1.

INTRODUCTION
Isopropyl alcohol (IPA) with its excellent properties is a growing-demand product worldwide.
Common names for it include IPA, rubbing alcohol, dimethyl carbinol, isopropanol, -propanol
and sec-propyl alcohol. IPA (C
!
"
#
$") is a flammable, colorless li%uid with a strong and slightly
pleasant odor. It is completely miscible with water, ethanol, acetone, chloroform, and ben&ene'
melting at -() C and boiling at ( C. It has an ad*antage of being soluble in non polar substances
and e*aporating %uic+ly. ,herefore, it is commonly used as either a sol*ent or a cleaning fluid. It
is *ery inexpensi*e and cost effecti*e which contributes to its widespread usage.-./-#/
In today0s society IPA has many practical uses from paint thinner to rubbing alcohol and has
extensi*e applications in pharmaceutical, pesticide, coatings, daily-use chemical and organic
synthesis sectors. ,he primary usage for IPA is as an industrial sol*ent for many oils, al+aloids,
gums and resins,but it has many more usages. In the stores, rubbing alcohol generally consisting
of #12 isopropanol is sold in order to be used for a *ariety of uses such as cleaning, sterili&ing
s+in or helping to get rid of swimmers ear. As a cleaning agents IPA is used on electronics
de*ices such as contact pins (li+e those on 3$4 cartridges), magnetic tape dec+ and floppy dis+
dri*e heads, the lenses of lasers in optical disc dri*es (e.g. C5, 565) and remo*ing thermal
paste from CP78s. It is also used to clean glass computer monitor screens, and is used by many
music shops to gi*e second-hand or worn records newer loo+ing sheens. It cleans dry-erase
boards *ery well and other unwanted in+ related mar+s. In biology isopropanol can be used in a
strong solution as a preser*ati*e to replace formaldehyde. Another common use for IPA is as an
additi*e in gasoline so that fuel lines don0t free&e in the winter. It is also used in manufacturing
acetone, glycerol and isopropyl acetate. -#/
$n the other side toxicology is a matter fact to be considered for human health. ,here is no ris+
of cancer, ris+ of malformation in an unborn fetus or ris+ of heritable genetic effects. 9ut, s+in
contact o*er a long period of time may cause dermatitis. ,herefore, body care products including
IPA are not ad*iced with respect to a clinical research.-(/-)/
,he total capacity of isopropyl alcohol is around .! million t:a in the world, !#2 in the 7nited
;tates, <2 in Canada, !2 in =atin America, !(2 in >est ?urope, (2 in @apan and A12 in the
Asian-Pacific 3egion. ,he 7nited ;tates, @apan and >est ?urope are also maBor consumers in
the world and the consumption accounts for #12 of the world total. In these countries and
regions isopropyl alcohol is mainly used as sol*ent and in acetone processing and the
consumption in these two fields0 accounts for .1 - #12 of the total. In terms of isopropyl alcohol
A
deri*ati*es, the demand in cleaning agents is ma+ing the most rapid growth and the consumption
in chemical intermediates is also ha*ing a rapid increase. ,he demand in pharmaceuticals,
surfactants and in+s has been stable in the recent years and the demand in coatings and pesticides
has presented a declining trend.-A1/
,here are three commercial routes to IPA are used. ,he indirect hydration of refinery-grade
propylene uses sulphuric acid to form isopropyl sulphate which is then hydrolysed with steam to
form sulphuric acid and IPA. ,hen, the crude IPA is distilled to the desired purity. ,he
disad*antage of this process is being corrosi*e and high energy demanding for acid
reconcentration and a%ueous waste treatment.,he direct hydration of chemical grade ()1-))2)
propylene is a more modern method which a*oids the need for sulphuric acid. ,his process uses
thermally stable polymeric catalyst. ,he third method uses acetone as the starting material unli+e
the first two methods. A *ery small amount of IPA is produced by the hydrogenation of acetone
in the li%uid phase. ,his process is only suitable where excess acetone is a*ailable. In 7;A
indirect hydration is commonly used' whereas in ?urope direct hydration process is more
common. -AA/-A/
,his proBect deals with direct li%uid phase hydration of propylene and water in the presence of a
strong acid solid catalyst for producing high %uality isopropyl alcohol. Cuality of the product,
low capital expenditures and sensiti*ity for en*ironment are ta+en in to consideration while
selecting this type of process. Isopropyl alcohol manufacturing plant is designed with a capacity
of <!,111 tons:year. ChemCA5 program is used to simulate the flow of the process and calculate
the inlet and outlet streams of the units.-AA/
Dirst EProcess ;election and 5escriptionF part of the report tells about fi*e different rele*ant
patents about this manufacturing process and describes them one by one. 9y comparing each of
them with respect to their properties, the patent which has better properties is selected. ,hen
grading of the processes are made according to their properties and units. ,his part lastly
describes the selected process in detail. ,hen, assumptions are implied at the beginning of the
calculation part. ,hen comes the E5iscussionF part which discusses the whole proBect. ,his part
contains the discussion of choice of the process, assumptions, calculations, chemcad and
discussion of the calculated design capacity. =astly the report ends with the EConclusionF part
which implies a general *iew of the proBect with technical information and %ualitati*e results.

2. MARKET INVESTIGATION AND CAPACITY DETERMINATION OF ISOPROPYL

ALCOHOL PRODUCTION
2.1 Market Invet!"at!#n
;hell, ?xxon4obil, ;asol and 5ow are the largest producers of IPA and they ha*e o*er #2 of
world capacity. It is ober*ed that o*ersupply resulted in decreased demand and two maBor plant
closed because of lower margins in >estern ?urope in the last few years. ;hell closed its
;tanlow, 7nited Gingdom IPA plant in 11! which has a )1 thousand metric tons of annual
capacity and also 9P shut its A11 thousand metric ton-per-year Port ,albot, 7nited Gingdom IPA
plant in 11<.,he following pie charts shows world consumption of IPA in 11H and world
consumption of IPA by end use,respecti*ely. -A!/
F!"$re 2.1 >orld Consumption of IPA 11H -A!/
In direct sol*ent applications IPA is consumed o*er H12 of total demand. It is also used in
surface coatings, in+s, pesticide formulations, electronic applications, reagents and as a
processing sol*ent in the production of resins.-A!/
,he largest use for IPA is as a sol*ent. ,he second largest use is as a chemical intermediate. IPA
is also found in many e*eryday products such as paints, in+s, general-purpose cleaners,
disinfectants, room sprays and windshield deicing agents. It is also used as an ingredient in
cleaners and polishers, as a chemical intermediate, and as a dehydrating agent and extractant.
-AH/
!
Isopropyl alcohol is cheaply a*ailable. As a preser*ati*e for biological specimens, it is cost-
effecti*e when compared to pure ethanol and comparati*ely non-toxic alternati*e to
formaldehyde and other synthetic preser*ati*es. -A</
Isopropanol is a maBor ingredient in Idry-gasI fuel additi*e. It helps water to solubili&e in
gasoline. >ith this way there exists no ris+ for free&ing and accumulating of water in fuel tan+s.
Isopropanol is often sold in aerosol cans as a windscreen de-icer. -A</
.
F!"$re 2.2 >orld Consumption of IPA by ?nd 7se 11H -A!/
Jlobal IPA that is based on acetone production is expected to decrease with the increase of
phenol capacity since acetone is a coproduct of phenol by the cumene peroxidation process.
>orldwide IPA consumption is forecast to grow at an a*erage annual rate of .1K.H2 . -A!/
<
2.2 Ca%a&!t' Deter(!nat!#n
5ata which the design capacity is based on is obtained from 5I?, ,ur+ish Institute of ;tatistics,
7nited Lations 5ata and ,3 Prime 4inistry ;tate Planning $rgani&ation. ;ince isopropyl
alcohol (IPA) with commercial code )1HA is not produced in ,ur+ey, the consumption of this
chemical is simply the difference between the imports and exports. -A./ -A#/
Ta)*e 2.1 ,ur+ey Import-?xport 5ata for IPA
2+1,-, I(%#rt.E/%#rt
Year
A(#$nt
0k"1
A))1 H!!)!1
A))A <(.)(.
A)) .)#H!#
A))< (#<(.##
A))H AA!((<.
A)). AA(<1#
A))( A<11.<.
A))) A<.A)11(
111 A)!.#A
11 A(#A.<1
11! 1.A!1(#
11< !)HA1
11. 11H..)
11# A!#A#<<
11( 1H1.A#.
,able .A is calculated from ,able A.A.9ecause the data de*iate within the years A))A and 11(,
it should be approximated using to !-year mo*ing and H-year mo*ing a*erage in order to obtain
a better fit.
H
IPA C#n$(%t!#n !n T$rke'
1.?M11
<.?M1.
(.?M1.
A.?M1#
.?M1#
.?M1#
.?M1#
A)(( A))1 A)) A))< A)). A))( 111 11 11< 11. 11( 1A1
'ear
k
"
,ur+ey
F!"$re 2.- Consumption of IPA in ,ur+ey A))1-11(
,he figure abo*e shows the actual *alue of IPA consumption in ,ur+ey for each year. As it can
be obser*ed abo*e, the data points do not re*eal a consistent pattern. ;o the ! year mo*ing and H
year mo*ing a*erage of the data are needed.
- Year M#v!n" Data #2 IPA C#n$(%t!#n !n T$rke'
1.?M11
<.?M1.
(.?M1.
A.?M1#
.?M1#
.?M1#
.?M1#
A)(( A))1 A)) A))< A)). A))( 111 11 11< 11. 11( 1A1
'ear
k
"
! Near
mo*ing
F!"$re 2.3 ! year-mo*ing consumption data of IPA in ,ur+ey A))A-11#
,he ! year mo*ing a*erage data points are more consistent with each other. Although the first
and the last data points are lost during ta+ing the a*erage, the remaining points are enough for
modeling.
.
4 Year M#v!n" Data #2 IPA C#n$(%t!#n !n T$rke'
1.?M11
H.?M1.
A.?M1#
.?M1#
.?M1#
!.?M1#
A)(( A))1 A)) A))< A)). A))( 111 11 11< 11. 11( 1A1
'ear
k
"
H years
a*erage
F!"$re 2.4 H year-mo*ing consumption data of IPA in ,ur+ey A))-11.
,his data is smoothed using a fi*e point mo*ing a*erage. 9ecause the first two and last two
points are lost during this calculation, the rest points are not satisfactory to fit a model although
the points seem more consistent with each other.
,hus, the ! year mo*ing a*erage data are more suitable in order to estimate production capacity.
;ome models are fit to data obtained from ! year mo*ing a*erage. ,he model e%uations are
shown belowO
Polynomial Dit of th 5egreeO
y P -<HH.!.!Hx

M A(!!.A#.HAx - A(<1A(.A(.).A with 3Q P 1.)(1

?xponential DitO
y P y P !?-.#e
1.1(<(x
with 3Q P 1.(()
=ogarithmic DitO
y P A<#A<<<)#.H)ln(x) - A.!1<.HA)...1 with 3Q P 1.)H1
=inear DitO
y P A1#!((<.1#x - A!A(1<A#!.( with 3Q P 1.)H1
#
F!tte5 M#5e* t# - Year M#v!n" Avera"e
y P !?-.#e
1.1(<(x
3

P 1.((()
y P -<HH.!.!Hx

M A(!!.A#.HAx - A(<1A(.A(.).A
3

P 1.)(
1.?M11
<.?M1.
(.?M1.
A.?M1#
.?M1#
.?M1#
.?M1#
!.?M1#
!.?M1#
A))1 A)) A))< A)). A))( 111 11 11< 11. 11(
'ear
k
"
3andom ?xpon. (3andom) Poly. (3andom) =og. (3andom) =inear (3andom)
F!"$re 2.6 4odels fit to ! year mo*ing a*erage data
Pr#7e&te5 M#5e*
1.?M11
.?M1#
<.?M1#
..?M1#
(.?M1#
A.?M1(
A.?M1(
A))1 A))H 111 11H 1A1 1AH 11 1H
'ear
k
"
linear exp poly log consumption
F!"$re 2.8 4odels fit to ! year mo*ing a*erage data
(
( )
log
log A
i
Turkey
GDP
GDP
N

=
+
,he 3

*alues for polynomial, exponential, logarithmic and linear models are 1.)(1, 1.((), 1.)H1
and 1.)H1 respecti*ely. 9ecause the 3

*alues are *ery close to each other and each model is

acceptable to present the IPA consumption of ,ur+ey up to year 11(, the IPA consumption of
the countries which ha*e similar economic structures to ,ur+ey should be ta+en into
consideration. ,ur+ey is a de*eloping country. ,he IPA consumption cur*es in de*eloped
countries such as Austria, Drance, Jermany, Jreece, Italy, ;pain, ;wit&erland and ?ngland
which ha*e similar economic structure to ,ur+ey can gi*e an idea how will the IPA consumption
of ,ur+ey be in the next 1 years. In order to estimate it, it should be calculated how many years
are the economy of these countries ahead from ,ur+ey. Dirst of all, Jross Lational Products per
capita of the countries mentioned abo*e and ,ur+ey, the annual growth rate of ,ur+ey for each
year are found.(,able A.)
,he Consumption of the ?uropean countries can be found by'
Consumption P Production M Import - ?xport
,able A.< and ,able A.H are used for this e%uation.
Ta)*e 2.2 IPA Consumption for ?uropean Countries
AUSTRIA FRANCE GERMANY GREECE ITALY SPAIN S9IT:ERLAND ENGLAND TURKEY
2006 #1!.A)) <.<HH11 H.#<1A11 .1!)<
!<1(<#
)
<#((<#.
H A!!<<<). <.<)) 1AA1HH<
2005 .)<<1(< !<H!H.11 H<!((11 A()<H.
!A<)!<(
<
<H!<).
( A!.<.1A1 <##.()H) A(1111
2004 <(!..!1 <A.(AA11 H1#<!A11 H<!)..
()1)!!
#
H1#!H
! A<(1<#( A<!(1H <A#))<
2003 H)(A# <((111 .1)<A1. #.((.
!<(#!A
.
<!(<!1
1 A!.).A.# H(11.< 1#.((1!
2002 .()A() HH#H(!11 H<(#1#<. A<)(A)
)<A#<.
)
).#).1
H AH.#AH (1(###( A(#<(#(H
2000 #).(A!) H1HH!11 H#A#1#<1 1H!A.)
!H..1A.
A
!!!(!<(
# ))<H<1# !).!)1 A)(!AH)
1999 H1.#(() H<<<AA.( H#!!A(<1 )!!)1
!.1HAA

<!H(A)1
!1#)).< H1!<H) A<.1)))1
1998 )<#!HH. HH).#(( H##<<.< (..H#
!<.H)HA
#
<<.)(#H
< A.H<)H! !#A(H1< A<1H#1H(
1997 A1.A)1H1 H.<.A<) H#1H)(< ))...
!<##!#
#
<!#H)1.
# AH1#.AH1 <<.!< AH!1#AH!
1996 )!H!1H H<()H< H#)#.)1< <.#<1(
!#!11
H
<#H
) A.#(.1. <#AH..< AA(H1!)(
1995 )1(1.1< <!H.(1#( (A!<((< HA!<
!#(<A

!(<!)<#
. AHAA.<A. .<AA<A. AA!)!<.
1994 )#!A#(1 <.<)(1 !(.1)HA. A#A!AH#
!!)!)(1
#
!HA.<
A<)#!#.! A)(.1A (#H.A<A
1993 <#<)!#. A#)..H
!1#<)!!
) A<11A#1 .H(## (!AHAH)
1992 H1H#!#A A#<(.!)
1A!1<A
< AH)A. .!1(1H
Drom the annual growth of ,ur+ey and J5P *alues of countries (,able A.!), it is calculated how
many years are the economy of each specific country at specific years ahead from ,ur+ey *ia the
e%uationO
)
-A/
LO years a country ahead from ,ur+ey
RO annual growth of ,ur+ey
J5PO Jross 5omestic Product
Drom now on, Jermany is chosen as the sample country and all of the calculations will be shown
according to the data of Jermany.
Dor year 11. for Jermany,
J5P ,ur+eyO )1#! S
J5P JermanyO !A#<< S (,able A.!)
Jrowth rate of ,ur+ey at 11.,R O ..A2 (,able A.)
( )
!A#<<
log
)1#!
A.AHA
log A 1.1.A
N



= =
+
year difference between 11. Jermany and ,ur+ey
,he same calculation is done for each year and each country
Ta)*e 2.- Near difference between de*eloped countries and ,ur+ey
Year 5!22eren&e )et;een 5eve*#%e5 &#$ntr!e an5 T$rke'
Year A$tr!a Fran&e Ger(an' Gree&e Ita*' S%a!n
S;!t<er*an
5
UK
2,,6 !.1.( .1A< A.AHA A#.A.) 1.H.A A).!.! <.AH! .#)
2,,4 A).!#) A(..( A#.(1( A<.!< A#.<<< A..!< 1.!!1 A).A1
2,,3 A..#(H A..H# AH.<## A.!1 AH.!(A A<.1#H A#.H. A...!<
2,,- ..<(. H..) <.HA) A)..A <..H< .<!) #.#< ..1)A
2,,2 1.1<) A).H.( A(.#<( A<.H A(.)A. A#.11H A.( A)..A)
2,,, 1.#H( 1.A!. A).!.# A!.H## A).<!1 A#.A<! .A<H A).#!H
1++= <..A!. <<..H. <!.)< ).1(( <!.!1( !#.1) H1.A.< <<.A!(
1++8 A).A(# A(.H)) A(.A.) A.1#A A(..! AH.<( A.1A! A(.!).
1++6 A.1H) 1.<AA A).))< A!.#. 1.1. A..H(. !.1A) 1.1<
1++4 1.(H< 1.<.H 1.1#! A!.!)# 1.A!. A..H< !.A1< A).(H<
1++- A#.)(! A#.#A) A#.!A) AA.<#! A#.<. A<.1<A 1.H.( A..#<(
1++2 H.1A) <...H <.A) A..H)A !.)<H A).#(1 (.!.H .#H
1++1
A.<.A
H
A.!.!1
!
AH)..H(
AA...
#
AH).)
1
A!.!
1
A)1.1A. AH.!A#
A1
Drom these *alues, the corresponding years of ,ur+ey is calculated with respect to the de*eloped
countries.
Ta)*e 2.3 Corresponding years of ,ur+ey to de*eloped countries
C#rre%#n5!n" 'ear #2 T$rke' t# 5eve*#%e5 &#$ntr!e
Year A$tr!a Fran&e Ger(an' Gree&e Ita*' S%a!n S;!t<er*an5 UK
2,,6 1) 1( 1# 1! 1# 1H 1!1 1)
2,,4 1< 1< 1! 1A) 1 1A 1H 1<
2,,3 1A 11 1A) 1A. 1A) 1A( 1 1A
2,,- 1) 1) 1( 1 1( 1H 1!A 1)
2,,2 1 1 1A 1A. 1A 1A) 1! 1
2,,, 1A 11 1A) 1A< 1A) 1A# 1 11
1++= 1<< 1<! 1<A 1# 1<A 1!H 1<( 1<
1++8 1A. 1A. 1AH 11) 1AH 1A 1A( 1AH
1++6 1A# 1A. 1A. 11) 1A. 1A! 1A) 1A.
1++4 1A. 1AH 1AH 11( 1AH 1A 1A( 1AH
1++- 1AA 1AA 1A1 11< 1A1 11# 1A< 1A1
1++2 1A# 1A# 1A. 11) 1A. 1A 11 1AH
,his result means that ,ur+ish economy is supposed to reach to the le*el of 11. Jerman
economy at 1#.
Low the population and IPA consumption per capita of each countries should be ta+en into
consideration.
In order to calculate 1# population of ,ur+ey , 11H year is ta+en as basis.
Population of ,ur+ey at 11H O #!)111
Population growth of ,ur+ey at 11HO A.!2 -A./
( ) 1# 11H
#!)111 (A 1.1A!) )(<1#(1.

+ =
In order to calculate 1# J5P of ,ur+ey , 11H year is ta+en as basis.
J5P of ,ur+ey at 11H O (<1( S
J5P growth of ,ur+ey at 11HO #.<2
( ) 1# 11H
(1<( (A 1.1#<) <1(#.

+ = S
,he consumption per capita for Jermany'
H.#<1A11
1..()
()!111

=



S
AA
,he consumption per capita for ,ur+ey at 1#'
( ) ( )
,1#
,11.
: :
Turkey
Turkey Germany
Germany
GDP
consumption capita consumption capita
GDP

=





<1(#.
1..() 1.(((
!A#<<

=


S
In order to find the capacity of ,ur+ey at 1# consumption per capita is multiplied by predicted
population of ,ur+ey at 1#'
1.((( )(<1#(1. (#!#A!)A.A# =
Gg:year
Power purchasing parity (ppp) has to be ta+en into consideration in order to reach reasonable
data.
PPP
,ur+ey, 11H
P 1.(1 -A./
PPP
Jermany, 11H
P 1.)A
,he capacity of ,ur+ey at 1# considering power purchasing parity'
1.(
(#!#A!)A.A# ( ) #.((.(<.#A
1.)A
=
Gg:year
Ta)*e 2.4 Calculation of capacity with respect to Jermany
GER
P#%>T$r>2$t$r
e
GDP>T$r>2$t$re &#n?&a%!ta>GR &#n?&a%!ta>TR Ca%a&!t'>e/&>%%% Ca%a&!t'
2,,6 )(<1#(1H <1(#..H< 1..() 1.((( (#!#A!)A.A# #.((.(<.#A
2,,4 )!1!))( ))(1.111 1..!. 1..!. H)A(.(H.A). H1(1#..)#!
2,,3 ()AA#< !.!<.A.H 1..AH 1.H1H <<)#1!HH.<() !)H#!)A.(!1
2,,- )((#.<.H <A).<.A(. 1.#!( A.A AA1)#(.(.!#( )#.A.H<.A#
2,,2 )1H)..A1 H(#)... 1...H 1..!< H#<..)#).A( H1H#1)<A.#A
2,,, (())<)A! !<<).H<< 1..)H 1..! H.<1.!A.(H <)<)A#H..11.
1++= AA(A!1)1< AAA).)! 1..)( !.!1( !)1#))A.<) !<!)1!#.#!(
1++8 (<)#).H A#!##.< 1..)H 1.H. <<!.)H))..H! !)1<H<#..)H
1++6 (H11!!< A(<!1.H(H 1.#1# 1.H(# <))(AH!.11. <!)(!#<1.<H
1++4 (<A))#! A#H#.)!. 1.!<< 1.#< !1#.<AA.!HH 1!1#<A.))!
1++- #)A#(#AA A)A.A(( 1.H(! 1.!H) (!)(H.##< <)(H.(...(A
1++2 (H!<).) A(.1).!.< 1..H 1.H(. H11!<H..1H <<1!1<A<..1H
A
,his calculation is done for each year and each country.(,able A.#, A.(, A.), A.A1, A.AA, A.A,
A.A!).,hen they are plotted together.
1.?M11
H.?M1#
A.?M1(
.?M1(
.?M1(
!.?M1(
!.?M1(
A))1 A))H 111 11H 1A1 1AH 11 1H 1!1 1!H 1<1
'ear
k"?'ear
expo model
linear
poly
log
Austria
Drance
Jermany
Jreece
Italy
;pain
;wit&erland
?ngland
,ur+ey
;eriesA!
F!"$re 2.= Consumption ProBections of IPA 3esins in ,ur+ey Including ?uropean Countries
1.?M11
H.?M1#
A.?M1(
.?M1(
A))1 A))H 111 11H 1A1 1AH 11 1H 1!1 1!H 1<1
'ear
k"?'ear
expo model
linear
poly
log
Austria
Drance
Jermany
Jreece
Italy
;pain
;wit&erland
?ngland
,ur+ey
;eriesA!

F!"$re 2.+ Consumption ProBections of IPA 3esins in ,ur+ey Including ?uropean Countries
A!
Dinal consumption data for ,ur+ey are plotted in Digure .). As can be seen in the figure, ,he
logarithmic model fits best as a consumption proBection of IPA in ,ur+ey. Drom this model, the
capacity for the IPA production process in 1H was determined as <!,111 tons:year.
-. PROCESS SELECTION AND DESCRIPTION
-.1. Re*evant (et@#5 an5 %r#&ee
Isopropyl alcohol (IPA) is produced by combining water and propylene. ,here are three
processes in order to obtain it. ,wo of them use propylene as the starting material. ,hese are'
indirect hydration which is +nown as sulfuric acid process and direct hydration with a
heterogeneous polymeric acid catalyst. In the third process acetone is used as the starting
material. =ow %uality propylene is used during indirect hydration and it is commonly used in
7.;.A.' whereas direct hydration re%uires high %uality propylene and is commonly used in
?urope. -A/
Indirect hydration is used in order to produce IPA by using sulfuric acid. $lefins are hydrated to
alcohols by a two stage process. In the first step, olefins are esterified with sulfuric acid to al+yl
sulfates. In the second step these al+yl sulfates are hydroly&ed. ,he whole reaction ta+es place at
low temperature. ;ince this process is corrosi*e and demands high energy for acid
reconcentration and a%ueous waste treatment, it is not preferred in this proBect as the production
process.
5irect hydration process uses thermally stable polymeric catalyst. ;ince its product %uality
impro*ement is high, its capital expenditures are low and it is less en*ironmentally sensiti*e' it is
chosen as the production process.-A(/ ;imple reaction mechanism of direct hydration process is
shown below and it is an exothermic reactionO
propylene water isopropanol +
! . !
1 ( ) C H H CH OH OH +
A<
-.2. C#(%ar!#n #2 t@e %r#&ee )ae5 #n env!r#n(enta*A te&@n!&a* an5 e&#n#(!&a* a%e&t
-.2.1 D!!#%r#%'* Et@er Rever!#n !n I#%r#%an#* Pr#5$&t!#n
Patent n#B US 3A-42A+34
Date #2 %atentB O&t. 4A 1+=2
F!"$re -.1 5iisopropyl ?ther 3e*ersions in Isopropanol Production
,he aim of this in*ention is to produce isopropyl alcohol and blending into gasoline by hydration
of propylene. Digure !.A represents the flow diagram of this process. In this diagram some
amount of produced 5IP? is recycled' it is good to reuse some components, not to discharge
them. And there are no en*ironmental effects of the byproducts and units used.
In this patent, there is sufficient information about hydration reaction type, which is a down
flow, tric+le bed configuration using ion exchange catalyst in acid form, and dimensions used in
AH
production of water, IPA and 5IP?. In the hydration stage, the percent propylene con*ersion is
preferably maintained about .#2 which is a high number but below #H2 that is stated in the
selected patent. ,he temperature for the hydration reactor is A<!-A#)
1
C , which is reasonable.
Also high production of 5IP? as a byproduct results in an extra unit called re*ersion and so a
larger scale of plant is needed that increases the cost. After re*ersion unit, propylene, IPA and
water are separated and propylene is recycled into the hydration unit.
Dor the separation part, the flow sheet and the description are not clear and well defined. It is
stated that after hydration part a distillation tower, to separate IPA and water from 5IP?, and a
second one to separate water from IPA which is an a&eotropic distillation. >hile in the selected
patent, an a&eotropic distillation is not needed. In addition there exists limited information about
the distillation column in this patent, but in the selected one the reflux ratio, number of plates and
dimensions of the column are gi*en.
Additionally, it can be obser*ed that the data as molar flow rates and compositions at the inlet
and outlet streams of all the units are missing in this patent, while clearly well defined in the
selected one.

All in all, since this patent is lac+ of a lot of necessary information and re%uires more units, it is
not satisfactory to design an efficient plant using it.
-.2.2 Pr#&e 2#r Pr#5$&t!#n #2 A*&#@#*
Patent n#B US 6A=--A3=-
Date #2 %atentB De&. 21A 2,,3
A.
F!"$re -.2 A ;chematic 5iagram of a Catalytic 5istillation Column "a*ing two Catalyst 9eds
for the Catalytic 5istillation Process
,his process is related to production of alcohols *ia catalytic hydration of an olefin to the
corresponding alcohol and dehydration of an a&eotropic mixture including a first alcohol and
water to produce the first alcohol in a substantially anhydrous state. ,here is more than one flow
diagram in this patent, so one of them was chosen as a representati*e.
,his in*ention was formed as an alternati*e to older con*entional ones because of their
complexity and loss of efficiency. 4olar flow rates of all streams are a*ailable generally and
there are a temperature range between #1C K A(1C and a pressure range between 1.H4Pa K
.H4Pa, which are not so high, but suitable for such a process. Purity of products is nearly
A112.
And there are no en*ironmental effects of end-products and units used.
7p to now, there is no problem with this patent, but there are also some disad*antages of it
which can not be ignored during a process design. Dirst, a catalytic distillation column is used in
the flow diagram for both cataly&ing reactions and distillation process. ,his column operates as a
reactor and as a distillation column, so operating conditions of this unit should be chosen
specifically from a narrow range in order to obtain high con*ersion and design of this unit can
A#
not be performed in Chemcad simulation, which is the maBor reason for not choosing it. ;ince a
reactor and a distillation column can not be designed as a single unit in this simulation program,
this in*ention was not chosen. As another disad*antage, although the purity of end-products is
nearly A112 pure, con*ersion of main reactions ta+ing place in catalytic distillation column
changes between H-!H2, which can be accepted as a low con*ersion range.
In *arious flow diagrams of the patent, generally, fixed bed reactor was used as reactor type and
an acidic cation exchange resin catalyst was used as catalyst type. 9ut different feed streams
were used such as propene, isobutene and -methyl--butene in different flow diagrams. ?nd
products are not isopropyl alcohol in all processes. ,his patent is used for description of general
production of alcohols, not for a specific alcohol production such as isopropyl alcohol which will
be the desired product of the plant.
>hen ta+ing these reasons into considerations, this process is not the most rational one. ,hese
disad*antages are enough not to choose this process.
-.2.- Pr#&e 2#r t@e %r#5$&t!#n #2 !#%r#%'* a*&#@#*
Patent n#B US 3A86,A2,-
Date #2 %atentB A$". 1=A 1+=8
A(
F!"$re -.- Dlow ;heet of the ;ump Process of the In*ention
>ith the help of this patent, isopropyl alcohol can be produced by reacting a propene-containing
hydrocarbon stream with water in the presence of a strongly acidic, solid hydration catalyst.
As it can be seen in Digure !.A, !. and !.!, there are many reactors which are interconnected.
,hroughout these reactors, the total con*ersion le*el reaches up to ))2. $n the other hand, the
same con*ersion le*el can be reached with a single reactor in the selected patent.
,he temperature and pressure range during the process is between A1
1
C - 11
1
C and (1bar K
A1 bar respecti*ely. ,he range is close to the selected patent' howe*er there are more data in the
description of the selected patent.
,here is not any information about dimensions of the units. Although there are many data
corresponding to each example, it does not seem enough for the whole design of the
plant.,hrough the reactor &ones, water and olefin flows counter currently instead of parallel
flow. ,he main ad*antages of this fact are that high olefin concentration in the feed is not
necessary, olefin con*ersion is *ery high and selecti*ity of IPA is *ery high.
Drom these facts, one may conclude that, the patent <,#.1,1! is a useful one but it does not
include all of the data set re%uired for a plant design. Durthermore, the writing style of the patent
is *ery hard to understand. It is a handicap to select it.
A)
-.2.3 Pr#&e 2#r %r#5$&!n" !#%r#%'* a*&#@#* 0e*e&te5 %atent 2#r t@! 5e!"n %r#7e&t1
Patent n#B US 4A86-A6+-
Date #2 %atentB C$n. +A 1++=
F!"$re -.3 Dlow 5iagram of an Isopropyl Alcohol Production Process
,his patent relates to production of isopropyl alcohol by direct li%uid phase hydration of
propylene and water. ,he feed enters to a Bac+eted reactor with a strong acid cation exchange
solid catalyst. ,he reaction product discharged from the top of the reactor is sent to the
distillation column where the unreacted propylene is separated and recycled continuously to the
reactor as a feed. ,he li%uid phase drawn out from the upper portion of the reactor is fed to the
extractor where propane is fed to the system as an extractor agent. >hile the li%uid drawn out
from the bottom of the reactor is recycled to the reactor, the extract is drawn out from the top and
sent to the li%uid-li%uid separation column which results in the final desired product, isopropyl
alcohol.
In the process' the data a*ailability is *ery high. ,he dimensions of the reactor, the distillation
column and the extractor are gi*en details including the inner diameters and the heights. ,he
molar flow rates of the feed, inlet and outlet streams and the detailed stream compositions are
well defined. ,he temperature and pressure range of each stream is gi*en, so mass and energy
balances can be calculated. In addition, the features of distillation column such as reflux ratio,
1
plate number and the feed plate are gi*en which ma+es the distillation column easily designed.
,he ;:D ratio of the extraction is also gi*en in the patent.

$ne of the most important characteristic of a process is the purity of the product. In this process
the end product is ()2 by weight isopropyl alcohol, A12 water and about A2 di-isopropyl ether.
,his states that the desired product, isopropyl alcohol, has high purity and the unwanted by-
product di-isopropyl ether is produced at *ery low amounts. ,he high purity of the product
which is approximately )12 is highly acceptable. ,he high selecti*ity of isopropyl alcohol
which is approximately ))2, also ma+es this process ad*antageous. ,his can only be achie*ed
by controlling by-production of isopropyl ether during the reaction with the re%uirement of at
least ten times in moles as much water as that of the raw material propylene to be supplied into
an inlet of the reactor.
,he process of li%uid phase direct hydration of propylene using a solid catalyst results in a high
con*ersion rate of the reactor as #H2, if the reaction conditions are selected ade%uately. ,he
formation of the isopropyl alcohol is more fa*orable at low temperatures and high pressures. ,he
operation temperature and pressure gi*en in the patent are approximately AH1
o
C and (1 atm
respecti*ely. ,he temperature is stated according to the thermal resistance of the selected
catalyst. A %uite high pressure is re%uired to dissol*e raw material propylene into the li%uid
phase. ,herefore, the gi*en temperature and the pressure is preferable.
,he flow sheet, including the units and the streams is clear and well defined. =ow complexity of
the flow sheet ma+es this process fa*orable.
-.- Gra5!n" #2 t@e %r#&ee
A
Ta)*e -.1 ?*aluation of each process described in pre*ious section
COMPARED
PROPERTIES
Se&t!#n -.2.1
Patent n#B
US 3A-42A+34
Se&t!#n -.2.2
Patent n#B
US 6A=--A3=-
Se&t!#n -.2.-
Patent n#B
US 3A86,A2,-
Se&t!#n -.2.3
Patent n#B
US 4A86-A6+-
Ra; (ater!a*
propylene,
water
not clarified
propene,
water,
hydrocarbon
mixture
propylene,
propane,
water
En5 %r#5$&t
isopropyl
alcohol
different types
of alcohol
isopropyl
alcohol
isopropyl
alcohol
C#nver!#n D .#2 H-!H2 )(2 #H2
Rea&t#r T'%e tric+le bed fixed bed
sump or
tric+le Dixed bed
Cata*'t t'%e
Acidic ion
exchange
resin
acidic cation
exchange
resin
sulfanic acid
cation
exchange
acidic cation
exchange
resin
P$r!t' #2
%r#5$&t
not clarified ))2 ))2
()2
Env!r#n(enta*
E22e&t
no ha&ardous
effects
no ha&ardous
effects
no ha&ardous
effects
no ha&ardous
effects
O%erat!n"
C#n5!t!#n
a*ailable a*ailable a*ailable a*ailable
Data
Ava!*a)!*!t'D
moderate moderate low high
Ener"'
C#n$(%t!#n
not clarified not clarified not clarified low
C#(%*e/!t' #2
t@e %r#&e
moderate low complex low
E&#n#(!&
a%e&tD
expensi*e
no sufficient
data
expensi*e cost effecti*e
RESULT POOR VERY POOR
MODERAT
E
GOOD
Ta)*e -.2 Cualitati*e e*aluation of each process

COMPARED
PROPERTIES
Se&t!#n -.2.1
Patent n#B
US 3A-42A+34
Se&t!#n -.2.2
Patent n#B
US 6A=--A3=-
Se&t!#n -.2.-
Patent n#B
US 3A86,A2,-
Se&t!#n -.2.3
Patent n#B
US 4A86-A6+-
Ra; (ater!a*
M - M M
En5 %r#5$&t M - M M
C#nver!#n M - M M
Rea&t#r T'%e M M M M
Cata*'t t'%e M M M M
P$r!t' #2
%r#5$&t
- M M M
Env!r#n(enta*
E22e&t
M M M M
O%erat!n"
C#n5!t!#n
M M M M
Data
Ava!*a)!*!t'
- - - M
Ener"'
C#n$(%t!#n
- - - M
C#(%*e/!t' #2
t@e %r#&e
- M - M
E&#n#(!&
a%e&t
- - - M
Ta)*e -.- Cuantitati*e e*aluation of each process
!
COMPARED
PROPERTIES
Se&t!#n -.2.1
Patent n#B
US 3A-42A+34
Se&t!#n -.2.2
Patent n#B
US 6A=--A3=-
Se&t!#n -.2.-
Patent n#B
US 3A86,A2,-
Se&t!#n -.2.3
Patent n#B
US 4A86-A6+-
Ra; (ater!a*
031 A1 ) A1 A1
En5 %r#5$&t
01,1 A1 # A1 A1
C#nver!#n
0=1 ) ! A1 )
Rea&t#r T'%e
041 A1 A1 A1 A1
Cata*'t t'%e
061 A1 A1 A1 A1
P$r!t' #2
%r#5$&t
081 H A1 A1 A1
Env!r#n(enta*
E22e&t
061 A1 A1 A1 A1
O%erat!n"
C#n5!t!#n
061 A1 A1 A1 A1
Data
Ava!*a)!*!t'
01,1 H H ! A1
Ener"'
C#n$(%t!#n
061 H H H (
C#(%*e/!t' #2
t@e %r#&e
0+1 H # ! (
E&#n#(!&
a%e&t
0=1 ! ! ! #
Total 626 537 571 728
-.3 De&r!%t!#n #2 t@e Pr#&e
<
101
107
108 109
110
114
115
116
118
119
117
121
K101
E101
E102
M101
M102
R101
V101
V102
E103
K103
M103
K104
V103
E104
V104
123
124
125
103
112
113
102
104
P101
120
122
K102
111
106
105
A101
F!"$re -.4 Dlow diagram of the selected process
-.3.1 Genera* De&r!%t!#n #2 t@e Pr#&e
,he aim of the process is to con*ert the mixture of propylene and water to isopropyl alcohol.
Digure !.# presents the flow sheet of this process. A1A is a propylene-propane mixture feed pipe
and A1 is water feed pipe. GA1A, GA1, GA1! and GA1< are compressors used to compress feed
streams before the reaction ta+es place. Additionally a pump and a *al*e are used to transport
li%uids. ?A1A, ?A1! and ?A1< are coolers and ?A1 is a heater. 4A1A, 4A1 and 4A1! are
mixers used in the process where mixing is re%uired. ;treams AA<-A1) are recycled propylene
circulation pipes. ;tream AA is recycled water circulation pipe. GA1 is the expander used in the
flow sheet. 3A1A is the reactor within reaction of isopropyl alcohol production ta+es place. 6A1A
is a component separator and it is used to separate output streams of the reactor. In
stoichiometric reactor model of Chemcad there is only one exit stream, so one stream is di*ided
into two different ones by using this unit. 6A1 is a distillation unit. 6A1! is an extraction
column with an extraction agent feed, namely stream AA#. 6A1< is a simple gas-li%uid
component separator.
-.3.2 Deta!*e5 De&r!%t!#n #2 t@e Pr#&e an5 Un!t
H
Deed A1A ha*ing a composition of ).2 propylene and <2 propane at a molar flow rate (H(H<
mol:h enters to the system at )(G and Aatm. Deed A1 as water enters to the system at a flow
rate )A<H! mol:h under the same conditions. 9oth feeds are compressed from A atm to (1 atm in
a compressor and a pump GA1A and PA1A, respecti*ely. ,hey operate with an efficiency of 1.(,
which is an ideal *alue for centrifugal compressors. ;tream A1! enters to cooler ?A1A at .A<G
and (1 atm and lea*es the cooler at <!G and (1 atm. ;tream A1< enters ?A1 at )(G and
(1atm and lea*es it at <!G and (1 atm, too. In 4A1A, both feed streams A1. and A1#, recycled
water stream AA - with a composition of A!#<#!mol:h water and AHH1Hmol:h propane - from
extraction column and recycled propylene stream A1) K with a composition of AAH#mol:h
propane and#<)(mol:h propylene - are mixed before they are sent through the reactor 3A1A.
?ntering pressures of these streams are set to (1 atm which is the re%uired pressure for the
reaction.
;tream AA1 enters reactor 3A1A with a composition of A<.!)Hmol:h water, 11AAmol:h
propane and A1)))!mol:h propylene at <1.G and (1 atm. 3A1A is a pac+ed bed reactor with a
catalyst type ha*ing a strong acid cation exchange resin in its tubes. ,he reaction which is ta+en
place in the reactor is named as direct hydration of propylene and its simple reaction mechanism
is shown belowO
propylene water isopropanol +
! . !
1 ( ) C H H CH OH OH +
;ince dissol*ing raw material propylene into the li%uid phase where hydration reaction is carried
out re%uires high pressure and low temperature, reaction pressure of 3A1A is +ept at (1atm and
approximately <1!G during the reaction. $*erall reaction is ta+en place with a con*ersion of
#H2. 3A1A operates adiabatically. ?xit stream AAA consists of both li%uid and gaseous phases in
it because of selection of stoichiometric reactor, and then they are di*ided into two streamsO AA
as gaseous phase and AAH as li%uid phase with the desired product. ;tream AAA enters separator
6A1A at <!1G and (1 atm with a composition of A!(A<!Amol:h water, 11mol:h propane,
(<)Hmol:h isopropanol and #<)(mol:h propylene.
7ncon*erted propylene and a little amount of propane are separated with stream AA with a
composition of #<)(mol:h propylene and #1HHmol:h propane at <(G and (1atm, it is sent to
distillation column 6A1. 9efore being sent to 6A1 its pressure is lowered from (1atm to !1atm
which is re%uired pressure for distillation by using *al*e AA1A. In 6A1 unreacted propylene is
.
collected by means of distillation and recycled to the reactor 3A1A as stream AA< at <!G and
!1atm. ;tream AA< has a composition of #<)(mol:h propylene and AAH#mol:h propane. It has a
composition which has a similar ratio to the feed stream ().2 propylene and <2 propane). It is
again compressed from !1atm to (1atm by using compressor GA1! before being mixed with feed
streams and the other recycled stream. ;tream AA< lea*es the compressor GA1! as stream A1) at
HA.G and (1atm with the same composition of stream AA<.
;tream AAH as the li%uid phase product of 3A1A is the reacted phase of the reaction and has a
composition of A!(A<!mol:h water, A).#mol:h propane and (<)Hmol:h isopropanol at <(G
and (1atm. 9efore it is sent to the extraction column 6A1!, it is cooled in the cooler ?A1! from
<(G to !!G and lea*es ?A1! as stream AA.. Actual desired temperature for the extraction is
<1!G, but it is satisfied after mixing with the extraction agent stream in 4A1!.
;tream AA# is propane feed as the extraction agent at a molar flow rate of #)H.<<mol:h at )(G
and Aatm, and it is compressed from Aatm to (1atm in compressor GA1< in order to be reached
optimum pressure for the extraction. ,hen, stream AA. as the li%uid phase of the reacted mixture
and stream AA( as the extraction agent are mixed in 4A1! before being fed to the extraction
column. Actually, these streams enter the column separately, their entrance points are different,
but in stoichiometric units there is only one entrance for these type separators, so they are fed to
the column together in Chemcad simulation. ;tream AA) is the mixture of them and at <1!G and
(1atm. ,he lower the extraction temperature is, the more selecti*ely the alcohol can be extracted.
Pressure has also great influence on extracted amount and extraction selecti*ity. "igh pressures
are preferable for more efficient extractions. ,he extraction column 6A1! is a counter-current
multistage contact type extractor. =i%uid-li%uid extraction is carried out. In 6A1!, isopropanol is
exracted by using propane from the li%uid phase mixture or raffinate at <1!G and (1atm.
,he maBor amount of the raffinate mainly consisting of water is recycled from the bottom of
6A1! to the reactor3A1A along stream AA with a composition of A!#<#!mol:h water and
AHH1Hmol:h propane at <1!G and (1atm. ;tream A1 is the extracted phase' it contains propane
as the extraction agent, isopropyl alcohol as the desired product and a little amount of water with
molar flow rates of #)!A1.mol:h, (<)Hmol:h and ()H(mol:h, respecti*ely. Pressure of stream
A1 is reduced in AA1A from (1atm to !1 atm in order to separate a%ueous isopropyl alcohol
solution from the extracted phase. Low, stream A has a pressure of !1 atm which is suitable for
separation of product and extraction agent. It is cooled to !H!G from <1!G by using cooler ?A1<.
After stream A! lea*es the cooler, it is ready for separation and sent to the gas-li%uid separator
#
6A1<. ;ince the conditions for separation of propane from isopropyl alcohol a%ueous solution is
satisfied by reducing its temperature and pressure, in 6A1< they are separated from each other.
;tream A< contains propane as the only component with a molar flow rate of #)!A1.mol:h.
Dinally, stream AH contains isopropyl alcohol as the final desired product with a composition of
)12 isopropyl alcohol and A12 water at !H!G and !1atm. (,heir molar flow rates are
(<)Hmol:h and ()H(mol:h, respecti*ely.)
;tream A< as collected extraction agent is not recycled to the extraction column, because it is
needed to be re-compressed to the extraction pressure. In this process the solution is separated
from the extracted phase li%uefied by cooling, the pressure is still high. It is more ad*antageous
than recycling of extraction agent in terms of power re%uired.
3. CALCULATIONS
(
3.1 A$(%t!#n
Compressors, expanders and pump used in the process operate with an efficiency of 1.(.
,he reactor where direct hydration reaction ta+es place operates adiabatically.
,he reactor type is chosen as pac+ed bed reactor.
;ide reaction is ignored which results in a little amount of diisopropyl ether (5IP?) as
A2 of the final product.
,he main reaction ta+es place with a con*ersion of 1.#H in the reactor.
Composition of final product is ta+en as )12 IPA and A12 >ater instead of ()2 IPA,
2A1 >ater and 2A 5IP?.-/
3.2 Ener"' Ea*an&e ar#$n5 t@e @eat e/&@an"er
Dirst of all composition, pressure, temperature, and mole numbers of the inlet and outlet streams
of the heat exchangers should be made.
Drom the thermodynamic point of *iew, enthalpy can be calculated li+e that
-!/ (<.A)
;ince the process is at constant pressure
-!/ (<.)
Dor mechanically re*ersible, constant pressure, closed-system processes and for the transfer of
heat in steady-flow exchangers where T?
G
and T?
P
are negligible and >P1, ,hen
-!/ (<.!)
Dor ideal gas mixtures
)
-!/ (<.<)
;o then, A, 9, C, 5 constants for the mixture are found in order to use in e%uation shown below.
A for the mixture is obtained from the multiplication of the A *alues of each component with the
molar ratio. ,hen A, 9, C, 5 *alues are inserted to the e%uation below.
(<.H)
3.- Ener"' F C#(%#nent Ea*an&e ar#$n5 t@e C#(%#nent Se%arat#r
3.-.1 C#(%#nent Ea*an&e ar#$n5 t@e C#(%#nent Se%arat#r
;ince there is no reaction in the separator, mole numbers of the components in the inlet stream
and at the exit are conser*ed. ;o instead of mass balance, component balance is enough. Dor the
component balance the e%uation below is usedO
(<..)
3.-.2 Ener"' Ea*an&e ar#$n5 t@e C#(%#nent Se%arat#r
C
p
*alues of each component at the inlet and outlet streams at gi*en temperatures are found
according to the e%uation belowO
-!/ (<.#)
,hen the C
p
*alue of the mixtures at inlet and outlet streams is found according to the e%uation
belowO
-!/ (<.()
After that, for finding the enthalpy of the inlet and outlet streams, total number of moles, C
p
of
the mixture and temperature of the mixture multiplied and enthalpies of the streams are found.
!1
"PnUC
p
U, (<.))
Low, the e%uation below is used for the calculation of the enthalpy difference between the
streams.
T"P "
inlet
- "
outlet A
-"
outlet
(<.A1)
3.3 Ener"' Ea*an&e ar#$n5 C#(%re#r
3.3.1 P#;er Ca*&$*at!#n
Compressor is an adiabatic compressor with an efficiency of 1.(.
C
p
calculation of the inlet stream is done according to the e%uation belowO
-!/ (<.AA)
"eat capacity ratio becomes
-</ (<.A)
If VP1.(, for an adiabatic compression
-</ (<.A!)
Power is calculated by the rele*ant e%uationO
U> -</ (<.A<)
3.3.2 Te(%erat$re Ca*&$*at!#n at t@e &#(%re#r #$t*et
Around the compressor, the enthalpy difference is e%ual to the wor+ done on the system.
(<.AH)
!A
(<.A.)
>here (<.A#)
9y inserting e%uation <.. into e%uation <.H and ma+ing iterations, the outlet temperature can be
found.
3.4 Ener"' Ea*an&e ar#$n5 t@e M!/er
3.4.1 Te(%erat$re &a*&$*at!#n at t@e (!/er #$t*et
Dor the ideal case enthalpy difference around the mixer is e%ual to 1.

(<.A()
A, 9, C, 5 *alues for e%uation abo*e are found from the multiplication of A, 9, C, 5 *alues of
each component with corresponding molar ratios. 4olar ratios for the inlet and outlet streams are
multiplied by (-) and (M), respecti*ely.
After inserting A, 9, C, 5, and 3 *alues in the e%uation abo*e, outlet temperature can be found
by trial and error.
3.6 Ener"' an5 C#(%#nent Ea*an&e ar#$n5 t@e Rea&t#r
3.6.1 C#(%#nent Ea*an&e ar#$n5 t@e Rea&t#r
$ne reaction occurs in the reactor with a con*ersion of 1.#H which is gi*en below. -AH/
C
!
"
.
M "

$ C
!
"
#
$"

!
,he sum of the feed rate to reactor and the change within reactor should be e%ual to the effluent
rate from reactor which can be expressed as the e%uation belowO
Ta)*e 3.1 Component balance around reactor
Fee5 rate t# rea&t#r C@an"e ;!t@!n Rea&t#r E22*$ent Rate 2r#( Rea&t#r
S%e&!e 0(#*?@1 0(#*?@1 0(#*?@1
C
-
H
6
D
1 " C
. !
(-)D
1 " C
. !
(1.#H) D
1 " C
. !
(A-1.#H)
H
2
O D
$1 "

(-)D
1 " C
. !
(1.#H) D
$1 "

- D
1 " C
. !
(1.#H)
C
-
H
8
OH 1 (M)D
1 " C
. !
(1.#H) D
1 " C
. !
(AM1.#H)
3.6.2 Ener"' Ea*an&e ar#$n5 t@e Rea&t#r
Dor adiabatic operation
1
1
- ( )/
i
i
Rxn R i P P R
i P P
X H T C T X C T
T
C X C

+ +
=
+
-H/ (<.A))
Dor the reactions occurring in the reactor, enthalpy at reference temperature ()( G) is
calculated. T" of reaction at )( G are calculated.
1 1 1
1 1 1
i i i
i
A A A
F C y
F C y
= = =
-H/ (<.1)
*alues for all components are found by di*iding their flow rates to limiting reactant.
b c d
A C
a a a
+ +
Dor the reaction abo*e, o*erall change in the heat capacity per mole of A reacted can be found
asO
!!
D C A
p P P P P
d c b
C C C C C
a a a
= + (<.AA)
1
i
i P
C T
,
P
X C T
r ,
i
i P
C
*alues are found and substituted into e%uation <.A) and , is found.
4. DISCUSSION
4.1 Pr#&e Se*e&t!#n
5irect hydration of propylene is chosen as the process in this proBect. 3easons of this choice are
impro*ement of its products %uality more than other two processes, its lower capital spending (it
means less acid resistant e%uipment is needed) and its en*ironmental sensiti*ity. >hereas direct
hydration has such ad*antages which are important when considering en*ironmental and
economic aspects' indirect hydration has some disad*antages. It is a corrosi*e process. ;ince
sulfuric acid is used, it is needed to reconcentrate the acid which demands high energy. A%ueous
waste treatment is another high energy demanding operation. All of these ma+e indirect
hydration more expensi*e and explain why it is not chosen. As a third process, production of
IPA from acetone is ta+en into account. 9ut this process method is not widely used and no
sufficient data was found about it. 9esides, IPA is used in production of acetone instead of usage
of acetone for production of IPA in most cases. As a result, it is decided that direct hydration of
propylene is the most suitable process in order to produce IPA among them.
4.2 Patent Se*e&t!#n F Gra5!n"
Dour different processes are e*aluated for the production of IPA. ,hese are diisopropyl ether
re*ersion in isopropanol production, process for production of alcohols, process for the
production of isopropyl alcohol and finally - the chosen one K process for producing isopropyl
alcohol. ,here are se*eral criteria which are determined by group members and important in
selection of a process. ,hese are con*ersion, data a*ailability, economic aspects as the most
important ones' and complexity of the process, raw materials, end products, reactor and catalyst
types, purity of products, en*ironmental effects, operating conditions and energy consumption.
!<
,hree different e*aluation methods are made. Dirst general characteristics of each process were
gi*en according to these criteria, and then they were e*aluated whether they affect the process
positi*ely or not. Dinally each criterion was ran+ed according to their importance' by multiplying
them their grade o*er A1, final total grades of them were found. In each e*aluation the selected
patent became the most suitable one. According to the results, the selected patent has higher data
a*ailability and is cost effecti*e. Its con*ersion is also high enough. =ow energy consumption in
this process has a positi*e influence on both its economy and en*ironmental effects. It is
important to ha*e a non-complex flow sheet. ,he selected one satisfies users with a lower
complex process when comparing with others. 9asing on these reasons, it can be easily
concluded that process for producing isopropyl alcohol is the most appropriate patent among
them.
4.- Pr#5$&t!#n Ca%a&!t'
,he design capacity is based on the data that is ta+en from 5I?, ,ur+ish Institute of ;tatistics,
7nited Lations 5ata and ,3 Prime 4inistry ;tate Planning $rgani&ation. IPA is not produced in
,ur+ey, so the consumption of this chemical is the difference between the imports and exports.
9ecause of the inconsistent data within the years from A))A to 11( as can be obser*ed in Digure
.!, it is approximated using both ! and H-year mo*ing a*erage in order to obtain a better fit.
>hen the ! year mo*ing a*erage data points, Digure .<, are compared with the H year mo*ing
ones, Digure .H, the points of latter figure seem more consistent with each other. "owe*er that
results in unsatisfactory data points to fit a model. ,hus, the ! year mo*ing a*erage data are
more suitable in order to estimate production capacity.
Polynomial, exponential, logarithmic and linear models are fit to the points and the models are
proBected to the future. ,he 3

*alues for polynomial, exponential, logarithmic and linear models

are found as 1.)(1, 1.((), 1.)H1 and 1.)H1 respecti*ely which are *ery close to each other.
,hen the IPA consumption cur*es in de*eloped countries such as Austria, Drance, Jermany,
Jreece, Italy, ;pain, ;wit&erland and ?ngland which ha*e similar economic structure to ,ur+ey
are found with rele*ant calculation steps which are mentioned in capacity calculation part in
detail. In these calculation steps, after ta+ing the J5P, population differences between the
countries into consideration, lastly the purchasing power parity *alues are multiplied since there
is an ob*ious difference between de*eloping and de*eloped countries.
!H
After repeating all steps for ( countries, final consumption data for ,ur+ey are plotted in Digure
.(. It is well +nown that the countries Jreece, ;pain, Italy and Austria ha*e the most similar
economies with ,ur+ey. >hen the Digure .) is ta+en into consideration, it is obser*ed that these
countries0 data are mostly around the logarithmic model. ,he reason of not choosing the
exponential model is mostly based on the results of mar+et research. As it is stated in that part,
reducing demand of IPA resulted in closing some plants that produce IPA in the last few years.
9y that fact, it has not seem realistic to select an exponential fit for a de*eloping country0s,
,ur+ey0s, consumption till 1H."ence, it can be concluded that logarithmic model fits best as a
consumption proBection of IPA in ,ur+ey. Drom this point of *iew, the capacity for the IPA
production process in 1H was determined as <!,111 tons:year.
4.3 A$(%t!#n an5 Un!t Ca*&$*at!#n
,he compressors used in the flow sheet are centrifugal adiabatic compressors' according to the
flow rates this one is the most desired one to achie*e the re%uired pressure increase. $n the other
hand, expenders are also centrifugal and adiabatic due to the same reasons. ,here is one,
adiabatically wor+ing centrifugal pump in order to increase the pressure of the li%uid. ,he
efficiencies of all these units are ta+en as 1.( because the centrifugal types ha*e efficiency
between 1.#H-1.)1. 1.( efficiency is an acceptable and feasible assumption. Dor all of these three
units, the energy and mass balance calculations are almost the same. ;o the compressor is ta+en
as sample and all of the calculations are made according to it. 9oth theoretical wor+s was
calculated by using the efficiency ratio 1.(. ;ince, the wor+ done by the compressor is e%ual to
the total enthalpy change' by using this enthalpy change final exit temperature *alues of
compressors were calculated by iterating a specified temperature *alue.
"eat exchangers are assumed to wor+ re*ersibly and at constant pressure. 5ue to the constant
pressure assumption, heat transferred within the exchanger is related to the enthalpy difference at
the inlet and outlet streams. ,here is no wor+ applied to the system, so beside +inetic and
potential energy, wor+, which normally should be ta+en into consideration for the calculation of
enthalpy, can be ignored.
4ixers used within the process are at constant pressures. ,here is also no heat applied to the
mixer because of the adiabatic conditions. 7nder these assumptions, the enthalpy difference
between inlet and exit is &ero. ,hen for finding temperature, iterati*e calculation is made.
!.
In the selected patent, the reactor types which are used in the examples are pac+ed bed reactors.
;o it is also chosen as pac+ed bed reactor for the process. ,he reaction process is carried out
adiabatically, because a good isolation is maintained around the reactor, the assumption seems
reasonable. $n the other hand, there is a side reaction beside the main reaction in the reactor.
,he by product is diisopropyl ether (5IP?). "owe*er, the molar percentage of the by product is
*ery low at the exit (A 2 of the final product). ,hus the side reaction is ignored and the
calculations are based on only the main reaction. 9ecause of the ignored side reaction, the exit
composition is ta+en as )1 2 IPA and A1 2 water instead of ()2 IPA, A12 water and A2 5IP?.
,he con*ersion is stated as #H 2 or higher in the reactor. ,hus, the assumption based on the #H
2 con*ersion in the reactor which is feasible.
4.4 C@e(&a5 !($*at!#n
At the beginning of the process additional compressors and heaters are used in order to reach
re%uired pressure and temperature for direct hydration reaction. 3eactor 3A1A is determined as
pac+ed bed, because in the patent it is told that pac+ed bed reactors are used generally for this
process. Catalyst type is determined according to gi*en information on the patent. ;ome little
changes in the amount of entering water and propane streams are made in order to satisfy
material balances for the whole process. Actually there is a side reaction which ta+es place with
hydration reaction simultaneously. Its final product is diisopropyl ether (5IP?), but its selecti*ity
is too low. 9y setting pressure of 3A1A to (1atm and temperature to <1.G, the selecti*ity of the
desired reaction is increased. ;electi*ity of hydration reaction is about A112 which is stated in
the patent, so 5IP? composition in streams is ignored because of its trace amount.
After 3A1A, a separator is used, since in stoichiometric reactor there is only one exit stream. In
actual process there are two streams exiting from the reactor as gaseous and li%uid phases. ;o,
3A1A and 6A1A can be thought as a single unit.
In extraction column, same procedure is followed. ;ince component separator is used instead of
actual extraction column, an extra mixer is added to the system in order to mix propane and
a%ueous reacted mixture and sent to the extraction column. In this unit, high pressure and low
temperature is re%uired in order to extract approximately the whole amount of IPA from raffinate
phase by using propane.
!#
6. CONCLUSIONS
,he concept of this proBect was the capacity determination and process selection for the
isopropyl alcohol production plant which is to be established in ,ur+ey. Conclusi*ely, the design
capacity of the chemical plant for 1H is determined as <!,111 tons:year according to statistical
data ta+en from 5I?, ,ur+ish Institute of ;tatistics, 7nited Lations 5ata and ,3 Prime 4inistry
;tate Planning $rgani&ation. ,he isopropyl alcohol consumption of ?urope and ,ur+ey were
in*estigated and rele*ant calculations are done in order to predict the future capacity of the plant
which is expected to operate AH years.
,he other obBecti*e of the proBect was to select the most appropriate process for IPA production.
Among three types of IPA production process, direct li%uid phase hydration process is selected
because of the high con*ersion of the reactor, high selecti*ity, and high purity of the product and
less complexity of the flow sheet. >ith the assistance of the selected 7nited ;tates Patent,
E"irata et al, Process for Producing Isopropyl Alcohol, A))(F, the plant is constructed in
ChemCA5 program with a design capacity of <!,111 tons:year. As a result, (H(H<mol:h of
propylene W propane mixture with a composition of ).2 propylene and <2 propane is fed into
the system in order to obtain )A<H!mol:h or <!,111 tons per year desired product is obtained
with a composition of )12 IPA and A12 water.
!(
NOMENCLATURE
A "eat capacity constant
9 "eat capacity constant
C "eat capacity constant
p
C
"eat capacity, @:+mol.G
5 "eat capacity constant
1 A
F
Initial molar flow rate of component A, mol:h
A
F
4olar flow rate of component A, mol:h
J5P Jross domestic product, S
H ?nthalpy, @:mol
L ,ime difference of a country from reference country, years
n 4ole number
P Pressure, Pa
p Power , @:s
PPP Power purchasing parity
C "eat, @:mol
3 Jas constant, @:mol.G
, ,emperature, G
r
T
3eference temperature, G

> >or+, @:s
X Con*ersion
x 4ass fraction
y 4ole fraction
!)
p
C
"eat capacity change, @:+mol.G
T?
G
Ginetic energy change, @:mol
T?
P
Potential energy change, @:mol
H ?nthalpy change, @:mol
R Annual growth rate
4ass flow rate, g:h
Y 3atio of heat capacities

3atio of molar flow rates

REFERENCES
G1H "ortaZsu,F[ner Gimya ;anayinde ?+onomi+ 5e\erlendirmelerF
G2HEProcess for producing isopropyl alcoholF , @un. ), A))(, Patent noO 7; H,#.!,.)!
G-H;mith.@.4., 6an Less.".C., Abbott 4.4., !ntroduction to C#emical $n%ineerin%
T#ermodynamics& #th edition, 4cJraw-"ill, 11H
G3HJean+oplis.C.@'& Transport Processes and (eparation Process Principles& <th edition,
Prentice "all, 11#
G4H". ;cott Dogler , $lements o) C#emical Reaction $n%ineerin% , <th edition , Pearson
?ducation International , 11.
On*!ne Re2eren&e
G6H httpO::chemicallandA.com:petrochemical:I;$P3$PAL$=.htm
G8H httpO::www.scienceray.com:Chemistry:Isopropanol..A!A!
G=H httpO::telecheminternational.com:IPA]3eagent]AC;.P5D
G+H httpO::www.allnaturalcosmetics.com:articles.php^article]idPA
G1,HhttpO::goliath.ecnext.com:coms:gi]1A))-A)!A(11:Imported-isopropyl-alcohol-occupying
half.html
G11H httpO::www.icis.com:*:chemicals:)1#.1A:isopropanol:process.html
G12H httpO::chemicallandA.com:petrochemical:I;$P3$PAL$=.htm
G1-H httpO::www.sriconsulting.com:C?":Public:3eports:..(..111:isopropyl21alcohol.gif
G13H httpO::en.wi+ipedia.org:wi+i:Isopropyl]alcohol
G14H httpO::www.dow.com:productsafety:finder:iso.htm
<1
G16H httpO::data.un.org:
G18H httpO::e+utup.dpt.go*.tr:ueg:11(:ueg11(.pdf
G1=H httpO::www.amberlyst.com:olefin.htm
G1+HhttpO::epp.eurostat.ec.europa.eu:portal:page^
]pageidPA1)1,!11#1.(,A1)1]!!1#.H#.W]dadPportalW]schemaPP$3,A=
G2,H httpO::indexmundi.com:united]+ingdom:population.html
APPENDICES
APPENDII A J Ta)*e #2 %r#5$&t!#n &a%a&!t' &a*&$*at!#n
Ta)*e A.1 ,ur+ey Import-?xport 5ata for IPA -A./
2+1,-, I(%#rt E/%#rt
Year
A(#$nt
0k"1
Va*$e
0USD1
A(#$nt
0k"1
Va*$e
0USD1
11( 1(!!<H! (A##A(1 !### .1.H<
11# AH))1)< .)#(!1 #!H1 <#.H(H
11. 1!H<1## A)#.A!1A )#(1( <H))!
11< H11!!< A(A#.1H1 A#1(< A(!#(!
11! 1(!H<A A(H(.11 !H !1)!1
11 A((!).H< ).!.1AH A!<A< )H
111 A)<#1!! ()<!(<A A)1!A AA)!##
A))) A<.#!A1( #<1A< H<A11 !.!(H
A))( A<1H((!# (H(H)<) H.A)A HA!!)
A)). AA(.#H!< #A#(<. H<. (!<
A))H AA!))1( )HAA(# A1(!. A<).
A))< (#H<#( <HHA.A .A1H .()1
A)) .!11H<# !1!1!) !1A1 !)<<
A))A <)!.A. !11!1 ..!1 #(1
A))1 H!<!AH !.!)1 !()H <!A
<A
Ta)*e A.2 Annual growth rate of ,ur+ey in different years -A./
Year
Ann$a* Gr#;t@
Rate #2 T$rke'
11. ..A
11H #.<
11< (.)
11! H.(
11 #.)
11A -#.H
111 #.<
A))) -<.#
A))( !.A
A))# #.H
A)). #
A))H #.
A))< -H.H
A))! (
A)) .
A))A 1.)
A))1 ).!
A)() 1.!
A)(( .A
A)(# ).H
A)(. #
A)(H <.
A)(< ..#
A)(! H
A)( !..
A)(A <.)
A)(1 -.H
A)#) -1..
A)#( A.H
A)## !.<
A)#. A1.H
A)#H #.
<
Nears J5P
Ta)*e A.- Jross 5omestic Product of ?uropean Countries in each year -A./
A$tr!a Fran&e Gree&e Ger(an' S%a!n Ita*' S;!t<er*an5 UK T$rke'
2,,6 !H,H.1 !!,<1( H,1#. !A,#<< (,HH< !1,.H< !#,)A) !<,)(! ),1#!
2,,4 !!,H!# !A,)1( !,!## ),)(1 .,#) ),1) !H,()! !!,A!H (,<1(
2,,3 !,1( !1,#() A,)#. (,(1( H,H. (,H#< !<,<A !A,#). #,.))
2,,- !1,(HA ),H11 1,H( #,.A <,HH. #,(! !!,1(1 !1,A#A .,)!1
2,,2 ),)<! (,(.# A),.) #,A! !,#H. #,<#A !,#H (,)#) .,H1
2,,1 ),)< (,#H A(,!1A .,.)# !,1.) .,))1 !,!!< #,() .,1!A
2,,, (,<(A #,<< A#,1H# H,#() ,11! H,)1H !A,<<. .,<#. .,<#A
1+++ #,111 H,#HA A.,1( <,<)1 1,.#! <,<(# ),((# H,!!H H,)))
1++= H,(! <,.( AH,!<H !,.## A),HHH !,.(# ),1 <,)H .,!A<
1++8 <,.). !,..) A<,#. ,)<< A(,H#H !,A1A (,A(! !,!< .,A..
1++6 !,(#1 ,(<# A<,1)( ,A1 A#,.!# ,!A! #,HH ,(! H,#<
1++4 ,(.A ,HA A!,.A A,.H A.,)!) A,#<# .,#! A,!. H,!.!
1++3 ,1HA A,<1< A!,A.H 1,(H( A.,A)! 1,## .,#< 1,!HA <,))<
1++- A,1!. 1,.A! A,#<. A),)(# AH,H!A A),(#H H,... A),A( H,#A
1++2 1,((A 1,<HH A,##) A),(. AH,!(( A),.AH H,!## A(,)( <,(.1
1++1 A),()( A),#!. A,H!( A),A1 A<,)H A),1!) H,1#! A#,((. <,H.)
1++, A(,##1 A(,)A! AA,(.H A#,.)1 A<,A. A(,A!A <,#<) A#,H#. <,<.A
1+=+ A#,<H. A#,(< AA,H1! A.,<) A!,A# A#,AA) !,A(1 A.,(H( <,1A
1+== A.,! A.,.(H A1,#!! AH,A( A,1() AH,).H A,.A< AH,)HH !,)<)
1+=8 AH,). AH,<(. ),)(. A<,1. AA,A<H A<,(A 1,!1( A<,#!< !,(A
1+=6 A<,.#H A<,#)A ),)(1 A!,.<! A1,!11 A!,)#( A),.<A A!,#H !,<#1
1+=4 A<,1.< A<,A( ),#<A A!,1!. ),#(. A!,)< A(,)() A,)#) !,<H
1+=3 A!,!A1 A!,H< ),HH A,!H! ),!A A,HH1 A#,(#H A,A)) !,1)H
1+=- A,(!A A,()) (,#(( AA,H!( (,(H! AA,#A A.,#.. AA,<(( ,(.H
1+=2 AA,)<A A,A)) (,H)H A1,()) (,<1# AA,A<) A.,AA! A1,.(H ,.)
1+=1 AA,1H! AA,<A (,<. A1,!<< #,(.) A1,<#! AH,<( ),(## ,HA
1+=, A1,A!. A1,A(H #,#H ),<H) #,#A ),H1H A!,)(< ),A.< ,<
1+8+ ),A! ),A( #,A1H (,H(H .,H#1 (,<< A,A)< (,H) ,AHH
1+8= #,))A (,H# .,<!A #,.A .,AA( #,!#( AA,11) #,#!! ,1<<
1+88 #,<#A #,<)# H,.#H .,()( H,.)( .,#1A A1,.A .,))< A,)1
1+86 .,#1) .,(.1 H,.H .,(! H,# .,A#1 ),!)A .,<A. A,#(
1+84 .,1.! .,<( <,#A H,.! <,((< H,<#! (,)< H,)1( A,HH)
<!
Ta)*e A.3 IPA Production data of ?uropean Countries in each year -A)/
A$tr!a Fran&e Gree&e Ger(an' S%a!n Ita*' S;!t<er*an5 UK T$rke'
2,,=
2,,8 ))). (!< (
2,,6 ))## .A! .!<
2,,4 A<(.
2,,3 (H<
2,,- A1) ((AH<
2,,2 A#(H A1A(#<
2,,1 A(H)
2,,, H!)
1+++
1++=
1++8 A.(1(1
1++6 A.#1<
1++4 <A.(. A#A#).
Ta)*e A.4 IPA Import-?xport data of ?uropean Countries in each year -A./
A$tr!a Fran&e Gree&e Ger(an' S%a!n Ita*' S;!t<er*an5 UK
2,,= <#).#11 A<1<A1 <)#HA<<
2,,8 .#(.1#) <#(AA<11 H!A<11 1 !<H(<##) <)!1HA A<A1A11 HAH(11.(
2,,6 #1!.A)) <.<HH11 H.#<1A11 .1!)< !!)(H1 <#((<AH A!!<<<). <.<.H)H
2,,4 .)<<1(< !<H!H.11 H<!((11 A()<H. !A<)A))( <H!<).( A!.<.1A1 <##.()H)
2,,3 <(!..!1 <A.(AA11 H1#<!A11 H<!).. ()1(<(! H1#!H! A<(1<#( A<!(1H
2,,- H)(A# <((111 .1)<A1. #.((. !<(#A)A# <!(<!11 A!.).A.# H#AAA1
2,,2 .()A() HH#H(!11 H<(#1#<. A<)(A) )<AH.(< ).#).1H AH.#AH #)(H)1<
2,,1 .A!1A.( HH<A!<11 H)H(<#11 A#H(..) ##.H !A<AA(.! A)<!#! !1<(<)!
2,,, #).(A!) H1HH!11 H#A#1#<1 1H!A.) !H.H#. !!!(!<(# ))<H<1# !).!)1
1+++ H1.#(() H<<<AA.( H#!!A(<1 )!!)1 !.1HAA <!H(A)1 !1#)).< H1!<H)
1++= )<#!HH. HH).#(( H##<<.< (..H# !<.H)HA# <<.)(#H< A.H<)H! !#A(H1<
1++8 A1.A)1H1 H.<.A<) H.(H#)1< ))... !<##!## <!#H)1.# AH1#.AH1 <<.!<
1++6 )!H!1H H<()H< H#(1)((1 <.#<1( !#!11H <#H) A.#(.1. <#AH..<
1++4 )1(1.1< <!H.!) #).!1(( HA!< !#(<A !(<!)<#. AHAA.<A. .<AA<A.
1++3 )#!A#(1 <.<)(1 !(.1)HA. A#A!AH# !!)!)(1# !HA.< A<)#!#.! A)(.1A
1++- <#<)!#. A#)..H !1#<)!!) A<11A#1 .H(##
<<
1++2 H1H#!#A A#<(.!) 1A!1<A< AH)A.
1++1 H1AH<#1( A.A1A(11 AH<#A1
1++, A.!)##) A(HA<)< A#.A##1A
1+=+ A<!A.1) A!...<.) AH!A<.#
1+== A#1.AH AH1AH1#
Ta)*e A.6 IPA Import-?xport data of ?uropean Countries in each year -A./
A$tr!a Fran&e Gree&e Ger(an' S%a!n Ita*'
S;!t<er*an
5
UK
2,,6
1#<<11
1
.1.<111
1
AAA!111 (H!#111 !)1.(111 H(<!H111 .)1(111 .1H!!111
2,,4
1<<11
1
H)(.!111
1
AAA11111 (H1A111 !)A()111 H(1##111 .).)111 .1A(111
2,,3
1A.(11
1
H)<H<111 AA1#)111 (<!(111 !))H111 H#<<111 #1A)111 H)(!<111
2,,-
A))!111
1
H)1<)111 AA1.1111 ()!111 !)!(#111 H#!))111 #1.111 H)HH<111
2,,2
A).(.11
1
H(.#!111 AA1!(111 (.1111 !)<#(111 H#!(111 #1(A111 H)!111
2,,,
A)A(#11
1
H(1#111 A1)#H111 (A.!111 !)#A111 H#1<<111 #A<111 H(((.111
1++=
A(#<A11
1
H#(<<111 A1(#.111 (1H#111 <1.!111 H.(#)111 #A()111 H(<#H111
1++8
A(H<!11
1
H#.H)111 A1(A!111 (1!#111 <1#1111 H.(H(111 #AA111 H(!A<111
1++6
A(!!)11
1
H#<.#111 A1#<1111 (1A111 <A!A<111 H.(<.111 #!1111 H(A.<111
1++4
A(A1<11
1
H#<1111 A1.H.111 (A(A#111 <11H111 H.(<.111 #<#111 H(1H111
1++- A1<11111 (A!!(111 <!!)(111 ##<111 H##A<111
1++2 A1)A111 (1)#H111 <<1.(111 #(#111
Ta)*e A.8 Population of ?uropean Countries -1/
A$ Frn Gree&e Ger S%a!n Ita*'
S;!t<er*an
5 UK
2,,6
1#<<11
1 .1.<1111 AAA!111 ()!111 !)1.(111 H(<!H111 .)1(111 .1H!!111
2,,4
1<<11
1 H)(.!1111 AAA11111 (<!(111 !)A()111 H(1##111 .).)111 .1A(111
2,,3
1A.(11
1 H)<H<111 AA1#)111 (H1A111 !))H111 H#<<111 #1A)111 H)(!<111
2,,-
A))!111
1 H)1<)111 AA1.1111 (H!111 !)!(#111 H#!))111 #1.111 H)HH<111
2,,2
A).(.11
1 H(.#!111 AA1!(111 (H!#111 !)<#(111 H#!(111 #1(A111 H)!111
2,,,
A)A(#11
1 H(1#111 A1)#H111 (.1111 !)#A111 H#1<<111 #A<111 H(((.111
1++=
A(#<A11
1 H#(<<111 A1(#.111 (1!#111 <1.!111 H.(#)111 #A()111 H(<#H111
1++8
A(H<!11
1 H#.H)111 A1(A!111 (1H#111 <1#1111 H.(H(111 #AA111 H(!A<111
1++6
A(!!)11
1 H#<.#111 A1#<1111 (1A111 <A!A<111 H.(<.111 #!1111 H(A.<111
1++4
A(A1<11
1 H#<1111 A1.H.111 (A(A#111 <11H111 H.(<.111 #<#111 H(1H111
1++- A1<11111 (A!!(111 <!!)(111 ##<111 H##A<111
1++2 A1)A111 (1)#H111 <<1.(111 #(#111
<H
Ta)*e A.= Calculation of capacity with respect to Drance
FRA
P#%>T$r>2$t$r
e
GDP>T$r>2$t$re &#n?&a%!ta>FR &#n?&a%!ta>TR Ca%a&!t'>e/&>%%% Ca%a&!t'
2,,6 ))HA1.(# <!<#!..). 1.1#A 1.1) )A.!<)!.!(. (!!(##(.)(
2,,4 )<1)H1A) !A)1(.111 1.1H( 1.1H( H<(<<A.H1A <)!)((A.#..
2,,3 )11!#1 <)(#.H(1 1.#1A 1.H.) HA1<#.(! <..A1.!1.##
2,,- A11!(.1H! <H.).)<H 1.(A# A..! A.(11#..!( AAH<1..).<H(
2,,2 )AH.1#H# #<!(..<< 1.)H1 1.)1! (#1.(#.HA# #H.!H!.))1
2,,, ()((!1<H <##.HH! 1.(.( 1.#)1 #1)(A1...H1 .<H)()(.1HA
1++= A1.(). A!.<...(! 1.)H. <.#() H#H#.HAAA.#)< H!)<.HA.#!!
1++8 (<#.#.!. A#)A).A<. 1.)#) 1.#<A .(<!)!.A(< H#A(.H##.#)#
1++6 (H..AH1. A()((.##( 1.)A! 1.#H) .H1)1(..H(< H)A#.<.(.#)A
1++4 (<.1((. A##<(.!HH 1.#.A 1..1# HA!#H!.<.#HH <.#HAH(A.)#
Ta)*e A.+ Calculation of capacity with respect to Jreece
GRE
P#%>T$r>2$t$r
e
GDP>T$r>2$t$re &#n?&a%!ta>GRE &#n?&a%!ta>TR Ca%a&!t'>e/&>%%% Ca%a&!t'
2,,6 )!<#<A() !1#.A..!< 1.!. 1.() #1A!)A!.!!A !1#)H(.A.A)#
2,,4 (()<H1!) !!##.111 1.A)# 1.A)# A#H<<H...)A 1111<H..(
2,,3 (HH<1!). A((<1.(.. 1.!1 1.A)# A.(!).)H.A! A)A)#H.<<1
2,,- )!(<1)A ((!1.<!# 1.H1 1.!H !<#H.!A.A)H !#1A).H.
2,,2 (H<(<)A< A(##!.< 1.A!. 1.A! AA!1<<(..H A((#AA<.!(
2,,, (H(A. AHH1)..#1 1.A(# 1.A#1 A<1<#.<!.<.( A.1A<!A!.HH!
1++= )(!.)( <1.)A.!. 1..< 1..)) .(#A#)H.(!! #(!<(<#.H1
1++8 ##)A!)< AA<<.11# 1.A! 1.A. A.A!H..H). A<!((!<..H1
1++6 #(AA)!( AA<1).!(1 1.!1 1.A(. A<H<<.1..A( A.HH#((H.A1H
1++4 ##!#<. A1#AH.<1( 1.!# 1.A(. A<!(.<1H.#H A.<11H1.H#
1++- #!<1(A (1)#.# 1.A.. 1.A1. ##H##.(.).< ((<!(H...A(
1++2 ##<!A(HH A1(.H.!A 1.A#1 1.A<< AAA(.(H..!) A#H!1A.11(
Ta)*e A.1, Calculation of capacity with respect to ;wit&erland
S9I
P#%>T$r>2$t$r
e
GDP>T$r>2$t$re
&#n?&a%!ta>S9
I
&#n?&a%!ta>TR Ca%a&!t'>e/&>%%% Ca%a&!t'
2,,6 A1)(!<A H1.<..AA( A.)! .H(1 .!)<AHH..) !(#))<1<.A<.
2,,4 ).AA)))< !H()!.111 A.)H( A.)H( A((A#A!.H<. #..#.((.)A!
2,,3 )AHH!#<( #<#.1!# .A1) A..(A AH!)AA!.A(. .<)<)(.1(<
2,,- A1!1HH1 H#HA..#A A.)!) !.1)! !A(#A!((.1(H <.(H1<<1.<(<
2,,2 )!H<H(HH !1().A# .1# .1( A)<#<!.1.)HA (.<<(A1.H)(
2,,, )<.A(< (H)!.!.( A.!). A..) AA#1)#!A).)1H A#A!!1.1..A
1++= A)1)A(< A(!AH.H!1 .!1 A<.<<! A(.<HA)<<.HH1 #<1(<!().<((
1++8 (#<HA(H1 A((..)# .1)A A.H#) A!(AA1A.A# 1!11H.A()
1++6 ((H)HH)1 (#!.(H( .H A.()1 A.#<AAA1.)) <.1)<!A.!)(
1++4 (#HH<)1) A<#.#!! .1(. A..# A<.!)A<)..#(! AHA)HH11.#A
1++- (H#.# AHH11.!(A A.)H A.A. )H)(#<)!.AAH A<AA1A.A<.(#)
<.
1++2 )1A<)H<< HA(A.H! .A(H .A.( A)H<H((<..!( (#!<H1!.).)
Ta)*e A.11 Calculation of capacity with respect to Austria
AUS
P#%>T$r>2$t$r
e
GDP>T$r>2$t$re &#n?&a%!ta>AUS &#n?&a%!ta>TR Ca%a&!t'>e/&>%%% Ca%a&!t'
2,,6 A11(#H1# <.(#.1!( 1.!!) 1.<<# <HA11<)).(# <1H!)##H.AH
2,,4 )<)<.H! !!H!#.111 1.!<1 1.!<1 !H!1!).H1 ())A<)..A(A
2,,3 )1.<1)! H)<(.!A1 1.<1 1.A)! A#HA<!).##( AH#<AHA(.)1
2,,- A1A<AAH# <()A.)A# 1... 1.<A. <1!H!<.)1! !#)!H#.A.#A1
2,,2 )A!A#<1 (!)#.(<# 1.!H1 1.!! !1H()#(.(#. #<).<!<.1<.
2,,, )1.1(1H! H()#.!!( 1.<AH 1.!#( !<A<))(.A.< !1#HH1H<.H)
1++= AH<#.(! A!#<(.H#H 1.H1H ..)1 !).(!...))< ).!<!#11...)
1++8 (H<A!AA A(.(..<<! 1.H#! 1.<!! !#1A1)H!.H) !!.(#.()A
1++6 (.!(1(AH A)((#.11H 1.HA1 1.<H !.#11)<..)) !)().AH.A#
1++4 (H1<#A! A(<(.A<< 1.H1 1.<11 !<1H1<(!.)) !1.1#A#..H.H
Ta)*e A.12 Calculation of capacity with respect to Italy
ITA
P#%>T$r>2$t$r
e
GDP>T$r>2$t$re &#n?&a%!ta>ITA &#n?&a%!ta>TR Ca%a&!t'>e/&>%%% Ca%a&!t'
2,,6 )#..1.A! !)A)1.!AA 1.HH< 1.#1) .)<)(..)#) ..#(#).1A.
2,,4 ).1!)< )1).111 1.H< 1.H< H1A!<A.A1) <(!)(!1<..(<
2,,3 ()1AA( !<#!.!A< 1.H1! 1.<A! !.#))..(.!#. !H<.)HH).((1
2,,- ))1<)1H! <!#1..< 1..1( 1.)H )A.!)H<!.!(A ((!##1.#(
2,,2 )1#)!1. .A)1.)1< 1.HA! 1.<)# <HA.HA!).)H. <!H!..H.1A(
2,,, ()1.#1H !HHH.1A 1..H 1..1A H!HH.11A.#! HA.1<.A)A
1++= AA(AH1A1 AA!1!.#H) 1..1) .(() !<A!<.(H!.!11 !)11)1AH.(
1++8 (<<11.)# A#<)<.H)# 1..A 1.<.! !)1()..(.!. !#.#.#((.#<(
1++6 (H#H.! A(H1.#(! 1..HH 1.H<< <.!H))!!.A)1 <<.(<#.)H<
1++4 (<.A<## A#!!H..) 1..H. 1.H! <<1HH1#H.A#< <<.#!.1H)
Ta)*e A.1- Calculation of capacity with respect to ;pain
SPA
P#%>T$r>2$t$r
e
GDP>T$r>2$t$re &#n?&a%!ta>SPA &#n?&a%!ta>TR Ca%a&!t'>e/&>%%% Ca%a&!t'
2,,6 ).A.1<<< !H)#..H.. A.. A<(<)##!<.A#1 AH!1H!.(.!(1 1H.!.!
2,,4 )AA..H!! .#).111 A.1(H )()H1!H(.1H A1A<(#H<..#1 1A.!<
2,,3 (#HA#(< A!(.).< A.)A )<H1.<).!#H ).)).#A.AH< 1A(.1#H
2,,- ).H<)!1 !.A#.!(# A.AA! AH#(!1(<A..1H A.A(###(... 1H.<!)
2,,2 ((H#)H1 (H1.)!< 1.#H .<1H#1H1.!1 .H.))H!(.##A 1A).11H
2,,, (.<#<(#. 111..)) 1.(<1 ..1(<#.#.H<! .###)<(.#. 1A#.A<!
1++= A1()<#) #A#!.<(# A.AA1 <<!.#.!#.(( <HH1H.)1.A!H 1!H.1)
1++8 (AA#.)! A<A1..H<H A.1#H ..<)(A).((! .#)<(H!!.A< 1A.<(
1++6 (AH!A(.H A<<H1.(H! A.1!< .)1(1AH.(1! #1(HA<AA.1(1 1A.H(.
1++4 (1<!).#! A!<A.(! 1.)AH H(((1<<.!( H)#(.1).H.# 1AA.H<
1++- #H().#<( )#..)# 1.#1) !!.#)<(..!!< !<H<!1..)1# 11#.1<A
1++2 (1.(#!. A!.<.H(. 1.<H# !.##<)... !!HAH!##.1H 1AA.#(1
<#
Ta)*e A.13 Calculation of capacity with respect to 7G
UK
P#%>T$r>2$t$r
e
GDP>T$r>2$t$re &#n?&a%!ta>UK &#n?&a%!ta>TR Ca%a&!t'>e/&>%%% Ca%a&!t'
2,,6 A11HAH.)< <H)H...1A 1.#1H )!1(.(..()) A11<(!H.## 1(.#)
2,,4 )<#!)H)< !!A!H.111 1.#)! #HAH!(1<.<< )(H.!...<H# 1<.A1
2,,3 )1<.!.(! H.#1.1)1 1.!HH H)!1.HA.H<< !<11#<AA.(.A 11..!<
2,,- A11)1<.! <.)<(.1)( 1.<! .##)11#).#)1 (()1H1..#. 1).1)A
2,,2 )A.A11. #H!(.H(# 1.<# <A1#<)!<.1) H!(.(#...1 1A..A)
2,,, ()<A)!( <1#<. 1.!). !A..#.(.<<1 <A(H)H.(! 1A).#!H
1++= AA)<H#A) AA)A.1..H< 1.<1. !#H)AH1A.(H. !AAH)H<A.#1 1<.A!(
1++8 (<H<H.!! A#..A.)! 1.<A) .(A.AA).1.1 !HA.(.(1.#!< 1AH.!).
1++6 (HH!#< A(<)<.HA1 1.<H !11.##..1. !)<!!1#(.(( 1A..1<
1++4 (!)H.1A A.))A.A(! 1.<HH !1<<.(.H.(#( !))!1!AH.)1. 1A<.(H<
1++- #(H)#AA< AA(11.<1! 1.1AA HH(H.H.( .().1#.!1 11).#<(
APPENDII E J Compared patents
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