Beruflich Dokumente
Kultur Dokumente
Project Supervisor
Dr.Farukh Jamil
Group Members:
Jawad Kashif (FA15-CHE-041)
Mubashir Rehmat (FA15-CHE-052)
Muhammad Iqbal Tabassum (FA15-CHE-068)
Rana Asad Ali (FA15-CHE-035)
Muhammad Kashif (FA15-CHE-074)
1. Ethanol has been used to a considerable extent as an anti-freeze, but it has largely been
replaced for such use by ethylene glycol for automobile radiator.
2. It is used as beverages.
3. It is used as a preservative for biological specimens as a low freezing (freezing point-
117 °C) and mobile fluid in scientific apparatus such as thermometer and spirit level.
4. It is used as a fuel for lamps and stoves. The combustion of ethanol is smokeless. The
calorific value is 7100 cal/kg which is slightly lower than that of coal. For the sake of
convenience, in transportation it is converted into solid state by dispersion in saturated
calcium acetate and a little stearic acid.
5. In hospitals it is used as an antiseptic.
6. End usage growth pattern of industrial alcohol. The uses of ethanol are the following:
Solvent 40%
Acetaldehyde production 36%
Miscellaneous chemical uses 15%
Ether, glycol ether, ethyl acetate and chloral 9%
Raw Material (Molasses)
Molasses (sometimes called blackstrap) can be defined as the final residue obtained in the
preparation of sugar by repeated crystallization. It is the residual syrup purged from a
massecuite incapable of crystallizing after concentration or cooling is called “blackstrap
molasses” in a raw sugar house and Refinery Blackstrap or barrel syrup in a refinery is a very
viscous product with a rather bitter taste. The approximate weight of one gallon is 12.8lb.
The US custom laboratory defines Blackstrap as molasses in which the non-sugar solids are
more than 60% of the total soluble solids excluding any foreign substance that may have been
added or developed in the product.
It is roughly estimated that 4 to 5 tons of molasses required to prepare one ton of alcohol. It has
been found that on average 4 tons of molasses (88Brix) sp. Gravity 1.47 is produced from every
100 tons of cane crushes [Error! Reference source not found.].
Literature Review
1.4 Available processes
By Keeping in mind demand of the ethanol, the production has recently seen that there is
increasing the production of the ethanol due to economic and environmental security concerns.
In the specific countries just like Europe, India, China, and Brazil, the ethanol production
is target for reducing petroleum import and increasing the consumption and production of
renewable fuel as the ethanol is renewable fuel. There are many ways for the production of
ethanol. These methods are including:
Fermentation of Starch/Cellulose
Fermentation of molasses
Hydration of ethylene
1.5 Fermentation of Starch/Cellulose
It was French chemist Anselme Payen, who discovered cellulose in 1838. Anselme Payen found
that the cellulose is consist of 44% to 45% Carbon, 6% to 6.5%of hydrogen and the remaining
part of the cellulose is mainly consists of oxygen. Then a chemist Staudinger proof in 1920 that
the cellulose in natural polymer of carbohydrates [Error! Reference source not found.].
Now, the cellulosic ethanol is ethanol which extracts from cellulosic materials such as forestry
or agricultural waste. For the production of cellulosic ethanol, the woods are commonly used as
raw material. The firstly in the history the extraction of ethanol from cellulose was published on
1819 by Baronet. After the research of Braconnet the door for the other researcher were opened.
After the research of Braconnet, Simonsen in 1894 put forward the method for treatment of
sawdust with diluted acid in the high pressure about 7-8atm to produce Ethanol. After that in
1899 Classen put forward another method to produce ethanol. He used the diluted sulphuric
acid as hydrolysis solvent for the hydrolysis of wood. For this process, he set the conditions as
150°C temperature and 7atm pressure for 4to 6 hrs., then the solid parts from the reaction was
removed by filtration and the ethanol fermented.
To produce the ethanol from the cellulose the most common procedure is consists of two steps:
a) Hydrolysis of the cellulose
b) Fermentation of the hydrolyzed cellulose
1.5.1 Hydrolysis of the Cellulose:
In this method we use acid for the hydrolysis of the cellulose (C6H10O5)n. This method was
introduced in the last 19th century and the starting of the 20th century. By hydrolysis of the
cellulose (C6H10O5)n we convert it to the glucose(C6H12O6) which has to be fermented and
covert to the ethanol. For hydrolysis we commonly we use sulphuric acid which may be used in
concentrated (25-80%) or diluted (3-8%).
1.5.2 Fermentation of the Hydrolyzed Cellulose:
This process is the chemical transformation of the glucose to ethanol in the presence of some
specific enzyme. It is earlier mentioned that the fermentation is the breakdown of the molecules
in the absence of air. The following reaction is involved in fermentation:
C6H12O6 2C2H5OH + 2CO2
In this process ethanol produced with94-96% purity.
1.6 Fermentation of Molasses
Molasses is sweet, dark and viscous byproduct of sugar manufacturing. It was a German
chemist Andreas Marggraf discovered the presence of sugar in the molasses first time in the mid
of 1700. Then in 1793 another German chemist named as Franz Karl Achard first time utilized
the molasses to extract sugar from it. The composition of molasses on dry basis 62.2% alcohol-
soluble sugars, 32.1% sucrose, 8.5% glucose and 15.1% of fructose. Some percentage of
nitrogen is also present in the form of amino acid, but it is not more than 1%.
As earlier mentioned, that the ethanol is the most valuable product. Its demand increased from
20th century due to energy crises, ethanol can reduce these crises because it is the renewable
fuel. For this reason, its market grew from a billion liters to 65 billion in from 1975 to 2008.To
over these energy crises many countries played their roles, which include Brazil, India, China,
Ireland, Japan and Indonesia. United States produced the largest amount of the ethanol, it
produces 50% of the global production of ethanol. Brazil is the second largest producer of the
ethanol by bio-mass it produces 39% global ethanol [Error! Reference source not found.].
To produce ethanol from the molasses the following steps are includes:
1.6.1 Dilution off molasses
First of all, molasses is diluted with water with the ratio of 1:5(Molasses: Water)
1.6.2 Addition of Ammonium Sulphate
Ammonium Sulphate is used for the growth of the yeast, the amount of the Ammonium
Sulphate is added depend upon the Nitrogen content in the molasses.
1.6.3 Addition of sulphuric acid
Sulphuric acid is added to the solution to give the optimum pH to the solution as 4.8. It will
increase the working of those enzymes which are useless.
1.6.4 Fermentation
The resulting solution then recovered in a fermenter for 48-70hours at 30°C. During this period
the reactions are taking placed in the presence of enzyme yeast and glucose converted into the
ethanol. The following reactions are here:
C12H22O11+H2O C6H12O6 +C6H12O6
C6H12O6 C2H5OH + 2CO2
1.6.5 Distillation
The ethanol which we obtained from fermentation called WASH, will 18-20% pure. For
increasing in the purity, we will distillate WASH and increased its purity.[Error! Reference
source not found.Error! Reference source not found.]
1.7 Hydration of Ethylene
Ethanol is produced by the direct hydration of ethylene. The method of direct hydration firstly
was introduced by Shell in 1997. Shell manufactured the ethanol bychemical reaction of the
ethylene (C2H4) with water.
1.7.1 Process for production
First of all, water is vaporized and then added to the vapors of ethylene at pressure 65-70 atm
and the reaction is proceed at temperature about 250°-300°C. The mixture of water and ethylene
is fed to the reaction tower from top of the tower. A catalyst solution of H3PO4 is also fed to the
top of the tower which will be the added as per required. The concurrent flow passes through
the packing material of catalyst [Error! Reference source not found.]. Due to presence of the
catalyst the following reactions are proceeding:
H2O + CH2=CH2 CH3CH2OH
Due to presence of impurities such as acetylene (C2H2), the following reaction also be
occurred.
b) Reaction Conditions
Temperature: 300°C
Pressure: 60-70atm
Catalyst: Phosphoric (v) acid
1.8.1 Effect of temperature
The reaction is controlled by Le-Chatelier’s principle and we need to shift the equilibrium to the
right and this can be done by lowering the temperature, but lower temperature make reaction get
slower, so we choose a compromise temperature of 300°C which give acceptable amount of
ethanol in short time over the catalyst.
1.8.2 Effect of pressure
There are 2 molecules on the left-hand side of equation and only 1 on the right-hand side. So,
when we increase the pressure the system will shift to the left-hand side and produce less
molecules and cause pressure to fall again. To produce as much ethanol, we need as much high
pressure as we can and achieving high pressure will be costly and 60-70 atm is not that high.
High pressures are expensive as we will need very strong pipes and containment vessels. Also,
at high pressures ethylene polymerizes to polyethylene.
1.9 Fermentation of molasses
Fermentation of molasses also known as ethanol fermentation is anaerobic pathway carried out
by yeasts in which simple sugars from molasses are converted to ethanol and carbon dioxide
[Error! Reference source not found.].
Reaction Conditions
Temperature: 30°C
pH: 4.5
1.9.1 Effect of pH
The effect of pH shows that pH = 4.5 produces the highest ethanol concentration and had the
highest ethanol yield.
1.9.2 Effect of temperature
The effect of temperature showed that at 30°C, the optimal temperature for alcoholic
fermentation which increases the rate of fermentation to achieve the maximum yield.
Comparison:
M2
M1 M4
SCRUBBER
M3
M5 M6
M4
DILUTER M7
Molasses composition
F.S = 45%
Inert sugar =5%
Other =19.6%
Ash =9.8%
H2O =20.6%
(X1) F. S = 0.45 (M4)F.S = 434.0745
(X1) I. S =0.05 (M4)I.S =48.2305
(X1) Oth =0.196 (M4)Oth =189.06356
(X1) Ash =0.098 (M4)Ash =94.53178
(X1) H2O =0.206 (M4)H2O =198.70966
(M4) S =794×964.610
=765.90 ton/day
(M4) H2O =206×964.610
=198.71 ton/day
M7 solid balance
X7s =0.17
x7L =0.83
(M7) S =M7×(X7) S
M7 =(M7) S/(X7) S
=765.9/1.7
=4505.29 ton/day
(M7) H2O =3739.39 ton/day
(M7) S =765.9 ton/day
H2O balance around diluter
M4+M5+M6 =M7
198.71+M5+273.756 =3739.39
M5 =3266.168471 ton/day
Around Sterilizer:
M9
M10
STERLIZER
M7 M8
M11 M12
M9A M13
SEEDING VESSEL
MOTHER TANK
M13
M16
Around Fermenter:
M16
M17
FERMENTER
M18
M10
M19
M21
M20 = M21
M21 = 4332.00634 tons/day
Around Stripper:
stripper
M21
M23
M22
M25
M23 = top product from stripper
M24 = aldehyde from surge
M25 = outlet from surge drum (feed to distillation column)
M23 = M24 + M25
M24 = M23 – M25
M24 = 318 – 7.63
M24 = 310.37 tons/day
Around Rectifying Column:
M27
M24
M28
M26
4514Tons/day = 4514Tons/day
So,
Mass In = Mass Out
Heat Balance
Around Fermenter:
CO2 40°C
Q =mCp∆T
512034589.2 = m× 0.99 kcal/kg°C×(40-30)
M = 51203459 kg
M = 51203.459 tons
Around Pre-heater:
Heat in = mCp∆T
=4332 × 1000/24 Kg / hr × .97kcal/kg°C(99-60)
=6828315 kcal/hr
Q for steam =Msλs
Ms = Q /λs
=6828315 /519.45
= 13145.27 kg/hr (mass Flow rate of Steam)
Around Stripper:
Mash 99°C
Slope 99°C
Heat In
Heat in = mCp∆T
= 4332× 1000/24Kg / hr×.97kcal/kg°C(99-30)
=12080865 kcal/hr
Heat out = mCp∆T
=4014×1000/24 Kg / hr ×1 kcal/kg°C (100-30)
=11707500 kcal/hr
Heat Out
Heat out =mCp∆T + mλ
=318×1000/24 Kg / hr ×0.727 kcal/kg°C(92-30)+318×1000/24Kg / hr×521.4
=597230.5+6907225
=7504455.5kcak/hr
Heat to be provided by steam = (7504455.5 +11707500)-12080865
=7131090.5 kcal/hr
Around Condenser 1:
92°C
MA
Reflux ratio =0
Mv =MA
MA = 318ton/day
Cp mean =.6×.581+.3735×.99+.0243×.269+.0026×.768
=0.727kcal/kg
Hl =mCp∆T
=1×.727kcal/kg°C×(92-30)
=45.074 kcal/kg
Hvap =45.074 +XH2Oλ+XC2H5OHλ+XF.Oλ+XAldehydeλ
=45.074 +139.845+122.4+3.31488+.3117
=310.94558kcal/kg
Hvap =318×1000/24Kg / hr×45.074 kcal/kg
=597230.5 kcal/hr
Hvap =318×1000/24Kg / hr×310.94558 kcal/kg
=4120028.935 kcal/hr
Duty =4120028.935 kcal/hr-597230.5 kcal/hr
= 3522798.435 kcal/hr
Mass of H2O required in condenser
mCp∆T = 3522798.435
m = 3522798.435kcal/hr/.99kcal/kg°C(40-30)
m = 355838.2258kg/hr
m = 8540.11tons/day
Around Condenser 2:
82°C
30°C
40°C
MA
MB MA
1.33 Scrubber
Water flow rate = 273.756 ton/day
= 11406.25 kg/hr.
CO2 flow rate = 182.504 ton/day
= 7604.33kg/hr.
Density of H2O = 997.045kg/m3
As, PV = (m/M) ×RT
Density = PM/RT
M = Molecular Mass of feed =44kg/mole
P = 1atm
Density = (1atm/298k)(44g/1gmol)(1gmol.K/0.08205L.atm)(1000L/1m3)(1Kg/1000g)
=1.79kg/m3
Uf = 0.07 2 [(fl-fv)/fv]1/2
= 0.07 [(997.045-1.79)/1.79)]1/2
= 1.65 m/s
Demister pad is not used so,
Uf = 0.15 × 1.65 = 0.2475m/s
Vapor volumetric rate = 7604.33/1.79 ×3600
= 1.18m3/s
Vessel area =A =Q/Uv
= 1.18/0.2475
= 4.76m2
Area = (π/4)×D2
D = [(Area × 4) /π ]1/2
D = [(4.76 ×4)/3.14]1/2
D = 2.46m
Allow a minimum hold time up to = 10min
Liquid volumetric flow rate = 11406.25/ (997.045 ×3600)
= 3.17 ×10-3
Volume held in vessel = 3.17 ×10-3×10 ×6
=1.902m3
Liquid depth = volume held up /vessel cross sectional area
= 1.902/ (3.14/4)× (2.46)2
= 1.902/4.75
=0.4m
Divergent zone = 0.3m
Total = 0.4+0.3 = 0.7m
Thickness of scrubber:
tm =9mm (Che. Engineering, Vol. 6, page 814)
OD = ID + 2tm
= 2.46 ×1000+2(9)
= 2478mm
= 2.478m
Area of material used = (Outer area – inner area) × L
= [(3.14/4) (OD)2] – [(3.14/4) (ID)2] × L
= [(3.14/4) (2.478)2-(3.14/4) (2.46)2] × (0.7)
= (0.0697) (0.7)
=0.05m3
Volume of top and bottom plate:
V = 2 × (3.14/4) (OD) 2×tm
= 2 × (3.14/4) (2478)2× 9
= 867650mm3
= 0.086 m3
Total volume = 0.086+0.05
= 0.136 m3
Carbon steel (material of construction)
Density = ρ = 7850 kg/m3
Weight of tank =V×ρ
= 7850 × 0.136
= 1067.4kg
1.34 Fermenter
Residence Time = 48hr
Mass Flow Rate = 4514.5Tons/day
= (4514.5×1000)/24 Kg/hr
=188104.58Kg/hr
Density = 0.85(1000) + 0.15(1474)
=1071.1Kg/m3
Temperature = 32°C
Pressure = 1atm
# of fermenters used =9
Mass Flow Rate in One Fermenter = 188104.58/9 Kg/hr
=20900.53Kg/hr
Vol. Flow Rate = 20900.53/1071.1m3/hr
=19.5m3/hr
Volume of Fermenter = Vol. Flow Rate × Residence Time
=19.5 × 48
=936m3
At 10% Allowance;
Volume = 936 × 1.1
=1029.6m3
Diameter and Length of Fermenter:
L:D = 3:1
L = 3D
Volume = Area × Length
1029.6 = (π D2/4) × 3D
D3 = (1029.6 ×4 )/(3×4.14)
By taking cube root
D = 7.58m
L = 3(7.58)
L = 22.7m
Volume occupied by head and bottom
=2(π×D3)/24
=2×3.14 × (7.58)3/24
= 113.96m3
Total Volume = 1029.6 – 113.96
=915m3
Pressure head due to liquid =ρ × g × h
Here, h = Volume / Area
Volume of liquid =Vol. of fermn. –Vol. of ellipsoidal Bottom
=936 – 113.96/2
= 879.02m3
H = 879.02 / [(π/4) (7.58)2]
=19.48m
Height of Ellipsoidal head = 0.5m
Total height =19.48 + 0.5
= 19.98m
Pressure head due to liquid =ρ × g × h
=1071.1 × 9.81 × 19.98
=209939.6N/m2
= 209. 94KN/m2
Material of construction is Carbon Steel
Working Stress of CS = 135000KN/m2
Thickness,
tm = PRi / (SE-0.6P) +Cc
P = 209.94 + 101.3 + 0.002
=311.24KN/m2
tm = [311.24 × (7.58/2)] / [(0.85×135000) – (0.6×311.24)] + 0.002
=0.012m
=0.472 inch
Outer Diameter = 7.58 + (2×0.012)
=7.604m
1.35 Heat Exchanger
T1 = 212οF
T2 = 174.2οF
t2 =140οF
t1 = 104οF
T1 – T2 = 37.8 t2 – t1 = 36
LMTD:
LMTD = ∆T2-∆T1/ln(∆T2/∆T1)
= (72 – 70.2)/ln (72/70.2)
R = (T1 – T2) / (t2 – t1)
R = 37.8 / 36
= 1.05
S = (t2 – t1) / (T1 – T2)
S = 36 / 212-104
= 0.33
For 1 shell, 2 tube passes
Ft = 0.95 (fig 18,Karen)
∆T = LMTD × Ft
= 71 × 0.96
= 68.16 οF
Since the temp difference on the hot and cold stream is less than 100οF, so average temp on
both stream can be used,
Ta = 212 + 174.2 /2
= 193.1οF
TB = 140 + 104 / 2
= 122οF
Assume
,Ud = 150 btu/hr.ft2.F
Q = UA∆T
A = q / Ud∆T
=13866732 / 150 ×68.16
= 1356.29 ft2
Tube diameter assume = 3/4 inch
Outer surface per line ft = 0.1963
BWG = 16
Length = 16 ft.
No of tubes = area / (length ×outer surface)
Area = 1356.29 ft2
Length = 16 ft
Outer surface per line ft = 01963 ft2
= 432 tubes
From table (a) for 2 pass the nearest tube is 460 at 27 inch inner diameter of shell.
Corrected UD:
Area = no of tubes ×L × outer surface
= 460 ×16 ×0.1963
=1444.768 m2
UD = Q / A∆𝑇
= 13866732 / (1444.768) (68.16)
= 141 Btu / hr.ft2 F
Tube side calculation (Mash)
Flow area = at/ = 0.302 inch2 (Table 10 )
/
at = Nt × at / 144 × n
= 460 × 0.302 / 144 × 2
= 0.4823 ft2
Mass velocity G = w / at
= 4332 ton / day
Conversion factor:
1 ton = 1000kg
1 kg = 2.2 lb.
1 day = 24 hr.
Then, G = 397100 lb / hr.
Gt = w / at
= 397100 / 0.4823
= 823346.4 lb/hr.ft2
For µ of mash at 122οF
µ = 0.662 CP × 2.42 (conversion factor)
= 1.602 lb / hr.ft
Inner diameter (I.D) = 0.62 / 12
= 0.0517 ft.
Re = DGL / µ
= 0.0517 × 823346.4 / 1.602
= 26571.16
Heat transfer coefficient:
Jh = 95 (from fig 24)
°
At t = 122 F
K = 0.339 btu / hr.ft.F
hi = Jh (K / D) (CPµ / K)1/3
= 95 (0.339 / 0.0517) (0.97 × 1.602 / 0.339 )1/3
= 95 ×6.55 × 1.66
= 1032 btu / hr.ft2.F
hio =hi × ID / OD
= 1032 × 0.62 / 0.75
= 853.12 btu / hr.ft2.F
Shell side calculation: -
Flow area a5
Baffle space = ID of shell / 5 (equation 11.4)
= 21.25 / 5
= 4.25
Clearance = 0.25
Square pitch Pt = 1 inch
Flow area=AS = ID × C/ B / 144 ×pt
= 21.25 × (0.25 × 4.25) / 144 ×1
=0.156 ft2
Mass velocity = GS = W / aS
W = 4014 ton / day
Conversion factors,
1 ton = 1000 kg
1 kg = 2.2 lb
1 day = 24 hr
W = 367950 lb / hr
GS = w / aS
= 367950 / 0.156
= 2358653.84 lb / hr.ft2
Diameter = 0.95 / 12
= 0.0792 ft
Re = De GS / µ
= 0.0792 × 2358653.84 / 0.876
= 213248
JH = 290 (Karen fig 28)
°
At t = 193 F
K = 0.353 btu / hr.ft.F
hο = JH (k / De) (CP µ / k)1/3
= 290 (0.353 / 0.0792) (1 × 0.876 /0.353)
=3200 btu / hr.ft2.F
Clean overall coefficient
UC = hio × ho / hio + ho
UC = 673.55 btu / hr.ft2.F
Dirt factor = Rd = uC – UD / UC × UD
= 673.55 – 141 / 673.55 × 141
=0.0256
Pressure drop (tube side)
NRe = 26571.16
f = 0.00018 ft2 / in2 (fig 26)
S = 0.87 (fig 6)
∆Pt = f Gt Ln / 5.22 × 10 × D × S × θT
2 10