 298.15, and 303.15) K". The Journal of Chemical Thermodynamics
39 :

97
21. Alcohol use and safe drinking. US National Institutes of Health the Biofuels
FAQs. The Biofuels Source Book, Energy Future Coalition, United Nations
Foundation 2008 World Fuel Ethanol Production". U.S.: Renewable Fuels
Association. Ethanol. essentialchemicalindustry.org

23. Great Britain (2005). The Denatured Alcohol Regulations 2005. Statutory
Instrument 2005 No. 1524.

24. Nienstaedt, H.; Zasada, J.C. 1990. Picea glauca (Moench) Voss. p. 204–226 in
Burns, R.M. and Honkala, B.H. (Tech. Coord.), Silvics of North America, Vol.
1, Conifers. USDA, For. Serv., Washington DC, Agric. Handbook 654

25. Pine Cone Craft Projects". Familycrafts.about.com. 2013.

26. Pringle, J. R., Broach, J. R. and Jones, E. W. (Eds.): The Molecular and
Cellular Biology of the Yeast Saccharomyces, Vol. 3. Cell cycle and Cell
Biology. Cold Spring Harbor Laboratory Press, Cold Spring Harbor, NY
(1997).

27. Yang. X. Zhao. H.T , Wang. J, Meng. Q, Zhang. H, Yao. L, Zhang Y.C, Dong.
A.J, Ma . Y, Wang. Z.Y, XU.D.C and Ding. Y.’’ chemical composition and
antioxident activity of essential oil of Pine Cones of pinus armandii from the
southwest region of China’’. 25 May, 2010.

28. David M Principles and calculation in Chemical Engineering 2nd edition

(1967) Prentice –Hall PP-59-62.

29. David M Basic Priciples and Calculation 2nd edition (1967) Prentice-Hall
PP(97-105)

30. Gray, J.H AND Handwork G.E(1989), Petroleum Refinary Technology and
economic s (2nd edition Ed), Maul and Dekka.inc.

31. National Institutes for Occupational Safety and Health, NIOSH P acked
Guide to Chemical Hazards, DHHS Publication(85-199),(1987).

32. Boardman, N.E,(2006), Cost benefit analysis, Concept and Practicle, (3 rd

edition) ,, upper saddie River, NJ; Prentice Hall

33. Boardman, N.E (2007), Cost –benefit analysis, Concept s and Practice(3 rd),
upper saddle River, NJ ; Prentice Hall.
98
34. Lehman M.M ., 198 : programm, Life-Cycles and Laws of software Evolution.
In Proceedings of , EEE, 68, (1060-1076).

35. Penny G, Armstrong A, Taking , 2003: Software Maintanance; Concepts and

Practcice , World Scientific Publishing Company.

99