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PROCESS INDUSTRIES

Unit I
CEMENT PRODUCTION PLANT

Cement
Cement is a crystalline pulverized compound of calcium silicates
and other calcium bearing compounds with impressive hydraulic
properties.

It develops binding forces due to reaction with water.


Very often, cements that harden upon reaction with water for the
formation of water-resistant product are called hydraulic cements.
Under ASTM C150 naming, Portland cement is a hydraulic
cement which hardens and remains stable under water.
The main components of Portland cement are compounds of
calcium silicates and some amount of gypsum.

Raw Materials of Cement


The main raw materials of cement along with their respective sources
are given in the following table.

Important components

Respective Sources

Lime ( CaO)

Limestone, Shale, Marl

Silica (SiO2)

Sand, Clay, Shale, Marl

Alumina (Al2O3)

Clay, Shale, Slag

Iron Oxide (Fe2O3)

Iron Ore, Clay, Mill Scale

Trace Sulfate (SO3)

Gypsum

Cement Production Process


The basic process of Cement production involves the following five
major steps:
1.

Acquisition of raw materials

2.

Preparation of the raw materials for pyro- processing

3.

Pyro -processing of the raw materials to form cement clinker

4.

Grinding the clinker to Cement, and

5.

Storage & Packing

Process flow diagram

Detailed process description


1- Acquisition of raw materials
The core raw material for the production of cement is
limestone rock .

After quarrying limestone reach rock, the next process is size


reduction.
Crushed limestone have an approximate size of 15 cm
during first stage of crashing.
The rock then goes to the next crashing stages ,most probably
hammer mills, for reduction to a size which is smaller than the
original size.

2- Preparation of the raw materials for pyroprocessing


Preheating of the raw materials of cement and subsequent pyroprocessing in a kiln have certain size requirements.
Hence , the main aim of this process is to grind the material to a
size of 90 microns or less which is suitable size for pyro processing.
This process is done in a unit equipment called raw mill.
Raw mill basically is a closed circuit ball mill equipped with high
efficiency separator.
After achieving ~ 90 microns size, the fine grinded material (raw
meal) is sent to the continuous blending silos for homogenization.
The homogenized material will then be extracted by means of load
cell hopper for the next step which is feeding to the kiln pre heaters.

3-Pyro -processing of the raw materials to form


cement clinker
During pyro-processing , the homogenized raw material is heated
to about 1,450 C in cylindrical steel rotary kiln lined with special
firebrick.
Normally the raw material is fed in to the higher end of an
inclined Kiln and at the lower end there exists a blast flame
produced by precisely controlled burning of powdered coal, oil or
gas under forced draft.

The combustion gasses and the raw material flow in countercurrent mode and the firebrick acts as insulator for protecting the
heat losses to the ambient.

Rotary kiln-pictorial representation

Pyro processing details

Kiln temperature dependency


The combustion flame temperature is affected by the following
factors:
(1) the calorific value (and chemical composition) of the fuel;
(2) the air-to-fuel ratio at which combustion takes place; and
(3) the initial temperature (preheat) of the air and fuel.

Chemistry in kiln
Water

(100 0C)
(100 -600)0C

Clay
Calcium Silicates

CaO +
C3A+C4AF

SiO2
Al2O3
Fe2O3

(800 -900)0C

10000C

~13500C

Evaporation
SiO2
Al2O3
Fe2O3
CaO + CO2

2Cao.SiO2=C2S
3CaO.Al2O3=C3A
4CaO.Al2O3.Fe2O3=C4AF

Liquid+ remained (caO+C2S)---- C3S

ASTM classification of Portland cement

Tricalcium silicate (C3S) or alite,


Dicalcium silicate (C2S) or belite,
Tricalcium aluminate (C3A) and
Tetracalcium aluminoferrite (C4AF) .
Gypsum (CSH2)

Energy flows
The cement making process is highly energy intensive accounting
for nearly 40 50 % of the production costs.
Energy flows:

Electrical Energy -mill drives, fans and conveying systems.

Thermal Energy-kiln and precalciner.


Thermal energy accounts for about half the energy costs incurred
in cement manufacture.

Energy flow-details

Assignment 1
The following table is a typical ultimate analysis data for dry ash free premier coal. The
calorific value is 20MJ/kg and was burned under exact amount of air . Calculate the value
of adiabatic flame temperature? What will be the value if 30% excess air is used for
combustion?
Ultimate Analysis
(DAF Basis)

Range

Typical

Carbon

73-78%

74%

Hydrogen

4-5%

4.3%

Nitrogen

1.2-1.4%

1.3%

Oxygen

16-21%

19.8%

Sulphur

0.3-0.8%

0.6%

Mass balance for 1kg of Cement

Flame Temperature

1. Energy Balance on a System


A simple steady-state thermal energy balance can be constructed
around a constant-pressure combustion system (such as a boiler).

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Before the energy balance is developed it is worth looking


more closely at the terms involved:
(a)
HR, HP and CV (calorific value) are all related to
the standard temperature of 25.
The enthalpy of the entering air is considered
to be sensible heat only (i.e., the fuel/air is
considered to be a dry mixture).
(b) The enthalpy of the flue gas must be consistent
with the calorific value of the fuel which is used
in the balance.

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If the gross calorific value is used, then HR should


contain a latent heat term equal to the mass of water
produced per kilogram of fuel multiplied by the latent
heat of evaporation of water at 25 (hfg).
If the net calorific value is used, then the flue gas
enthalpy will consist of sensible heat terms only.
In this chapter we are concerned with predicting the
temperature reached within the flame, hence the net
calorific value/sensible heat terms system is the more
appropriate.

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The energy balance about the system can be


written as:
CV + HR = HP + Qc + Qu
(1)
HR, the sensible heat in the air and fuel (ref. 25)
is very small and often neglected.
The case loss from the outside of the plant, Qc, is
also generally small compared to the other energy
fluxes and is similarly often considered negligible.

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2. Adiabatic Flame Temperature


The following table shows flame temperatures for some
common fuels. The higher the flame temperature, the greater
should be the effectiveness of the heat exchanger section.
Table Flame temperatures for some common fuels
Fuel
Adiabatic flame temperature ()
Natural gas
2,070
Kerosine
2,093
Light fuel oil
2,104
Medium fuel oil
2,101
Heavy fuel oil
2,102
Bituminous Coal
2,172
Anthracite
2,180
25

We can use the idea of the energy balance about


the combustion system to derive a straightforward
way of estimating the temperature of a flame.
It is assumed that combustion takes place under
adiabatic conditions, i.e. no heat transfer is
permitted across the boundary of the system.
The implication of this is that
Qc = 0
and Qu = 0
Hence equation (1) simplifies down to
CV + HR = HP
(2)

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It will be taken that CV is the net specific heat of the


fuel, hence HP contains only sensible heat terms.
The terms on the left-hand side of equation (2) are
simple to evaluate as CV will be known for the fuel used
and HR, the enthalpy of the fuel and air (ref. 25, can
easily be calculated from
Where ti is the initial temperature.
H R (ti 25) (mcP ) R

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The specific heats of the fuel, oxygen and nitrogen can be


evaluated at the mean temperature
(ti + 25)/2 and the enthalpy of the reactants is thus easily
evaluated.
The right-hand side of equation (2), however, is not so easily
evaluated as it is defined by

HP = (t f - 25) (mcP )P
where tf is the flame temperature. This relationship cannot be
solved explicitly for tf as there will be a considerable difference
between tf and the reference temperature 25, hence the value
of tf is required to evaluate the specific heats of the combustion
products.

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3. Specific Heats of Gases


Simple ideal gas theory predicts that the specific heat of a
gas is not a function of its temperature or pressure.
While the latter implication is effectively true in practice,
the specific heat of a gas does increase with temperature
above about 100. This effect arises because molecules
have vibrational (internal) energy as well as kinetic energy
due to the motion of the complete molecule.
This additional mode of storing energy will mean that
the specific heat of a gas will increase as its temperature
rises.
This cannot be modelled using the ideas of classical
mechanics but the effect can be predicted using quantum
theory.

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Empirical equations which allow the calculation of


specific heats as a function of temperature have
been in use for some time. A polynomial expression
is normally used, with either fractional or integer
powers.
A straightforward integer power series is most
convenient:
CP = a[0] + a[1]t +a[2]t2 + a[3]t3 +..
Values for the coefficients for the polynomials for
some gases are given in next slides.
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Site selection
The Site of cement processing pant is usually near to the
location of the main raw materiallime.

Waste water
No pronounced effect for dry processing.
But for processing plants that use coal mines as energy
source there may exist contamination of ground water.

Air pollution
Carbon dioxide emissions can be grouped as energyrelated, referring to emissions that result from the
combustion of fossil fuel, and process- related, referring to
the emissions from the decomposition of calcium carbonate.
Studies have shown that one ton of carbon dioxide gas is
released into the atmosphere for every ton of Portland
cement which is made anywhere in the world.
The only exceptions are so-called 'blended cements', using
such ingredients as coal fly ash, where the CO2 emissions are
slightly suppressed, by a maximum of 10%-15%.

Air pollution
Cement, (Portland cement), results from the calcination of

limestone (calcium carbonate) at very high temperatures of


approximately 1450-1500 C, and silico-aluminous material
according to the reaction.
5CaCO3 + 2SiO2 --> (3CaO,SiO2) + (2CaO,SiO2) + 5CO2
this means that the manufacture of 1 metric tonne of
cement generates 1 metric tonne of CO2 greenhouse gas.

Energy Efficiency Opportunities


Energy efficiency improvement reduces CO2 emissions
Reduction in CO2 emissions from the cement plant
involves a two pronged strategy.
1. By improving energy efficiency
2. By promotion of blended cements which can decrease
the clinker percentage in cement, thus reducing the process
CO2 emissions

Steps for Improving Energy Efficiency

UNIT II
ALCOHOL PRODUCTION

What is alcohol ?
A class of molecules withOH(hydroxyl) functional
group.

methanol- 1 carbon
ethanol- 2 carbons
propanol- 3 carbons
butanol- 4 carbons
pentanol- 5 carbons

Alcohol -Where does it come from?


Fundamental metabolic processes:
extracting energy from sugar

aerobic respiration

anaerobic respiration

- requires oxygen
- 36 ATP per glucose
molecule
alcoholic fermentation
- low energy waste
products, H2O and CO2

lactic acid
fermentation

Sources
Ethanol can be derived from agricultural sources or from
petrochemicals.

Ethanol derived from agricultural sources, as distinct from


petrochemical sources, is referred to as bioethanol.

Production schemes for bioethanol


Bioethanol is mainly produced in three ways.

1. sugar

2. starch

ethanol

sugar

3. cellulose and hemicellulose

ethanol
ethanol

Manufacturing Process
ENZYMES

Feedstock
Handling

PRE-TREATMENT
HYDROLYSIS
50% EtOH

95% EtOH
AZEOPTROPIC
DEHYDRATOR

6
5
4

6
5
4

3
2
1

3
2
1

RECTIFIER
99.6% FUEL
GRADE
ETHANOL

WATER

ENZYMES
YEAST
10% EtOH

STRIPPER

FERMENTATION

SOLIDS

Classification of Feedstock

Classified into 3 types depending upon the constituent


sugars

SACCHARINE: Directly fermentable 6 and 12 C sugars


Glucose, Fructose and Maltose
E.g. Sugar cane, Sugar beet, Whey, etc.

STARCH: Carbohydrates such as Starch and Inulin


E.g. Maize, Wheat, Potatoes, etc.

CELLULOSE: Common material in plants


Primary constituent of plant cell wall
Wood, wood waste, paper, straw, etc.

SACHHARINE
Fruits Molasses

STARCH
Grains
Potatoes

PRE TREATMENT

MILLING

MASHING

CELLULOSE
DRY
Green

SHREDDING

MASHING

DILUTION

DILUTION

DILUTION

LIQUEFACTION

HYDROLYSIS

HYDROLYSIS

FERMENTATION

DISTILLATION

DEHYDRATION

DENATURING

STORAGE

Process description
Feedstock Handling. Biomass goes through a size-reduction step to make
it easier to handle and to make the ethanol production process more
efficient. For example, agricultural residues go through a grinding process
and wood goes through a chipping process to achieve a uniform particle
size.
Biomass Pretreatment. In this step, the hemicellulose fraction of the
biomass is broken down into simple sugars.
Enzyme Production. The cellulase enzymes that are used to hydrolyze the
cellulose fraction of the biomass are grown in this step. Alternatively the
enzymes might be purchased from commercial enzyme companies.
Cellulose Hydrolysis. In this step, the remaining cellulose is hydrolyzed to
glucose. In this enzymatic hydrolysis reaction, cellulase enzymes are used to
break the chains of sugars that make up the cellulose, releasing glucose.
Cellulose hydrolysis is also called cellulose saccharification because it
produces sugars.

Continued..
Enzyme Production. The cellulase enzymes that are used to hydrolyze
the cellulose fraction of the biomass are grown in this step. Alternatively
the enzymes might be purchased from commercial enzyme companies.

Fermentation. The glucose is converted to ethanol, through a process


called fermentation. Fermentation is a series of chemical reactions that
convert sugars to ethanol. The fermentation reaction is caused by yeast
or bacteria, which feed on the sugars. As the sugars are consumed,
ethanol and carbon dioxide are produced.
Distillation. It is the main unit operation for concentrating ethanol.

Distillation
Distillation is a kind of seperation technique of two or more
volatile liquid compunds by using the difference in boiling points
and relative volatility.
The process takes place in a column, and two heat exchangers.

In the column two phases, liquid and gas, are distributed to


enrich the vapor in more volatile compounds and enrich the
liquid phase on less volatile compounds.
Mass transfer is the key to a successful distillation.

Distillation of Alcohol
Under 1 athmosphere pressure
boiling points of water and alcohol
are 100C and 78.3C.
Water and ethyl alcohol mixture
forms an azeotrope in athmospheric
pressure at a mole fraction of %89.4
of ethyl alcohol which means that by
simple distillation of ethyl alcohol, it
cannot be purified more than %95.6
w.
As distillation equipments, bubble
cap trays and tray columns are mostly
used in alcohol distillation.(Figure on
left)

Bio-Ethanol Production Processes

Starch-to-Ethanol Process

Starch-to-Ethanol Process

Corn-to-Ethanol Process

Materials

Starch expansion & solubilization

Liquefaction

Liquefaction

Liquefaction

Saccharification

Saccharification

Saccharification

Fermentation

Summary of Corn-to-EtOH Process

Corn to Ethanol Process flow diagram

Energy balance

Cellulose to Ethanol

Major composition

Cellulose to Ethanol Process

Pretreatment

Pretreatment

Pretreatment process
Physical pretreatment process.
Physico-chemical pretreatment
process.
Chemical pretreatment process.
Biological pretreatment process.

Pretreatment technology

Pretreatment technology

Steam explosion

Steam explosion

Physico-chemical Pretreatment

Ammonia Fiber Explosion


(AFEX)

Physico-chemical Pretreatment

Chemical Pretreatment

Chemical Pretreatment

Chemical pretreatment

Chemical pretreatment

Biological Pretreatment

Distillation and Dehydration

By-products

By-products

usage
Alcoholic beverages
Medicine
Fuel

Alcoholic beverages
Alcoholic beverages are divided into three groups:
malt liquors, fermented wines and distilled liquors.

Beer requires malted (germinated) grain to make the


carbohydrates fermentable, wines are produced by the
action of yeast on the sugar of fruit (commonly grape fruit),
and distilled liquors are fermented liquors which are then
distilled to increase the alcoholic content.
The common distilled liquors are Whisky, Gin, Areke
(Ouzo), Brandi, Cognac, Ferneit, Bitter and the like.

Fuel
Ethanol can be used as fuel in cars alone as power alcohol
or as a blend with benzene.

Wastewater of Etoh production

Waste water treatment


After

distillation remains waste from


bottom columns, termed stillage.
Silage is highly aqueous residue containing
organic soluble and is considered as a
troublesome and potentially polluting waste
due to its extremely high BOD and COD
values.
The typical odour emanating from
distilleries is due to silage.

Characteristics
Generally the effluents from molasses based
distilleries contain large amounts of dark brown
coloured molasses spent wash (MSW).
Because of its acidic pH, dark brown colour, high ash
content, high percentage of dissolved organic and
inorganic matter, it is one of the most difficult waste
products to dispose.
The biochemical Oxygen demand (BOD) and chemical
oxygen demand (COD) of MSW range between 35,000
50,000 and 100,000150,000 mg L-1, respectively.

Continued
Distillery
wastewaters
contain
phenolics
compounds, mainly gallic acid, p-coumaric acid and
gentisic acid, which impart high Antibacterial
activity.
Organic acids such as lactic acid (29% v/v), tartaric
acid (27% v/v), succinic acid (26% v/v), acetic acid
(10% v/v) and malic acid (8% v/v) also documented
in distillery wastewater.
Apart from the above listed cpds distillery waste
water also contains soluble proteins.

Example of Wastewater
distillery characteristics
Parameters such as the pH, alkalinity,
electrical conductivity (EC), total chemical
oxygen demand (COD), soluble chemical
oxygen demand (COD), five-day biochemical
oxygen demand (BOD), total organic carbon
(TOC), phenol, volatile fatty acids (VFA),
volatile solids (VS), volatile suspended solids
(VSS), total solids (TS), total suspended solids
(TSS), mixed solids (MS), mixed suspended
solids (MSS), total nitrogen (TN), ammonia
(NH4+), nitrates (NO3-), total phosphorus (TP)
and phosphates (PO43-) must be reported for
effective water treatment.

Toxicity of distillery waste


water
The

water bodies receiving colour wastes got


colored and affect the penetration of light in
aquatic Biological Treatment of Distillery Waste
Water .
Seriously affects ecosystems, which in turn affect
the aquatic life .
Therefore, it is essential to reduce the toxic level
of various pollutants in the distillery effluent before
discharging them into nearby watercourses or
lands.

Treatment Methods Of
Distillery Waste Water
There are several different methods for treatment
of distillery effluent. They are as follows:
Physico-Chemical Treatment Methods.
Biological Treatment Methods.
Aerobic Treatment.
Anaerobic Treatment.
Enzymatic Treatment.

Physico-Chemical Treatment
Methods
Coagulation: Reduction of repulsive forces through
addition of coagulant.

Flocculation: Physical process by which particle contact


and agglomeration occurs.
Ion Exchange: To separate ionized molecules (organic as
well as inorganic) from aqueous solution as well as
contaminants in organic streams.
Hydrodynamic Cavitation Technology: Cavitation is the
formation, growth and collapse of cavities/bubbles,
releasing large amount of energy & generating oxidizing
agents in waste water.

Continued
Membrane Technology: The effluent collected
from the distillery industry is highly acidic with PH
range of around 3. Hence, it is neutralized using
sodium hydroxide. The neutralized solution has a
lot of suspended solids, so the filtration is carried
out to remove the suspended solids with fine-pore
thin cloth or by using some membranes.

Biological Treatment Methods


Biological treatments have been recognized as
effective methods of treatment for highly polluted
industrial wastewaters. Both anaerobic and aerobic
systems are commonly used to treat the waste
waters from agro-industrial plants.

Continued
AnaerobicTreatment : Application of anaerobic digestion to
distillery effluents is a preferable primary treatment option. Since
aerobic processes have higher nutrient requirements and cause
operational difficulties in treating high organic strength
wastewaters, employing these methods in primary treatment of
stillage would result in lower cost-efficiency.
Aerobic Treatment: The post anaerobic treatment stage still has
high organic loading and is high dark brown in colour, hence it is
generally followed by a secondary, aerobic treatment. These are
some aerobic treatment methods:
Biocomposting: Biocomposting is an aerobic, thermophilic
process resulting in a product rich in humus which is thus used as
a fertilizer.

Enzymatic Treatment
Is

useful for colour removal.

Uses set different bacteria family.