Kurdistan Iraqi Region Salahaddin
University College of Engineering Chemical
& Petrochemical Department
Production of Acrylic Acid from Propylene
A Project Submitted to the Chemical & Petrochemical Engineering Department
University of Salahaddin-Erbil
in the Partial Fulfillment of the Requirement for the Degree of Bachelor of Science
in Chemical & Petrochemical Engineering Prepared by:
1. Ari Ahmad
2. Ahmad Ayad
3. Waleed Habbas
4. Halmat Hawar
Supervised by:
Supervisors:
Dr. Mohammed Jawdat
Mr. Ahmed
Dr. Hazim Omar
Aljawaree
2021-2022
1.1 Abstract
Acrylic acid (IUPAC: propenoic acid): - is an organic
compound with the formula CH2=CHCOOH. It is the
simplest unsaturated carboxylic acid, consisting of a vinyl
group connected directly to a carboxylic acid terminus.
This colorless liquid has a characteristic acrid or tart
smell. It is miscible with water, alcohols, ethers, and
chloroform.
2
Chapter One:
1.1 Abstract
1.2 contents
1.3 Introduction about Acrylic Acid & Propylene
1.4 Chemical and Physical properties
1.5 Application and Uses of Acrylic Acid
1.6 Method of Production,
1.7 Safety and Hazardous
3
1.3 Introduction about Propylene
Propylene is an organic compound having the chemical formula
C3H6 also known as propene . its colorless and highly flammable
gas . used in the production of wide petrochemical products such as
polypropylene , cumene , propylene oxide . its also used with in
refinery include alkylation , catalytic polymerization , and the
production of high octane gasoline blends . sources of propylene are
ethylene steam cracker plants , refinery fluid catalytic cracking
(FCC) , propane dehydrogenation .
4
1.3 Introduction about Acrylic Acid
Other names: -
Acrylic acid - Acroleic acid - Ethylenecarboxylic acid
Propene acid - Propenoic acid - Vinylformic acid.
Figure 1:2D molecule Structure Figure 2:3D molecules Structure
Acrylic acid is an important polymer as raw material for
many industrial and consumer products. It can numerous
to apply for surface coatings, textiles, adhesives, paper
treatment, baby diapers, feminine hygiene products
detergents and super absorbent polymers
5
1.4 Chemical and Physical properties
Acrylic acid is a clear and colorless liquid that finds extensive
use, owing to its chemical structure that facilitates easier
combination with large chain of compounds forming polymers.
Its molecular formula is C3H4O2 and its molecular weight is
72.06 . It is miscible in water and has a melting point equal to
14 °C, and boiling point equal to 141 °C.
10
1.4 Chemical and Physical properties
Name Acrylic Acid Propylene Acrolein Acetic Acid Oxygen
Formula C3H4O2 C3H6 C3H4O CH3COOH O2
Molecular 72.06 42.08 56.06 60.052 32
Weight g/mol
Boiling Point 141 -47.7 53 118.1 -183
at atm(c0)
Melting Point 14 -185.17 -88 16.6 -218.4
at atm(c0)
Density 1.05 0.00178 0.839 1.049 0.001429
g/cm3 at
(20c0)
Flash Point 54.5 -108 -26 39 -7.1
(c0)
Freezing 13 -59 -88 16.6 -218.8
Point
(c0)
Viscosity 1.3 0.00858 0.35 1.155 1.95
(mpa.s) at 25
c0
State at 25c0 Liquid Gas Liquid Liquid Gas
& atm
Critical 5600 4239 5000 5781 5046.962
Pressure Kpa
Critical 342 91.44 254 320 -118.6
Temperature
c0 11
1.5 Application and Uses of Acrylic Acid
The acrylic acid market has grown over the years,as
usage of this chemical has increased in various sectors,
ranging from cosmetic products, like acrylic nail polish,
to use chemical industries. Acrylic acid usage has also
run into various controversies as health agencies in US
have scrutinized its usage in various products. Acrylic
use has become extremely popular in two specific
areas—the production of Superabsorbent Polymers
(SAPs) and detergent polymers.
12
to this acid can be controlled by fire extinguishers, and
any spilling of this acid needs to be covered by sand to
avoid the damage that these acids can cause.
But generally used in:
1 Coatings
2 Elastomers
3 Water treatment
4 Leather finishing
5 Detergents
6 Hygiene products
7 Adhesives
8 Fibers
9 Plastics
10 Plastics
11 Textiles 12 Inks.
13
1.7 Method of Production
Figure3: Process Flow diagram
15
1.8 Safety and Hazardous
Acrylic acid
Propylene
Acetic Acid
17
Some Health Hazard information:
1. Acrylic Acid can affect you when inhaled and may be absorbed
through the skin.
2. Contact can severely irritate and burn the skin and eyes with
possible eye damage.
3. Inhaling Acrylic Acid can irritate the nose, throat and lungs.
4. Acrylic Acid may cause a skin allergy.
5. Long term exposure may affect the kidneys and lungs.
6. Cancer Hazard: while Acrylic Acid has been tested, it is not
classifiable as to its potential to cause cancer.
18
Chapter 2: MATERIAL BALANCE
Basis: 70 TPD of Acrylic Acid.
(Plant works continuously for 24 hours a day)
C3 H6 +O2 C3 H4O+ H2O ..1
Acrolein
C3 H4O + ½ O2 CH2=CHCOOH ..2
Acrylic Acid
Compound Molecular
weight
Propylene 42
Acrylic 72
Acid (AA)
Acetic acid 60
Acrolein 56
Oxygen 16
Carbon 44
dioxide
Propylene required to produce 70 TPD of AA
1 kmol of C3H 6 :1 kmol of AA
42 kg/hr of C3H 6 : 72 kg/hr of AA
C3H 6 required to produce 70 TPD of AA
= 70 x (42/72) = 40.83 TPD of C3H 6
At a yield of 78%
kmol of C3H 6 required = 40.83 / 0.78 = 52.35 TPD
52.35 × ( 𝑡𝑜𝑛𝑛𝑒) × ( 1000 𝑘𝑔 )×(
1𝑑𝑎𝑦
)×(
1 𝑘𝑚𝑜𝑙𝑜𝑓𝐶3𝐻6
)
𝑑𝑎𝑦 1 𝑡𝑜𝑛𝑛𝑒 24ℎ𝑟 42 𝑘𝑔𝐶3𝐻6
= 51.83 kmol/hr
Oxygen required:
1 kmol of C3H 6 requires 3/2 kmol of O2
Hence O2 required = 3/2 x 51.83 kmol/ hr
= 77.74 kmol/ hr
Main Product
Product
Main
FeedFeed
Acrolein = 36.28 kmol/hr
C3H 6 = 51.83 kmol/hr
Air = 401.68 kmol/hr
Reactor I Acrylic Acid=5.7 kmol/hr
Acetic acid = 4.925 kmol/hr
CO2 = 4.925 kmol/hr
Air = 401.68 kmol/hr
REACTOR I
Oxidation of Propylene to Acrolein.
C3 H6 +O2 C3 H4O+ H2O ..1
Acrolein
Main Feed Main Product
Acrolein =36.28 kmol/hr Acrylic acid =35.37kmol/hr
Reactor II By products formed =0.907 kmol/hr
REACTOR II
Oxidation of Acrolein to Acrylic acid
C3 H4O + ½ O2 CH2=CHCOOH ..2
Acrylic Acid
Off gases
CO2 = 5.3785 kmol/hr
N2 = 317.33 kmol/hr
O2 = 14.38 kmol/hr
Feed(inlet) AA (Acrylic Acid) =0.4107
Acrylic acid = 41.07 kmol/hr kmol/hr
Acetic acid = 5.3785 kmol/hr Acetic acid = 0.0538 kmol/hr
CO2 = 5.3785 kmol/hr
O2 = 14.38 kmol/hr
N2 = 317.33kmol/hr
Absorber
Steam = 230.64 kmol/hr
Outlet
Acrylic acid =40.66 kmol/hr
Acetic acid = 5.32 kmol/hr
Water = 1082.85 kmol/hr
Recycled stream from
solvent recovery column
Acrylic acid =0.205 kmol/hr
Acetic acid = 0.027 kmol/hr
Water = 129.94 kmol/hr
Solvent=500 kmol/hr
to solvent recovery
column
Feed
Acrylic acid =40.45 kmol/hr
Acrylic acid =40.66 kmol/hr SOLVENT Acetic acid = 5.29 kmol/hr
Acetic acid = 5.32 kmol/hr EXTRACTION Water = 21.677 kmol/hr
Water = 1082.85 kmol/hr Solvent=488 kmol/hr
COLUMN
Acrylic acid =0.415 kmol/hr
Acetic acid = 0.057 kmol/hr
Water = 1191.13 kmol/hr
Solvent=11.5 kmol/hr
recycled to extraction column
Acrylic acid = 0.205 kmol/hr
Acetic acid = 0.027 kmol/hr
Feed
Water = 21.657 kmol/hr
Acrylic acid = 40.45 kmol/hr.
Solvent = 488 kmol/hr
Acetic acid= 5.29 kmol/hr
SOLVENT RECOVERY
Water = 21.657 kmol/hr COLUMN
Solvent= 488 kmol/hr
Feed to Acid Tower
Acrylic acid =40.245 kmol/hr
Acetic acid =5.263 kmol/hr
recycled to extraction
column
Solvent= 11.5 kmol/hr
Water= 108.2 kmol/hr
Raffinate
Acrylic acid =0.415 kmol/hr
Acetic acid = 0.057 kmol/hr
Water = 1191.13 kmol/hr
Waste Tower
Solvent=11.5 kmol/hr
Acetic acid =0.156 kmol/hr
Acrylic acid =1.104 kmol/hr
Water =1082.845 kmol/hr
Top Product
Acetic acid = 5.19 kmol/hr
Acrylic acid = 0.05 kmol/hr
Feed
Acrylic acid =40.245 kmol/hr
Acetic acid =5.263 kmol/hr Acid Tower
Acrylic acid = 40.195 kmol/hr
Acetic acid = 0.197 kmol/hr
Chapter 3: Eenergy Balance
3.1 Energy balance on Reactor(R-101):
Qair =0
Q propylene =0 E.B.( Steam )
from Table ( 3-2 ) at Tavg =373+298/2 =335.5K
Cp= 34.698 kj/kg.k
Q= m ×Cp×(Tin-Tref) Q=556.42×34.698×(298-373)
=-1447999.54 KJ Qin=-1447999.54 KJ
Cp acr=70.5 Kj/Kg.k Qacr=mcp ∆T
= 549191.5 KJ
Cp N2=29.4 kj/kg.k Q N2=mcp∆T
=1214803.965 KJ
CpO2 =29 kj/kg.k
QO2=207427.6 KJ
Hr=Hf product − Hf react
Hr=295.9 KJ/Kmol
Q out=1971423.065 kj
Hr + Q = Qout- Qin
Q=3419126.8 KJ
3.2 Energy Balance on Fluidized Gasification(R-102) Qin=Qout =1971423.1kj
Q acr= mcp∆T
Cp acr= 155.79 kj/kg.k Q acr=4579303.91 Kj
Q N2= mcp∆T
Q N2=7536819.158 kj
Q O2=348528.46 kj/kmol Hr=242.51 Kj/kmol
Qout=12464651.5 kj
Hr + Q = Qout – Qin
Q=10492985.92 KJ
3.3 Energy Balance on Heat
Exchanger(E-101) Qair=0
Q propylene=0
E.B.(Steam)
From Table (3-2) at Tavg=373+298/2 =335.5 K
Cp=34.698 kj/kg.k
Q=m×Cp×(Tin-Tref) Q=556.42×34.698×(298-373)
=-1447999.54 KJ
Qin=-1447999.54 KJ
Qout=Qacr+QN2+QO2
Qacr=549191.5 KJ QN2=1214803.965 KJ
Hr = Hf product− Hf react Hr=295.9 KJ/kmol
Qout=1971423.065 KJ
Hr + Q = Qout-Qin Q=3419126.8 Kj
3.4 Energy Balance on Heat Exchanger(E-102)
Qin=Qout =1971423.1kj
Q acr= mcp∆T
Cp acr= 155.79 kj/kg.k Q
Qacr=4579303.91 Kj
Q N2= mcp∆T
Q N2=7536819.158 kj
Q O2==348528.46 kj/kmol
Hr=242.51Kj/kmol Qout=12464651.5 kj
Hr + Q = Qout – Qin
Q=10492985.92 KJ/hr
Chapter 4: Equipment Design
Introduction
From papers :The reaction is first order reaction and the
reaction constant for 1 hr equal to 23.4 hr-1.
Gas-solid reaction,the reactor is Fixed bed reactor.
The fixed beds of concern here are made up of catalyst
particles in the range of 5mm [Link] catalyst in a
reactor may be loaded as several packed tubes in a single
shell.
4.1Reactor design calculation
Reaction time =1hr WN2 =12718 Kg, x=0.63
WO2=1489.6 Kg, x=0.08
Wacrylic acid 5816.49 kg, x=0.29
W total=20024.09 kg x=1
p Acrylic acid=8.39kg/ m3
p Oxygen =9.69452 kg/m3
p Nitrogen =18.338 Kg/m3
pMixture=(0.63*18.338)+(0.08*9.69452)+(0.29*8.3)
=14.699 Kg/m3
V Acrylic acid=5816.49 / 8.39=693.2m3 =693.2*103 L
V oxygen= 1489.6 / 9.69452=153.5m3 =153.5*103 L
V Nitrogen= 12718/ 18.338=693.5m3 =693.5*103 L
V Total=1540.2*103
CA0= n _ 148.38 _A rjQ/:
VTotal “1540.2* 103 ’ ° kmol/L
FA0 =148.38 kmol
CA=CAo (1 - XA) = 0.096 (1 - 0.29)=0.0684 kmol/L
First order system (from
_4 - 4.5
paper) JA IT" =-0.111
K=6.5 x 10 - 3 s - V= ) ln(1 - XA) - SA XA] 1 =23.4 hr-1
148.38
V=23,4.o.o96- (- (1 - 0.111) ln(l - 0.29)-(-0.111*0.29)] V= 17.769m3
v4d2z
Z=3d
V=- d2 * 3d 4
17.769=f*3*(d3)
d=1.96m
Z=3*1.96=5.88 m
Mechanical design
1-Cylinderical section P=9 bar
Design pressure take 10% above operating pressure
P=9.1 bar
P=0.91 N/mm2
Design temperature= 150oC
From table13.2(vol.6 ) (page 809) typical design
stress (f )=135 N/mm2
The material is stainless steel
e_^21_= (13.39a)vol.6 page(812)
(2 j f - P) shell
thickness in [mm]
p=maximum working pressure [N/mm2]
D=wide diameter of shell [mm] f=maximum
allowable working stress [N/mm2] j=weld
efficiency factor (max. =0.8) (From table
0.91*1.96*1000
13.3 (vol.6) e = 2*135*0.8-o.9ie = 8.29 mm
Add corrosion allowance = 2mm
e= 8.29 mm+2mm e =10.29 mm
2- Domed head
Flat plates are used as covers for manways, and as the
channel covers of heat exchangers. Formed flat ends,
known as “flangeonly” ends, are manufactured by
turning over a flange with a small radius on a flat plate.
The corner radius reduces the abrupt change of shape, at
the junction with the cylindrical section;which reduces
the local stresses to some extent: “Flange-only” heads
are the cheapest type of formed head to manufacture,
but their use is limited to low-pressure and small-
diameter vessels. Standard
torispherical heads (dished ends) are the most commonly
used end closure for vessels up to operating pressures of
15 bar. They can be used for higher pressures, but above
10 bar their cost should be compared with that of an
equivalent ellipsoidal head. Above 15 bar an ellipsoidal
head will usually prove to be the most economical
closure to use. A hemispherical head is the strongest
shape; capable of resisting about twice the pressure of a
tori spherical head of the same thickness. The cost of
forming a hemispherical head will, however, be higher
than that
for a shallow tori spherical head. Hemispherical heads
are used for high pressures.
(a) Hemispherical
(b) Ellipsoidal
(c) tori spherical
Standard dished head (tori sphere)
A head of this size would be formed by
pressing J=0.8
P Rc Cs
Q =2 f j -P(Cs—0.2) Eq.(13.44) vol.6
Page(816)
46
where Cs = stress concentration factor
for tori spherical heads
Cs=I(3+^iiT)
Crown radius Rc = Di =1.96 m
3-Design Flat head
Though the fabrication cost is low, flat ends are not a structurally efficient
form, and very thick plates would be required for high pressures or large
diameters. The design equations used to determine the thickness of flat
ends are based on the analysis of stresses in flat plates. Values for the
design constant Cp and the nominal plate diameter De are given in the
design codes and standards for various arrangements of flat end closures.
The values of the design constant and nominal diameter for the typical
designs Bolted cover with a full face gasket , take Cp =0.4 and De equal to
the bolt circle diameter.
Fig 4.2 Bolted Cover
e = Cp *D e*Jf Eq.(13.42)vol.6 Page(815)
De =diameter let= 1.96 m
Cp =a design constant, dependent on the edge
constant For Bolted cover=0.4
e=0.4*1.96*1000*Vb.91/135 =64.36mm corrosion
allowance =2mm e=66.36mm
3-weight load
The major sources of dead weight loads are:
1- The vessel shell.
2.- The vessel fittings: manways, nozzles.
3- Internal fittings: plates (plus the fluid on the plates); heating
cooling coils .
4- External fittings: ladders, platforms, piping.
5- Auxiliary equipment which is not self-supported;
condensers,agitators.
6- Insulation.
7- The weight of liquid to fill the vessel. The vessel will be filled with
water for the hydraulic pressure test; and may fill with process liquid
due to misoperation.
Note: for vessels on a skirt support, the weight of the liquid to fill the
vessel will be transferred directly to the skirt. The weight of the vessel
and fittings can be calculated from the preliminary design sketches.
The weights of standard vessel components: heads, shell plates,
manways, branches and nozzles, are given in various handbooks;
Megyesy (2001) and Brownell and Young (1959).
Dm = mean diameter of vessel = (Di + t*10-3), m. Let H =4.95 m
Dm=(1.96 + 8*10-3 ) = 1.968m
Wv=240*1.15*1.968*(4.65+0.8* 1.968)* 8*10-3
Wv =27.04715 KN
Wv=27047.15 N Weight of plates:
Plate area = I*Dl =301m
Weight of a plate (see page 761 vol .6) =1.2 *Area =3.612 KN
2 plates = 2* Weight of a plate =7.224 KN
Shell 27.04715 KN
Total 30.659 KN
Plates 3.612 KN
4-skirt supports
The method used to support a vessel will depend on the size, shape, and
weight of the vessel; the design temperature and pressure; the vessel
location and arrangement; and the internal and external fittings and
attachments. Skirt supports are used for tall, vertical columns; The
supports must be designed to carry the weight of the vessel and contents,
and any superimposed loads, such as wind loads. Supports will impose
localized loads on the vessel wall, and the design must be checked to
ensure
that the resulting stress concentrations are below the
maximum allowable design stress. Supports should be
designed to allow easy access to the vessel and fittings for
inspection and maintenance. For straight
cylindrical skirt 0=90°
D =[1.96+1.96 [(70+0)* 10 ]]=2.09 m Fw
Loading (per linear meter)=Pw*Deff
Fw=1280*2.09=2675.2 N/m
_ Fw*h2 _
Mx--2—32774.5 N.m
Bending moment at base of skirt
Take height of skirt =52m Height of
reactor =4.95m 2 Total height
=4.95+52 =56.95m
4Ms
n (Ds+ts) ts Ds Eq.(13.88) vol.6 Page(846)
Bending M = Mx*
8bs =bending stress in the skirt Ms
=maximum bending moment
Ds=inside diameter let =1.591m
w
= ^ (Ds +ts) ts 2929.45 N/mm2
8w= the dead weight stress in the skirt
ts= thickness=6mm W=total weight g
= NApproximate weight= 7 p Total Weight =
^ *l.962*4.95* 1000*9.81=146438.74
Approximate weight + Total weight of vessel Total
weight = 146438.74
Criteria design:
maximum Ss(comp.) 6bs + Sw(test) Eq.13.87
vol.6 Page(846)
2929.45+3953.58= 6883.03 N/mm2 maximum
6s(tensile)= 6bs - Sw(operating) Eq.13.86 vol.6
Page(846) = 2929.45+4683.81 =7613.26 N/mm2
Base ring and anchor bolts Bolt circle diameter
=1.44m Circumference of bolt circle = 1.44*11
Number of bolt required = 6oo 3142°-6IOOO n
Closest multiple of 4= 8 bolt Take both design
stress = 125N/mm2
Ms=[Link]
Take W = Weight of vessel (operating valve)=
27047.15 N
Ab_ Nb*fb ^ Db - W) Eq. 13.92 vol.6 Page(848)
where Ab = area of one bolt at the root of the thread,
mm2, Nb = number of bolts, fb = maximum allowable
bolt stress, N/mm2; typical design value 125 N/mm2
(18,000 psi), Ms = bending (overturning) moment at
the base,
W = weight of the vessel, N,
Db = bolt circle diameter, m
Ab 8*125( 4*53167.47
*1000 1.44
-27047.15)=120640.2667mm2
Total compressive load on the base ring per unit
length
Eq.13.93 vol.6
27047.1
4*53167.47 *1000
+ + --------- 17634874.89 fbn/m
77 1.96 2
771.96 Page(848)
Taking the bearing pressure as 5 N/mm2
Eq. 13.94 vol.6 Page(848)
where Lb =base ring width, mm (Figure 13.29 vol.6),
fc = the maximum allowable bearing pressure on the
concrete foundation pad, which will depend on the mix
used, and will typically range from 3.5 to7 N/mm2
(500 to 1000 psi).
Flange ring dimensions Taking the bearing pressure
as 5 N/mm2
Take the skirt bottom diameter as 4m
Skirt base angle 0S =tan-1 =73 Keep the skirt thickness the same as that
calculated for the cylindrical skirt. Highest stresses will occur at the top of the
skirt; where the values will be close to those calculated for the cylindrical skirt.
Sin 73 =0.96, so this term has little effect on the design criteria
Refrences
-Varadarajan S.,D.J. [Link] upgrading of fermentation –derived organic
Acids Biotechnol Prog . 1999;(15(sad)845-854
-Carl L . Yaws . Handbook Physical,Thermodynamic,Environmental,
Transport,Safety And Health related Properties for Organic And Inorganic
Chemicals
-R.K. Sinnott ;Chemical Engineering Design , Volume six , 2nd Edition
-Gavin Towler,Ray Sinnott ;Chemical engineering Design.
