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A study report on the 246376677.

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A study report on the 246376677.doc
PREAMBLE
In the name of ALLAH ,the compassionate the
Merciful Read the name of your lord, who creates
man from the clot of blood, read, your Lord is most
Gracious who teaches you by mean of -Pen,
teaches man -what he does not now!"
A STUDY REPORT ON
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A study report on the 246376677.doc
RECOVERY OF THE LPG FRO M THE GAS CO #$%#&A TE


PROJECT ADVISORS
Dr. JAVAID RABBANI KHAN
Director NFC_IEFR_FSD
Dr. SHAHID RAA MALIK
H.O.D ! De"#rt$e%t o& c'e$ic#( E%)i%eeri%)
&'(MI))%$ (*
SESSION *++, - *++.
DEPARTMENT OF CHEMICAL ENGINEERING
NFC INSTITUTE OF ENGINEERING AND
FERTILIER RESEARCH
USMAN ALI RANA
M.ASIF HAYAT MALIK
HASSAN RIA
MUHAMMAD /ASEEM
MUHAMMAD UBAIR
*++,-UET-IEFR-c'e$-FD-00
*++,-UET-IEFR-c'e$-FD-1,
*++,-UET-IEFR-c'e$-FD-12
*++,-UET-IEFR-c'e$-FD-20
*++,-UET-IEFR-c'e$-FD-1*
3
A STUDY REPORT ON
Reco3er4 o& LPG &ro$ t'e GAS CONDENSATE
SESSION *++, - *++.
T'i5 "ro6ect i5 7ei%) 587$itte9 to c'e$ic#( e%)i%eeri%) 9e"#rt$e%t!
NFC i%5tit8te o& e%)i%eeri%) #%9 &erti(i:er re5e#rc'! F#i5#(#7#9 i%
t'e "#rti#( &8(;(($e%t o& 7#c'e(or<5 9e)ree i% c'e$ic#( e%)i%eeri%)!
A""ro3e9 o% ___________________
I%ter%#( E=#$i%er>
___________________________________
?Dr. JAVAID BABBANI KHAN@
?Dr. SHAHID RAA MALIK@
E=ter%#( e=#$i%er>
___________________________________
DEPARTMENT OF CHEMICAL ENGINEERING
NFC INSTITUTE OF ENGINEERING
AND FERTILIER RESEARCH
FAISALABAD
DEDICATED
To
M4 #A#7(e F#t'er
A symbol of success for me+ Always beha,e lie a friend -hose
mature, ,aluable .uidance, /inancial assistance, %nabled me to
percei,e and pursue Hi.her ideals in life"
M4 #9or#7(e Mot'er
A mine rate of lo,e, a0ection and indness -ho enli.htened me A
learnin. spirit I am learnin. much /rom her leap till now"
1
Brot'er5 B Si5ter5
5
All of us solemnly acnowled.e that all thans, .ratitude and
obli.ations are only for the almi.hty CALLAHC who bestowed
upon the coura.e and nowled.e and enabled us to wor out this
pro2ect report" -e o0er our humblest and sincerest words of
thans to !Holy Prophet! HARAT MUHAMMAD ?PBUH@
who is torch of .uidance and nowled.e"
-e own no words to pay our most respectful ad,isors D r . JAVAID
RABBANI KHAN! $irector
NFC_IEFR B D r . SHAHID RAA MALIK, Head of department,
department of chemical %n.ineerin. for his de,oted, sincere and
ind .uidance throu.h out the pro2ect" He encircled us with the
nowled.e for the -hole session" He did not sta..er at hard
times by eepin. our morale up abo,e the sy and by
continuously encoura.in."
-e also feel hi.hly pri,ile.ed here to ha,e the honor of our
family to whom a lot more than 2ust thans for there endless
support and encoura.ement" -e could not .et this sta.e with out
their help and .uidance"
%specially we ha,e no words for the special prayers of our
belo,ed Parents"
-e are hearty thanful to all the facility members, friends, class
fellows and e,ery person who helped us in worin. out this
pro2ect"
In the same way we hearty thanful to our respected teachers for
6
their perfect .uidance in all respects" All they were the pillars of
coura.e and a constant source of inspiration without whose
cooperation this entire world has been impossible"
A8t'or
5
USMAN ALI RANA
M. ASIF HAYAT MALIK
HASSAN RIA
MUHAMMAD /ASIM
MUHAMMAD UBAIR
7
PREFACE
)he history or LPG is not ,ery started from ,ery old a.es it started from
about 34-56 years a.o when a .as called a (lau .as was disco,ered in
7863 by Herman (lau in Germany" (ut at that time no body nows its
uses and si.ni9cance as a fuel" -ith the passa.e of time many
e:periments and obser,ations were studied on that .ases obtained
from re9nery .ases and natural .as analysis and it was found that
mi:ture of propane and butane at a de9nite ratio produce Li;ue9ed
Petroleum .as which can be substituted as a fuel" Its 9rst commercial
use was introduced in streets li.hts of #ew *or and then soon it was
used as a fuel in rural and urban areas of America in 78<6=s" After the
successful e:perimentation on LPG many companies and re9neries
started their business in LPG manufacturin. and distribution and 9llin.
stations as well" #ow LPG has a si.ni9cant share of world=s ener.y
supplies and sources but still its uses is limited to the de,elopin.
countries, its bene9ts are not reached to the poor and de,elopin. and
underde,eloped countries" In Paistan LPG manufacturin. was made in
78>6 and now its total share in the whole ener.y re;uirements of the
country is about 6"3?, it is rather nominal but .o,ernment is tryin. to
increase its share and many re.ulations policies are made by @GRA for
in,estment in LPG manufacturin. and distribution so that rural a,era.e
people can en2oy the bene9ts of /uel" LPG is most widely used in
cooin. and transportation sector in Paistan" LPG is bein. produced
by natural .as processin. and re9nery .ases, from crude petroleum
distillation, the .ases were obtained was processed further to produce
butane and propane and after .ettin. these .ases, they are mi:ed in a
de9nite ratio to produce LPG, the home user .rade LPG is further
processed as the LPG obtained after processin. of natural or re9nery
.ases is sour so puri9cation step in,ol,e sweetenin. process in which
odor and other particulate pollutants present in LPG is remo,ed" )he
use of LPG can be harmful if it is not used accordin. to the safety
measures, many or.aniAations
wored a lot the LPG safety measures and re.ulations" @&HA and
world LPG .as association are the two ma2or or.aniAations who ha,e
contributed a lot for the LPG speci9cations, standards, safety
precautions, safety installation procedures, stora.e and transportation
facilities speci9cations, etc" )hese standards are followed by e,ery
.o,ernment concerned authorities for the proper supply of LPG in their
country as well"
A8t'or
8
________________________________________________________________________
# Subject Page #
History
1) History of LPG 14
2) First Used for Street lightning 14
3) LPG production history in Pakistan 16
4) Energy consumption & demand statistics 17
in Pakistan
Introduction
1) What is LPG? 20
2) Why it is called Liquefed Petroleum Gas 20
3) What is commercial Propane & Butane 20
4) Why Propane & Butane are used in combination
USMAN ALI RANA
M.ASIF HAYAT MALIK
HASSAN RIA
MUHAMMAD /ASEEM
MUHAMMAD UBAIR
*++,-UET-IEFR-c'e$-FD-00
*++,-UET-IEFR-c'e$-FD-1,
*++,-UET-IEFR-c'e$-FD-12
*++,-UET-IEFR-c'e$-FD-20
*++,-UET-IEFR-c'e$-FD-1*
5) Properties of LPG 21
6) Natural Gas condensate 23
7) Composition of natural gas condensate 24
8) Separating the condensate from the raw natural
gas 25
Process
1) Membrane process 28
2) Catalytic hydro cracking process 31
3) Dehydration process 32
4) Catalytic process 32
I.Objective of the catalytic process 32
II.Detailed description 37
III.Synthesis gas production process 41
IV.Industrial applicability 46
Process equipment
1) Gas-gas exchanger 49
I.Introduction 49
II.Conventional gas-gas heat exchanger 49
III.Radial foe heat exchanger 50
IV.Plate type heat exchanger 51
V.Hot exchanger 52
VI.Cold exchanger 52
2) Turbo expander 53
9
I.Applications 53
a)Extracting hydrocarbon liquids from
natural gas 54
b)Power generation 55
c)Refrigeration system 57
3) Slug catcher 58
I.Basic operation 59
II.Slugs 61
III.Purpose of slug catcher 62
IV.Slug catcher design 62
4) Molecular sieves 63
I.Types of molecular sieve beds 64
II.Regeneration 68
III.Applications 69
5) De-ethanizer 70
6) De-butanizer 74
Plant location
1) Plant location & selection 78
2) Sitting factors 78
3) Environmental consideration 78
4) Labor availability & productivity 78
5) Living condition 79
6) Raw material availability 79
7) Accessibility to transportation 79
8) Property cost 79
9) Tax 79
10
10)Specifc plant site consideration 79
11)Conclusion 80
Cost estimation
1)Cost estimation 82
2)Investment & fxed capital investment 82
I.Working capital investment 82
II.Fixed capital investment
III.Direct cost 82
IV.Indirect cost 83
3)Factors efecting investment
& production cost 83
4)Types of capital cost estimate 84
5)Cost indexes 85
6)Method for estimating capital investment 85
7)Delivered equipment cost 86
8)Cost estimation (mathematically) 87
9)Indirect cost ( mathematically) 88
10)Direct cost (mathematically) 89
11)Processing cost 90
12)Fixed charges 90
13)General expenses 91

Instrumentation & control process

11
1)Instrumentation & process control 94
2)Feed back control 94
I.Negative feed back control 94
II.Positive feed back control 94
3)Components of the control system 94
I.Process 94
II.Measuring elements 95
4)Analysis of the measurement variables to be
measured 95
5)Variable to be recorded 95
I.Controller 95
II.Final control element 95
6)Characteristics of the controller 96
7)Modes of the controller 96
8)Flow controller 97
9)Temperature controller 97
10)Pressure controller 97
11)Level controller 97
12)Transmitters 97
13)Control valves 98
14)Instrumentation & control objectives 98
15)Programmable logic control 98
16)Integral control system 99
12
Advantages, disadvantages, transportation,
application,Storage sales & uses
1)Advantages of the LPG include 101
2)Draw backs of LPG include 102
3)Transportation 103
4)Application areas 104
5)Storage 105
6)Sales & uses 106
108
13
C'#"ter D E
14
Hi5tor4 o& LPG
)he birth of Li;ue9ed petroleum .as industry in 7863 was too
si.ni9cant historically to be recorded on the passin. record of
time, but in half century that followed it had such phenomenal
.rowth and brou.ht so many economic and personal bene9ts
to the people in the rurall areas of the world" It is truly may
be said a destiny awaited it from the ,ery be.innin. and that a
lar.er measure of such destiny has been attained by the year
of 785B" (ottle .as is now 34 years old almost half a century"
Its history be.an in 7863 in Germany with the de,elopment of
!(lau.as! by Herman (lau amon. German chemist" LPG was a
mi:ture of permanent .ases, li;uid .as, and li.ht fractions of
.asoline, all synthetically produced by a modi9cation of the
pre,alent practice of manufacturin. illuminatin. .as from oil"
(lau.as was e:pensi,e to produce and e,en more e:pensi,e to
handle It was stored in cylinders in which the pressure ran.ed
from C56 to 7566 psi" )he cost of manufacture was rou.hly
76D per lb and the users had to pay two-way frei.ht on Clbs of
steel to .et 7 lb of fuel"
)he utiliAation system consisted of a .as 9red ,aporiAer, a
series of li;uid and ,apor re.ulator to reduce tan pressure to
4 oA and a small stora.e tan to the prepared ,apor" )he same
e;uipment introduced into America carried installation char.es
of D<66 e,en bac in the days when a dollar would buy a lot"
Fir5t U5e9 For Street Li)'te%i%)
(lau.as was used for li.htenin. streels and homes and for
domestic cooin." It achie,ed moderate popularity amon. the
%uropeans who could a0ord it, and plants were later installed
in se,eral countries in %urope" #ine American companies were
formed to maret the product in '&A" )wo of which the #orth -
western (lau.as Eo St.
Paul and (lau.as Eo" @maha sur,i,ed throu.h the adoption of
LP .as when it became a,ailable"
Li;ue9ed petroleum .as as we now them now, came into
bein. trou.h the in,esti.ations and e:perimental e0orts of
se,eral worers of unusual ,ision in the petroleum and related
9elds" )echnical paper #o"76 of the '"&" (ureau of Mines
published in 787< and written by Ir,in. E" Allen and Geor.e A"
(urrel l Fnow president of Atlantic &tates Gas Eo"G notes that
the li;uid condensin. out of natural .as in pipelines contained
in.redients of .aseous nature which should ha,e commercial
possibilities" $urin. the two or three years prior to the
15
publication of this report, $r" -alter @" &nellin., an e:plosi,es
specialist for the (ureau of &tanfards, was worin. on the
production
and utiliAation of these same .aseous components" As early as
May 787<, he had de,eloped a worable system of storin. the
Li;ue9ed .aseous e:tract of this pipeline !drip .asoline! in
steel cylinders and installin. the .as systems in rural homes
for li.htenin. and heatin." His description of the merits of the
product, as re,ealed in newspaper accounts of that period,
sound stran.ely lie the product story which we use today"
At about the same time E"L" Herr and his cousin A"# Herr who
later founded the Roc.as products Eo" of Pittsbur.h, Pa and
the Imperial Gas Eo, of lon. beach calif produced a similar
material by re-condensin. the ,apors which escape durin. the
weatherin. of natural .asoline at their Ri,erside @il Eo
re9nery at &isters,ille, -" Ia Mr" &nellin. and the Herrrs
formed the American Gasol Eo" the 9rst company to bottle and
sell li;ue9ed .as e:tracted from natural .as and natural
.asoline"
)he third product was called !Gasol! they had not yet found
out how to fractionate it properly, and so much hea,y material
was included in the 9rst season=s output that they e:perienced
diJculty ,aporiAin. it durin. the cold weather"
)he problem was o,er come in a short time by securin. raw
stoc with a more fa,orable boilin. ran.e from another source
and by de,elopin. e;uipment which enable them to mae a
product which was more predominantly (utane and Propane" It
still continued considerable %thane, and the re;uired stora.e
pressure was to hi.h that hea,y steel cylinders were re;uired to
hold it" -hile the product pro,ed to be a practical fuel, with
many ad,anta.es o,er oil and natural .as, it was not possible
to merchandise it widely at that time because of the .reat
wei.ht of containers" Its domestic use was con9nes to
li.htenin. and cooin. in homes closely surroundin. the
production plant" )he 9rst homes in which the installation of
the new .as were made in the ,icinity of -aterford and Le
(oef Pa in the sprin. of 787<"
@f in,aluable technical assistance durin. this early period was
the wor of /ran R Peterson an associate of the Herrs, who
was en.a.ed in de,elopin. impro,ed e;uipment for processin.
natural .asoline" In 787 7 he 9lled a patent application
co,erin. the 9rst practical method of obtainin. the LPG
fractions in ;uantities, direct from natural .as" His process
se.re.ated the hea,ier in.redients of the .as into stable
natural .asoline, hi.hly ,olatile .asoline blendin. stoc and
li;ue9ed petroleum .ases consistin. of butane, isobutene,
propane and a small ;uantity of ethane" -ith uncanny
16
foresi.ht, the list of uses included in the patent application
included illuminati on, fuel for operatin. .as en.ines, weldin.,
braAin., cuttin. metals and in sur.ery as an anesthetic" (efore
Mr" Peerson had been issued his patent he had an e:perimental
automobile operatin. on the streets of #ew *or city which used
a mi:ture of (utane and Propane for the fuel"
Reasonable producer price for their product and a retail price
respecti,ely" After promul.ation of the oil and .as re.ulatory
authority F@GRAG
@rdinance <66< all LPG re.ulatory functions as en,isa.ed in LPG"
FP1$G Rules <667 were transferred to @GRA in March <66B" )his
policy
aims at increasin. LPG supplies, streamlinin. its distribution
at a0ordable prices, especially to LPG star,ed areas of the country
and promotin. healthy competition for .rowth of LPG maret while
ensurin. minimum safety standards across the LPG supply chain"
)o achie,e this .oal, issues re.ardin. LPG production, LPG
licensin., safety standards, pricin., distribution in under de,eloped
areas and import of LPG ha,e been addressed"
LPG "ro98ctio% 'i5tor4 i% P#Fi5t#%
LPG was ori.inally introduced in Paistan in 78>>" Initially, the Paistan
LPG maret was a fully re.ulated one, where "supply was restricted to
only indi.enously produced LPG and where the Go,ernment of Paistan
controlled pricin." A sea chan.e occurred in 7883-7885, when imports
were allowed, leadin. to complete industry dere.ulation by April <667"
Althou.h LPG=s share in the country=s ener.y re;uirements has been
nominal to date, o,er the past decade, .rowth by ,olume has been at a
rate of around 73? per annum" )his is e:pected to continue .rowin.
si.ni9cantly with increasin. LPG supplies a,ailable from both local and
imported sources" Eurrently about 7>66 tonsKday LPG is bein. produced
domestically contributin. 6"3 ? to the total ener.y supply mi:" (ecause
of its characteristics LPG is fast becomin. a fuel of choice in the areas,
where natural .as distribution networ is not a,ailable" Eurrently out of
<5 million households in Paistan, 3"B million are connected to natural
.as networ and the rest are relyin.
on LPG and con,entional fuels lie coal, 9rewood, erosene, dun. cae
etc" In Lune <666, the /ederal Go,ernment decided to dere.ulate the
LPG industry with a ,iew to main. it in,estor friendly, foster healthy
competition, impro,e safety standards, and ensure better consumer
ser,ices" Accordin.ly, in supersession of LPG FProduction 1 $istributionG
Rules 78C7, LPG FProduction 1 $istributionG Rules <667 we1e formulated
under which LPG allocations made by the Ministry of Petroleum 1
17
#atural Resources FMP#RG prior to dere.ulation were .i,en protection to
the e:tent of terms of e:istin. a.reements between the maretin.
companies and producers" )hese Rules also empower the producers and
maretin. companies to 9: a reasonable producer price for their
product and a retail price respecti,ely" After promul.ation of the oil
and .as re.ulatory authority F@GRAG
@rdinance <66< all LPG re.ulatory functions as en,isa.ed in LPG"
FP1$G Rules <667 were transferred to @GRA in March <66B" )his
policy
Aims at increasin. LPG supplies, streamlinin. its distribution
at a0ordable prices, especially to LPG star,ed areas of the country
and promotin. healthy competition for .rowth of LPG maret while
ensurin. minimum safety standards across the LPG supply chain"
)o achie,e this .oal, issues re.ardin. LPG production, LPG
licensin., safety standards, pricin., distribution in under de,eloped
areas and import of LPG ha,e been addressed"
ENERGY CONSUMPTION AND DEMAND STATISTICS IN
PAKISTAN
%ner.y sector in Paistan comprises electricity, .as, petroleum and
coal" )he primary commercial ener.y supplies increased by 3"B
percent about 5C"8 million tones of oil e;ui,alent FM)@%G durin.
<665-6> as compared to 55"5 FM)@%G in <663-65" )he supply of
ener.y increased by 8"< percent and 4 percent in <663-65 and
<66B-63 respecti,ely" )he slower .rowth of primary ener.y supplies
durin. <665-6>, can be attributed to lower consumption of Hi.h
&peed $iesel F'&$G in transport sector, and sharp reduction in coal
imports by Paistan &teel" )he decline in primary ener.y supplies
has been compensated by siAeable increase of <6"< percent in
hydral .eneration durin. <665-6>" )he share of natural .as in
primary !ener.y supplies durin. <665-6> reached 56"3 percent
followed by oil F<4"3 percentG, hydro electricity F7<"C percentG, coal
FC"6 percentG, nuclear electricity F7"6 percentG and LPG F6"3
percentG "
Primary %ner.y &upplies by &ource F<665-6>G
18
$urin. the last ten years F788>-8C to <665-6>G, the consumption of
petroleum products has decreased by an a,era.e rate of 6"3 percent per
annum" )he consumption of .as, electricity and coal on the other hand,
has increased at an a,era.e rate of C"4 percent, 5"7 percent and 4"4
percent per annum, respecti,ely" )he annual trend of ener.y
consumption for the period 788>-8C to <665-6> is .i,en in )able "It is
important to note that a structural chan.e is tain. place in ener.y
consumption pattern in Paistan since <666-<667" -hile consumption of
petroleum products is declinin. e:cept in <663-65, the consumption of
other components of ener.y is risin." )he a,era.e consumption of
petroleum products has in fact, re.istered a decline of <"4 percent per
annum since <666-<667, due to lower consumption of oil in the
household and a.riculture sectors" @n the other hand, since <666-67
consumption of .as, electricity and coal ha,e .rown at a,era.e rates of
8"> percent, >"4 percent and 7>"C percent, respecti,ely"
19
C'#"ter D *
20
/'#t i5 LPG G
LPG or LP Gas is Li;ue9ed Petroleum Gas" )his is a .eneral description of
Propane Fchemical formula EBH4G and (utane Fchemical formula E3H76G,
either stored separately or to.ether as a mi:"
LiH8e;e9 Petro(e8$ G#5 is the .eneric name for mi:tures of
hydrocarbons Fmainly propane and butaneG" -hen these mi:tures are
li.htly compressed Fappro:" 466 Pa or 7<6 psiG, they chan.e from a
.aseous state to a li;uid and become more dense Fby appro:" <C6
timesG" e." 7 litre of LPG li;uid is e;ual to <C6 litres of LPG ,apour"
/'4 i5 it c#((e9 LiH8e;e9 Petro(e8$ G#5G
)his is because these .ases can be li;ue9ed at normal temperature by
application of a moderate pressure increase, or at normal pressure by
application of coolin. usin. refri.eration"
LPG comes from two sources" It occurs naturally in oil and .as 9elds and
is separated from the other components durin. the e:traction process
from the oil or .as 9eld" LPG is also one of the by-products of the oil
re9nin. process"
)here are two di0erent .rades or blends of LPG and they are not
interchan.eable" @ne is for automoti,e use only Fcalled auto.asG and will
contain butane and propane" )he other is propane only, which is used for
decantin. into cylinders for cara,ans, barbecues, campin. and
household use"
/'#t i5 co$$erci#( Pro"#%e B B8t#%eG
Ideally products referred to as !propane! and !butane! consist ,ery
lar.ely of these saturated hydrocarbonsM but durin. the process of
e:tractionKproduction certain allowable unsaturated hydrocarbons lie
ethylene, propylene, butylenes etc" may be included in the mi:ture
alon. with pure propane and butane" )he presence of these in moderate
amounts would not a0ect LPG in terms of combustion but may a0ect
other properties sli.htly Fsuch as corrosi,eness or .um formationG"
/'4 #re B8t#%e #%9 Pro"#%e 85e9 i% co$7i%#tio%G
-hile butane and propane are di0erent chemical compounds, their
properties are similar enou.h to be useful in mi:tures" (utane and
Propane are both saturated hydrocarbons" )hey do not react with other"
(utane is less ,olatile and boils at 6">
6
E" Propane is more ,olatile and
21
boils at - 3<
6
E (oth products are li;uids at atmospheric pressure when
cooled to temperatures lower than their boilin. points" IaporiAation is
rapid at temperatures abo,e the boilin. points" )he calori9c FheatG
,alues of both are almost e;ual" (oth are thus mi:ed to.ether to attain
the ,apor pressure that is re;uired by the end user and dependin. on
the ambient conditions" If the ambient temperature is ,ery low propane
is preferred to achie,e hi.her ,apor pressure at the .i,en temperature"
Pro"ertie5 o& LPG>
LPG isN
Eolourless"
@dourless" FIt=s normal to odorise LPG by addin. an odorant prior to
supply to the user, to aid the detection of any leasG"
/lammable"
Hea,ier than air"
Appro:imately half the wei.ht of water"
#on to:ic but can cause asphy:iation"
LPG e:pands upon release and 7 litre of li;uid will form appro:imately
<56 litres of ,apour"
Relati,e density of li;uid propane and butane at 75
6
is 6"564 and
6"5CB respecti,ely"
Relati,e density of ,apour propane and butane at 75
6
is 7"54 and <"6>
respecti,ely"
Iapour pressure of the propane and butane at -76
6
Eare <5> and 3
Hpa respecti,ely and at 6
6
E are B44 and 36Hpa respecti,ely F.au.eG"
/ire point of propane and butane are 576
6
E in air and 386
6
E in air
respecti,ely"
(urnin. ,elocity of both propane and butane in air is B< cmKs"
22
Eharacteristic 'nits
Propan
e
n-
(utane
Ehemical formula E
B
H
4
E
3
H
76
Modular wei.ht 33,683 33,683
/reeAin. Point of li;uid at C>6 mm H. FOEG -74C,C -7B4,B
(oilin. Point of li;uid at C>6 mm H. FOEG -3<,7 -6,5
&peci9c -ei.ht of li;uid at 75,5 OE FH.rKltG 6,56C 6,56<
Relati,e density of ,apour Fair P 7G at
&"E"
7,5<< <,66>
Eritical )emperature FOEG 8>,4 75<,6
Eritical Pressure Q absolute FbarG 3<,> B6,6
Iapour to li;uid ratio at &"E" <C<,C <BC,4
Latent Heat at (oilin. Point and C>6
mm H.
FHcalKH.G 767,C 8<,B
FHcalKltG 57,5 5B,7
Hi.h Ealori9c Ialue at &"E"
FHcalKH.G 7<634 77457
FHcalKltG <<C>> <84C5
Air re;uired for burnin. at &"E"
Fm
B
airK7 m
B

,apourG
<B,4< B6,8C
FH.r airK7 H.r
,apourG
75,C7 75,38
&peci9c Heat of ,apour at &"E" REpS FHcalKH.rOEG 6,B44 6,B8C
&peci9c Heat of ,apour at &"E" RE,S FHcalKH.rOEG 6,B3B 6,B>7
/lash Point FOEG -765 ->6
Low /lammability Limit of ,apour K air
mi:ture FL/LG
<,BC 7,4>
Hi.h /lammability Limit of ,apour K
air mi:ture FH/LG
8,56 4,37
@ctane #umber 7<5 87
23
N#t8r#( G#5 Co%9e%5#te>
#atural .as condensate is a low-density mi:ture of hydrocarbon li;uids
that are present as .aseous components in the raw natural .as
produced from many natural .as 9elds"
It condenses out of the raw .as if the temperature is reduced to below
the hydrocarbon dew point temperature of the raw .as"
)he natural .as condensate is also referred to as simply condensate, or
.as condensate, or sometimes natural .asoline because it contains
hydrocarbons within the .asoline boilin. ran.e" Raw natural .as may
come from any one of three types of .as wellsN
Cr89e oi( Ie((5 Q Raw natural .as that comes from crude oil
wells is called associated .as" )his .as can e:ist separate from
the crude oil in the under.round formation, or dissol,ed in the
crude oil"
Dr4 )#5 Ie((5 Q )hese wells typically produce only raw natural
.as that does not contain any hydrocarbon li;uids" &uch .as is
called non-associated .as"
Co%9e%5#te Ie((5 Q )hese wells produce raw natural .as
alon. with natural .as li;uid" &uch .as is also non-associated
.as and often referred to as wet .as"
A low-9e%5it4, hi.h-API )r#3it4 li;uid '49roc#r7o% phase that
.enerally occurs in association with natural .as" Its presence as a
li;uid phase depends on temperature and "re558re conditions in
the re5er3oir allowin. condensation of li;uid from ,apor" )he
"ro98ctio% of condensate reser,oirs can be complicated because
of the pressure 5e%5iti3it4 of some condensatesN $urin.
production, there is a ris of the condensate chan.in. from .as to
li;uid if the reser,oir pressure drops below the dew point durin.
production" Reser,oir pressure can be maintained by Tuid in2ection
if .as production is preferable to li;uid production" Gas produced in
association with condensate is called wet .as" )he API )r#3it4 of
condensate is typically 56 de.rees to 7<6 de.rees"
Gas condensate 9elds are .ettin. more important due to an increasin.
share of .as produced from these 9elds within the .lobal structure of .as
production" @ne of the essential problems of .as condensate 9eld
de,elopment is condensate reco,ery optimiAation" $e,elopment of
24
depleted .as condensate 9elds is followed by reser,oir pressure
depletion and retro.rade condensation of hi.her boilin. hydrocarbons
FcondensateG with some dropped out in li;uid phase and lost to
formations due to the fact that this condensate becomes immobile
re.ardless of further Tuid Tow" As a result, up to B6->6? of initial
condensate reser,es can remain in the formation" &o far, only one
stimulation techni;ue is used for
condensate reco,ery enhancement and that is cyclin.-process, which is
a rein2ection of dry .as into the formation" Howe,er, in many cases the
application of cyclin.-process is not applied due to economic and other
reasons" )hus, the .as industry is in desperate need for updatin.
e:istin. stimulation techni;ues applied in .as condensate 9elds and is in
search of new technolo.ies to enhance condensate reco,ery by both,
maintainin. the reser,oir pressure thereby pre,entin. condensate loss
to formation, and by e:tractin. retro.rade condensate already dropped
out in formation"
Co$"o5itio% o& %#t8r#( )#5 co%9e%5#te>
)here are hundreds of wet .as 9elds worldwide and each has its own
uni;ue .as condensate composition" Howe,er, in .eneral, .as
condensate has a speci9c .ra,ity ran.in. from 6"5 to 6"4 and may
containN
Hydro.en sul9de FH
<
&U
)hiols traditionally also called mercaptans Fdenoted as R&H,
where R is an or.anic .roup such as methyl, ethyl, etc"G
Earbon dio:ide FE@
<
G
&trai.ht-chain alanes ha,in. from < to 7< carbon atoms
Fdenoted as E
<
to E
7<
G
Eyclohe:ane and perhaps other naphthenes "
Aromatics FbenAene, toluene, :ylenes and ethylbenAeneG
25
Se"#r#ti%) t'e co%9e%5#te &ro$ t'e r#I %#t8r#(
)#5>

&chematic Tow dia.ram of the separation of condensate from raw natural .as
)here are ;uite literally hundreds of di0erent e;uipment con9.urations
for the processin. re;uired to separate natural .as condensate from a
raw natural .as" )he schematic Tow dia.ram to the ri.ht depicts 2ust one
of the possible con9.urations"
)he raw natural .as feedstoc from a .as well or a .roup of wells is
cooled to lower the .as temperature to below its hydrocarbon dew point
at the feedstoc pressure and that condenses a .ood part of the .as
condensate hydrocarbons" )he feedstoc mi:ture of .as, li;uid
condensate and water is then routed to a hi.h pressure separator ,essel
where the water and the raw natural .as are separated and remo,ed"
)he raw natural .as from the hi.h pressure separator is sent to the main
.as compressor"
26
)he .as condensate from the hi.h pressure separator Tows throu.h a
throttlin. control ,al,e to a low pressure separator" )he reduction in
pressure across the control ,al,e causes the condensate to under.o a
partial ,aporiAation referred to as a Tash ,aporiAation" )he raw natural
.as from the low pressure separator is sent to a !booster! compressor
which raises the .as pressure and sends it throu.h a cooler and on to
the main .as compressor" )he main .as compressor raises the pressure
of the .ases from the hi.h and low pressure separators to whate,er
pressure is re;uired for the pipeline transportation of the .as to the raw
natural .as processin. plant" )he main .as compressor dischar.e
pressure will depend upon the distance to the raw natural .as
processin. plant and it may re;uire that a multi-sta.e compressor be
used"
At the raw natural .as processin. plant, the .as will be dehydrated and
acid .ases and other impurities will be remo,ed from the .as" )hen the
ethane FE
<
G, propane FE
B
G, butanes FE
3
G and E
5
plus hi.her molecular
wei.ht hydrocarbons Freferred to as E
5
VG will also be remo,ed and
reco,ered as byproducts"
)he water remo,ed from both the hi.h and low pressure separators will
probably need to be processed to remo,e hydro.en sul9de before the
water can be disposed of or reused in some fashion"
&ome of the raw natural .as may be re-in2ected into the .as wells to
help maintain the .as reser,oir pressures"
)he hydrocarbon dew point is the temperature Fat a .i,en pressureG at
which the hydrocarbon components of any hydrocarbon-rich .as
mi:ture, such as natural .as, will start to condense out of the .aseous
phase" It is often also referred to as the H$P or the HE$P" )he ma:imum
temperature and the pressure at which such condensation taes place is
called the cricondentherm" )he hydrocarbon dew point is a function of
the .as composition as well as the pressure"
)he hydrocarbon dew point is uni,ersally used in the natural .as
industry as an important ;uality parameter, stipulated in contractual
speci9cations and enforced throu.hout the natural .as supply train, from
producers throu.h processin., transmission and distribution companies
to 9nal end users"
)he hydrocarbon dew point of a .as is a di0erent concept from the water
dewpoint, the latter bein. the temperature Fat a .i,en pressureG at
which water ,apor present in a .as mi:ture will condense out of the .as"
27
C'#"ter D J
28
/ollowin. are the some important processes for the reco,ery of LPG
Membrane process
Eatalytic hydro-cracin. process
$ehydration process
Eatalytic process
Me$7r#%e Proce55
)he present in,ention is a process for reco,erin. hi.h purity LPG from a
.as condensate stream, from any source such as re9nery .ases,
especially .as condensate wells which contain hydro.en, methane,
ethaneKethylene, li.ht .ases containin. heteroatoms Fsulfur, o:y.en,
nitro.en, e".", mercaptansG as well as the E
B
V
fraction ,alued as LPG and
simultaneously reco,erin. a hi.h purity hydro.en rich stream by the use
of two membranes separation units" In the present in,ention, the 9rst
membrane separation unit is located before a 9rst optional compressor
and a nocout drum and the second membrane separation unit is
located after the nocout drum with recycle of the E
B
V
rich stream from
the second membrane unit for combination with the crude LPG feed for
repassa.e throu.h the nocout drum" )he current in,ention results in
the production and reco,ery of hi.h purity LPG from the nocout drum
and the production and reco,ery of hi.h purity hydro.en retentate from
the 9rst membrane" )his hi.h purity hydro.en obtained from the 9rst
membrane unit is of suJcient purity to be utiliAed as a hydro.en stream
component for a re9nery hydroprocessin. process" )he retentate of the
second membrane unit contains mainly other li.hter hydrocarbons such
as Ei and E
<
, i"e", a E
<
!
enrichedKLPG lean stream as is .enerally utiliAed
as fuel .as"
)he
bul of the crude LPG stream is sent 9rst to a membrane separation unit
under the pressure at which it is recei,ed from its source such as 56 to
7666 psi Fno pre-compression step bein. practicedG and the crude
29
stream is di,ided into a H
<
lean and E
B
V
LPG enriched permeate stream
and a H
<
rich retentate stream" )he permeate stream, at reduced
pressure, and of reduced ,olume due to the remo,al of the H
<
and some
E
<
!
retentate stream can be fed as such to the nocout drum or can be
recompressed in a 9rst optional compressor before bein. sent to the
nocout drum" (ecause of the reduced ,olume of this stream, if a
compressor is re;uired in the present process, a smaller compressor can
be utiliAed than if the hydro.en was not remo,ed prior to the
compression step upstream of the noc-out drum" )his results is both
lower in,estment costs and lower ener.y consumption"

In one embodiment of the process of the present in,ention as presented
raw LPG feed from whate,er source is fed at whate,er pressure it is
recei,ed from its source, typically 56 to 7666 psi, ,ia line into a 9rst
membrane unit wherein it is contacted with a rubbery polymer
membrane " )he raw LPG feed is separated by the membrane into a
retentate product stream enriched in hydro.en, and into a lowerKreduced
pressure permeate stream enriched in LPG hydrocarbons and a reduced
concentration of hydro.en as compared to the feed stream" )he lower
pressure permeate stream enriched in E
B
V
LPG concentration but still
containin. some hydro.en albeit at a reduced concentration is passed
,ia line thou.h optional ,al,e to optional compressor wherein its
pressure can be increased at least bac up to the pressure of the of the
crude LPG, e".", 56 to 7666 psi and then throu.h line to nocout drum
wherein hi.h purity E
B
V
LPG is li;ui9ed and reco,ered as product ,ia line
and a ,aporous phase is reco,ered as o,erheads ,ia line and sent to a
second membrane unit where it is contacted with a rubbery polymer
membrane In the second membrane unit the ,aporous o,erheads
stream from nocout drum is separated into a retentate stream rich in
E
7
and E
<
and of reduced E
B
V
LPG content and into a reduced pressure
permeate stream rich in E
B
V
LPG" )he permeate stream is fed ,ia line
without the use of the optional compressor shown as to a point upstream
of compressor where it is combined with the permeate stream from the
9rst membrane separation unit"

In another embodiment, if the pressure of the permeate stream in line is
suJcient, compressor may be omitted" In this alternate embodiment,
the permeate is fed to nocout drum ,ia line " In the second membrane
unit , the ,aporous o,erheads stream from nocout drum is separated
into a retentate stream rich in E
7
and E
<
and of reduced E
B
V
LPG content
and into a reduced pressure permeate stream rich in E
B
V
LPG" )he
permeate stream is fed ,ia line to compressor which is employed in this
embodiment" )he compressed permeate stream is recycled ,ia line into
line for combinin. therein with the permeate from line for
introductionKreintroduction into the nocout drum "
30
-hile compressors and are identi9ed as optional, one or the other is
re;uired to repressuriAe the streamFsG reco,ered at reduced pressure as
permeate either from the 9rst membrane separation unit stream or from
the second membrane separation unit stream so as to facilitate the
processin. andKor recyclin. of these streams in the processin. circuit"
Passa.e throu.h each membrane unit results in a permeate reco,ered at
a pressure lower than that of the feed to the membrane unit"
Eompressor can be omitted if the pressure of the reduced pressure
permeate in line is still hi.h enou.h to permit e0ecti,e separation in the
nocout drum membrane unit circuit" If not, then recompression in a
compressor is necessary" If the pressure in line is suJcient without
recompression in compressor for passa.e to nocout drum and
membrane unit the permeate reco,ered from membrane unit in line will
be at yet a still lower pressure so recycle of this permeate for recycle to
the nocout drum would re;uire depressuriAation by compressor "

In the membrane separations units, .as molecules sorb Fi"e", either
absorb or adsorbG onto the polymer 9lm used as the membrane on the
feed side of the membrane, usually under pressure Fusually an applied
pressureG" )his sorption creates a concentration .radient of molecules
from the feed side to the permeate side of the membrane 9lm" Gas
molecules di0use throu.h the membrane 9lm from the feed side to the
permeate side under the inTuence of the concentration di0erence with
the sorbed materials desorbin. from the permeate face of the
membrane 9lm into the lower pressure permeate side of the membrane
separation unit" )his pressure di0erential may be the result of a hi.her
or applied pressure on the feed side of the membrane than the pressure
on the permeate side of the membrane andKor the permeate side can be
under a partial or full ,acuum to create the necessary pressure
di0erential"

In .as separation most of the membranes used are .lassy polymers such
as cellulose acetate, polysulfone, polyamide, polyimide, etc", and
combination of such polymers" In .lassy polymers the polymer molecule
is ri.idly paced in the membrane 9lm, therefore di0usion in restricted
and the di0usion rate controls the separation" Lar.er molecules ha,e
slower di0usion rates" )hus, .lassy polymer membranes can be used to
separate small molecules such as hydro.en Finetic diameter <"48 AG
from lar.er molecules such as methane Finetic diameter B"4 AG and
propane Finetic diameter 3"B AG but because of the reduced di0usion
rate the rate of separation is low"
In the reco,ery of LPG, as
practiced in the present in,ention use is made of rubbery polymer such
as polysilo:ane, polybutadiene, etc" In this rubbery state, the polymer
molecules in the membrane 9lm are paced relati,ely loosely resultin. in
31
hi.h Te:ibility of the rubbery polymer 9lm and Te:ibility between the
di0erent polymer strands that comprise the membrane" )hus, di0usion
rate di0erences between smaller molecules and lar.er molecules are
insi.ni9cant" Herein, the selecti,e separation is primarily dri,en not by
di0erentiation in molecular siAe but instead by aJnity of the membrane
for certain constituents in the feed" )he sorption on the feed side in LPG
reco,ery usin. these rubbery polymer membranes fa,ors lar.e E
B

molecules rather than the smaller hydro.en, E
7
or E
<
molecules"

(ecause of the hi.her sorption of the E
B
V
molecules, more E
B
V
molecules
sorb on the feed side resultin. in more E
B
V
molecules permeatin.
throu.h the membrane to the permeate side resultin. in the separation
@f E
B
V
molecules from the hydro.en and E
7
and E
<
molecules present in
feed" In a preferred embodiment, the process of the present in,ention
will produce a E
B
V
rich product stream that has a E
B
V
purity of at least C6
mol?, more preferably at least 46 mol?" In a preferred embodiment, the
process of the present in,ention produces a E
B
V
rich product stream
wherein the
wt? of the E
B
V
component in the E
B
V
rich product stream is at least 46 wt
? of the E
B
V
component in the hydrocarbon-containin. feed stream to
the process" More preferably the process of the present in,ention
produces a E
B
V
rich product stream wherein the wt? of the E
B
V

component in the E
B
V
product stream is at least 86 wt? of the E
B
V

component in the hydrocarbon-containin. feed stream to the process"
&imilarly, a rubbery polymer membrane
such as polysilo:ane, polybutadiene, etc", can be utiliAed in the 9rst
membrane separation unit to produce a lower molecular wei.ht
hydro.en-rich stream as a retentate at hi.h purities F.reater than C6 mol
?G and produce a E
<
V
rich permeate stream which can then be further
puri9ed for LPG reco,ery" In a preferred embodiment, the process of the
present in,ention will produce a hydro.en rich product stream that has a
hydro.en purity of at least C6 mol?, more preferably at least 46 mol?"
In a preferred embodiment, the process of the present in,ention
produces a hydro.en rich product stream wherein the wt? of the
hydro.en component in the hydro.en rich product stream is at least 36
wt? of the hydro.en component in the hydrocarbon-containin. feed
stream to the process" More preferably the process of the present
in,ention produces a hydro.en rich product stream wherein the wt? of
the hydro.en component in the hydro.en rich product stream is at least
56 wt?, and e,en more preferably at least >6 wt? of the hydro.en
component in the hydrocarbon-containin. feed stream to the process"
)he preferred rubbery polymers useful in the present process
are those which ha,e a .lass transition temperature below <6
6
E, i"e",
32
which are rubbery at room temperature or hi.her Fabout <6
6
E or hi.herG"
)he same or di0erent rubbery polymer membranes may be used in each
membrane separation unit"

C#t#(4tic H49ro r#Fi%)
A catalytic hydro cracin. process which
pro,ides for the simultaneous production of LPG and distillate
hydrocarbons" )he feedstoc is introduced into a de-nitri9cation and de-
sulfuriAation Aone and then passed directly to a hot, hi.h pressure
stripper utiliAin. a hot, hydro.en-rich strippin. .as to produce a 9rst
li;uid stream boilin. in the ran.e of the feedstoc
and a 9rst ,apor stream comprisin. hydro carbonaceous compounds
boilin. at
a temperature below the boilin. ran.e of the feedstoc" )he 9rst li;uid
stream is hydro craced in a 9rst hydro cracin. Aone and then passed
to
the denitri9cation and desulphuriAation Aone" At least a portion of the
9rst ,apor stream is condensed to produce a second li;uid stream
comprisin. hydro carbonaceous compounds boilin. at a temperature
below the
boilin. ran.e of the feedstoc" At least a portion of the second li;uid
stream is hydro craced in a second hydro cracin. Aone containin. a
second
hydro cracin. catalyst to produce LPG boilin. ran.e hydro
carbonaceous
compounds"
De'49r#tio% Proce55

In the dehydration process of .as
condensate, we obtain LPG, natural .as and other hi.her hydrocarbon
lie naphtha erosene oil etc"

In the dehydration process the .as condensate from the slu.
catcher mo,e towards the three sections"
7 .as dehydration unit
< LPG unit
B water treatment unit
In the .as dehydration unit the .as pass throu.h feed chiller, separators,
.as 9lters, molecular sie,e beds, murccury .uard beds, dust 9lter and
then it .oes to the LPG section"
33
In the LPG unit condensate from the slu. catcher re9ned after passin.
throu.h condensate chiller, condensate coalaser 9lter, deeathaniAer,
debutaniAer"
C#t#(4tic Proce55
)his in,ention relates to a catalyst for producin.
a li;ue9ed petroleum .as containin. propane or butane as a main
component by reactin. carbon mono:ide with hydro.en"
)his in,ention also
relates to a process for producin. a li;ue9ed petroleum .as containin.
propane or butane as a main component from a synthesis .as usin. the
catalyst" )his in,ention also relates to a process for producin. a li;ue9ed
petroleum .as containin. propane or butane as a main component from
a carbon-containin. startin. material such as a natural .as usin. the
catalyst"
O76ecti3e o& T'e C#t#(4tic Proce55
An ob2ecti,e of this in,ention is
to pro,ide a less deteriorati,e catalyst for producin. a li;ue9ed
petroleum .as with a lon.er catalyst life, which can produce a
hydrocarbon containin. propane or butane as a main component, i"e", a
li;ue9ed petroleum .as FLPGG, by reactin. carbon mono:ide and
hydro.en, with hi.h acti,ity, hi.h selecti,ity and hi.h yield"

Another ob2ecti,e of this in,ention is to pro,ide a process for stably
producin. LPG with a hi.h concentration of propane andKor butane from
a synthesis .as in a hi.h yield for a lon. period, usin. the catalyst" A
further ob2ecti,e of this in,ention is to pro,ide a process for stably
producin. LPG with a hi.h concentration of propane andKor butane from
a carbon-containin. startin. material such as a natural .as in a hi.h
yield for a lon. period"
)he present in,ention
pro,ides a catalyst for producin. a li;ue9ed petroleum .as, which is
used for producin. a li;ue9ed petroleum .as containin. propane or
butane as a main component by reactin. carbon mono:ide and
hydro.en, comprisin. a Pd-based methanol synthesis catalyst
component" Moreo,er, the present in,ention pro,ides a process for
producin. a li;ue9ed petroleum .as, comprisin. the step ofN
34

Reactin. carbon mono:ide and hydro.en in the presence of the catalyst
for producin. a li;ue9ed petroleum .as as described abo,e to produce a
li;ue9ed petroleum .as containin. propane or butane as a main
component"
Moreo,er, the
present in,ention pro,ides a process for producin. a li;ue9ed petroleum
.as, comprisin. the steps ofN
F7G "ro98ci%) # 54%t'e5i5 )#5 from a carbon-containin. startin.
material and at least one selected from the .roup consistin. of H
<
@, @
<
and E@
<
F&ynthesis .as production processGM and
F<G &ee9i%) t'e 54%t'e5i5 )#5 to a catalyst layer comprisin. the
catalyst for producin. a li;ue9ed petroleum .as as described abo,e to
produce a li;ue9ed petroleum .as containin. propane or butane as a
main component FLi;ue9ed petroleum .as production processG"
Herein, synthesis .asW means a
mi:ed .as comprisin. hydro.en and carbon mono:ide, and is not limited
to a mi:ed .as consistin. of hydro.en and carbon mono:ide" A synthesis
.as may be, for e:ample, a mi:ed .as comprisin. carbon dio:ide, water,
methane, ethane, ethylene and so on" A synthesis .as produced by
reformin. a natural .as .enerally contains, in addition to hydro.en and
carbon mono:ide, carbon dio:ide and water ,apor" A synthesis .as may
be a coal .as produced by coal .asi9cation or a water .as produced
from a coal coe"
A catalyst for
producin. a li;ue9ed petroleum .as accordin. to this in,ention
comprises a Pd-based methanol synthesis catalyst as a methanol
synthesis catalyst component" )he catalyst for producin. a li;ue9ed
petroleum .as accordin. to this in,ention can
produce a hydrocarbon containin. propane or butane as a main
component, i"e", a li;ue9ed petroleum .as FLPGG with hi.h acti,ity, hi.h
selecti,ity and a hi.h yield, by reactin. carbon mono:ide and hydro.en,
and has a lon.er catalyst life with less deterioration"
/irst, on the methanol synthesis catalyst
component, methanol is formed from carbon mono:ide and hydro.en,
while dimethyl ether is also formed by dehydro-dimeriAation of
methanol" )hen, methanol thus formed is con,erted to a lower-ole9n
hydrocarbon comprisin. propylene or butene as a main component at an
acti,e site in a pore in the Aeolite catalyst component" In the reaction,
methanol would be dehydrated to .i,e a carbene FH
<
ENG, which is
35
sub2ected to polymeriAation to .i,e a lower ole9n" )he lower ole9n thus
.enerated is released from the pore in the Aeolite catalyst component
and is rapidly hydro.enated on the methanol synthesis catalyst to .i,e a
paraJn comprisin. propane or butane as a main component, i"e", LPG"

Herein, a methanol synthesis catalyst componentW means a compound
which can act as a catalyst in the reaction of E@V<H
<
XEH
B
@H" And a
Aeolite catalyst componentW means a Aeolite which can act as a catalyst
in a condensation reaction of methanol into a hydrocarbon andKor a
condensation reaction of dimethyl ether into a hydrocarbon"
As a methanol synthesis catalyst, a EuYZn-based
catalyst Fa composite o:ide containin. Eu and ZnG and a ZnYEr-based
catalyst Fa composite o:ide containin. Zn and ErG are widely used"
Howe,er, suJcient catalyst performance cannot be always achie,ed
when usin., in place of a Pd-based methanol synthesis catalyst, a EuY
Zn-based methanol synthesis catalyst or a ZnYEr-based methanol
synthesis catalyst as a methanol synthesis catalyst component in a
catalyst for producin. a li;ue9ed petroleum .as in production of LPG by
reactin. carbon mono:ide and hydro.en" /urthermore, suJcient catalyst
performance cannot be always achie,ed when usin. a Aeolite as a
catalyst component in case a Pd-based methanol synthesis catalyst is
used as a methanol synthesis catalyst component in a catalyst for
producin. a li;ue9ed petroleum .as"
)he reaction of carbon mono:ide and hydro.en for producin. LPG
depends on a ,ariety of factors" )herefore, the reason why the catalyst
for producin. a li;ue9ed petroleum .as of this in,ention e:hibits
e:cellent performance is not clear, but the followin.s mi.ht be assumed"
A reaction of carbon mono:ide and hydro.en for formin. methanol
FE@V<H
<
XEH
B
@HG is an e;uilibrium reaction" And, the e;uationN
E@V<H
<
PEH
B
@HV766 L indicates that the e;uilibrium of methanol
formation is more ad,anta.eous as a temperature is lower" Howe,er,
when reactin. carbon mono:ide and hydro.en to produce LPG, methanol
formed on a methanol synthesis catalyst component is rapidly con,erted
to a lower-ole9n hydrocarbon at
an acti,e site in a pore in the Aeolite catalyst component" )here are,
therefore, substantially no restrictions to the e;uilibrium of methanol
formation" )hus, it is not necessarily re;uired to conduct the reaction at
a lower temperature for achie,in. a suJciently hi.h yield" @n the other
hand, it is ad,anta.eous to conduct the reaction at a hi.her temperature
in terms of a reaction rate" In the li.ht of acti,ity of the Aeolite catalyst
component, it is desirable that the methanol synthesis catalyst
component has .reat heat-resistance to some de.ree" &peci9cally, the
36
methanol synthesis catalyst can be used preferably at <C6O E" or hi.her,
more preferably B66O E" or hi.her, further preferably B<6O E" or hi.her"
Amon. methanol synthesis catalysts, a EuYZn-based catalyst is
.enerally used at a relati,ely lower temperature Fabout <B6 to B66O E"G
and its heat resistance is not so hi.her than other methanol synthesis
catalysts" -hen producin. LPG by reactin. carbon mono:ide and
hydro.en at an ele,ated temperature for achie,in. hi.her acti,ity and
hi.her yield, it is not necessarily preferable to use a con,entional EuY
Zn-based catalyst as a methanol synthesis catalyst component"

@n the other hand, amon. methanol synthesis catalysts, a ZnYEr-based
catalyst is .enerally used at a relati,ely hi.her temperature Fabout <56
to 366O E"G" )here does not appear to be a particular problem in usin. a
ZnYEr-based catalyst as a methanol synthesis catalyst component when
main. a reaction temperature hi.her"
Howe,er, when producin. LPG by reactin. carbon mono:ide and
hydro.en, a methanol synthesis catalyst component is re;uired to act as
a catalyst in a hydro.enation reaction of an ole9n into a paraJn" A
con,entional ZnYEr-based catalyst does not, howe,er, ha,e suJcient
hydro.enatin. ability" )hus, when producin. LPG by reactin. carbon
mono:ide and hydro.en, it is not necessarily preferable to use a
con,entional ZnYEr-based catalyst as a methanol synthesis catalyst
component"
A Pd-based methanol synthesis catalyst,
which is used as a methanol synthesis catalyst component in this
in,ention, is nown to act as a catalyst in the methanol synthesis
reaction FE@V<H
<
XEH
B
@HG, but it is not widely used as a methanol
synthesis catalyst" Howe,er, in the li.ht of its hi.h thermal stability and
hydro.enatin. ability, it is suitable as a methanol synthesis catalyst
component in a catalyst used in producin. a li;ue9ed petroleum .as by
reactin. carbon mono:ide and hydro.en, particularly at an ele,ated
reaction temperature"

As a methanol synthesis catalyst component, it is particularly preferable
to use a catalyst in which 6"7 to 76 wt ? Pd is supported on a silica
support ha,in. a speci9c surface area of 3<6 m
<
K. or more"

Howe,er, an important factor for a Aeolite catalyst component may not
37
be limited to a pore siAe and a &i@
<
KAl
<
@
B
molar ratio" @ther factors such
as an acid stren.th, a pore structure and a crystal siAe may be also
important for a Aeolite catalyst component" Performance of a catalyst for
producin. a li;ue9ed petroleum .as, particularly its acti,ity and LPG
selecti,ity, stron.ly depends on the balance amon. three parameters,
the ability of a methanol synthesis catalyst component to form
methanol, the ability of a methanol synthesis catalyst component to
hydro.enate an ole9n into a paraJn, and the ability of a Aeolite catalyst
component to form a hydrocarbon from methanol, and they are thou.ht
to be inTuenced by a ,ariety of factors"
A nicel catalyst, for e:ample, is
widely used as a catalyst in a hydro.enation reaction of an ole9n into a
paraJn" (ut if a substance cannot act as a catalyst in a methanol
synthesis reaction FE@V<H
<
XEH
B
@HG, it is, of course, unpreferable as a
methanol synthesis catalyst component used in this in,ention"
)he reaction conditions are
also important for stably producin. LPG for a lon. period with a hi.h
con,ersion, a hi.h selecti,ity and a hi.h yield by reactin. carbon
mono:ide and hydro.en in the presence of a catalyst for producin. a
li;ue9ed petroleum .as of this in,ention" )his in,ention may be
particularly e0ecti,e when carbon mono:ide and hydro.en are reacted
at a reaction temperature of B66O E" to 3<6O E" Fboth inclusi,eG and
under a reaction pressure of <"< MPa to 76 MPa Fboth inclusi,eG"

Accordin. to this in,ention, for e:ample, e,en after 56 hours from the
reaction be.innin., the catalyst can e:hibit such a hi.h acti,ity that a
con,ersion of E@ is 56? or more, speci9cally >6? or more, more
speci9cally C6? or more, further speci9cally 46? or more, to .i,e a
hydrocarbon with the total content of propane and butane of >6? or
more, speci9cally C6? or more"
/urthermore, accordin. to this
in,ention, LPG with the total content of propane and butane of 86 mol ?
or more, speci9cally 85 mol ? or more Fincludin. 766 mol ?G, for
e:ample, can be produced" And, accordin. to this in,ention, LPG with a
content of propane of 56 mol ? or more, speci9cally >6 mol ? or more
Fincludin. 766 mol ?G, for e:ample, can be produced"
Det#i(e9 De5cri"tio%
%:amples of a Pd-based methanol synthesis
catalyst component include Pd, preferably metallic Pd, supported on a
support" In the li.ht of catalytic acti,ity, Pd is preferably supported on a
support in a hi.hly dispersed manner"
38
)he amount of supported Pd in a Pd-based methanol synthesis catalyst
component is preferably 6"7 wt ? or more, more preferably 6"5 wt ? or
more, particularly preferably 7 wt ? or more" In the li.ht of
dispensability and economical eJciency, the amount of supported Pd in
a Pd-based methanol synthesis catalyst component is preferably 76 wt
? or less, more preferably 4 wt ? or less, particularly preferably > wt ?
or less" (y ad2ustin. the amount of supported Pd in a Pd-based methanol
synthesis catalyst component within the abo,e ran.e, propane andKor
butane can be produced with a hi.her con,ersion, a hi.her selecti,ity
and a hi.her yield"
(y ad2ustin. the amount of
supported Pd to be 6"7 wt ? or more, more preferably 6"5 wt ? or more,
particularly preferably 7 wt ? or more, carbon mono:ide and hydro.en
can be con,erted into methanol with a hi.her con,ersion, and methanol
produced can be con,erted into a li;ue9ed petroleum .as comprisin.
propane or butane as a main component with a hi.her selecti,ity" @n the
other hand, by ad2ustin. the amount of supported Pd to be 76 wt ? or
less, more preferably 4 wt ? or less, particularly preferably > wt ? or
less, methanol produced can be con,erted into a li;ue9ed petroleum .as
comprisin. propane or butane as a main component with a hi.her
con,ersion"
A support for Pd may be selected from nown supports
without limitation" %:amples of a support include silica Fsilicon dio:ideG,
alumina, silica-alumina, carbon Facti,ated charcoalGM and o:ides of
Airconium, titanium, cerium, lanthanum, iron or the lie, and composite
o:ides containin. two or more types of these metals, and composite
o:ides containin. one or more types of these metals and one or more
types of other metals" &uch supports may be used alone or in
combination of two or more"
A support is preferably neutral to
basic" (y usin. a neutral to basic support, hi.her acti,ity and selecti,ity
can be achie,ed in methanol synthesis"
Amon. others, a preferable support for Pd is
silica" (y usin. silica as a support, methanol can be produced with a
hi.her selecti,ity and a hi.her yield without producin. a hydrocarbon
and carbon dio:ide as a by-product"
A silica support preferably has a speci9c surface area of 3<6
m
<
K. or more, more preferably 356 m
<
K. or more, particularly preferably
3C5 m
<
K. or more,
further preferably 566 m
<
K. or more" (y usin. a silica support ha,in. a
speci9c surface area within the abo,e ran.e, hi.her catalytic acti,ity can
39
be achie,ed and propane andKor butane can be produced with a hi.her
con,ersion and a hi.her yield"
)he upper limit of a speci9c surface area of a silica
support is not particularly restricted, but is .enerally about B66 m
<
K."
A silica
support preferably has an a,era.e pore siAe of 5"5 nm or less, more
preferably 5 nm or less, particularly preferably 3"5 nm or less, further
preferably 3 nm or less" (y usin. a silica support ha,in. an a,era.e pore
siAe within the abo,e ran.e, hi.her catalytic acti,ity can be achie,ed
and propane andKor butane can be produced with a hi.her con,ersion
and a hi.her yield"
)he lower limit of an
a,era.e pore siAe of a silica support is not particularly restricted, but is
.enerally about 7 nm"
-hen
silica is used as a support, it can support one or more types of basic
metals, in addition to Pd" (y supportin. a basic metal in addition to Pd
on a silica support, catalytic acti,ity may be further impro,ed and
propane andKor butane may be produced with a hi.her con,ersion and a
hi.her yield"
Herein, a basic metalW means a
metal whose o:ide is a basic o:ide"
%:amples of a basic metal include alali metals,
alaline earth metals, lanthanoid metals and low-,alence transition
metalsM speci9cally, Ea, &r, La, #d, M., Li, #a and the lie" (asic metals
may be used alone or in combination of two or more"
Amon. others, a preferable basic metal
is Ea" (y usin. Ea as a basic metal, dispensability of Pd can be
impro,ed, and thus hi.her catalytic acti,ity can be achie,ed and
propane andKor butane can be produced with a hi.her con,ersion and a
hi.her yield" )he total amount of basic metals supported on a Pd-based
methanol synthesis catalyst component is preferably 6"67 wt ? or more,
more preferably 6"5 wt ? or more" )he amount of supported basic
metals within the abo,e ran.e can result in suJcient e0ect of
supportin. a basic metal on silica as described abo,e"
@n the other hand, the total
amount of basic metals supported on a Pd-based methanol synthesis
catalyst component is preferably 5 wt ? or less, more preferably B wt ?
or less" (y ad2ustin. the amount
40
of supported basic metals within the abo,e ran.e, dispensability of Pd
can be impro,ed, and thus hi.her catalytic acti,ity can be achie,ed and
propane andKor butane can be produced with a hi.her con,ersion and a
hi.her yield"

In this in,ention, a Pd-based methanol synthesis catalyst component
may be a silica support on which other components, in addition to Pd
and a basic metal, are supported as lon. as the desired e0ects of the
catalyst are maintained"

A Pd-based methanol synthesis catalyst component in which Pd, a basic
metal or the lie are supported on silica, may be prepared by a nown
method such as an impre.nation method and a precipitation method"
#e:t, there will be described a process for producin. a li;ue9ed
petroleum .as comprisin. propane or butane, preferably propane, as a
main component by reactin. carbon mono:ide and hydro.en usin. a
catalyst for producin. a li;ue9ed petroleum .as accordin. to this
in,ention as described abo,e"
A reaction temperature is preferably
B66O E" or hi.her, more preferably B<6O E" or hi.her, particularly
preferably B36O E" or hi.her" (y controllin. a reaction temperature within
the abo,e ran.e, propane andKor butane can be produced with a hi.her
con,ersion and a hi.her yield"

@n the other hand, a reaction temperature is preferably 3<6O E" or lower,
more preferably 366O E" or lower, in the li.ht of the restricti,e
temperature for the use of the catalyst and easy remo,al or reco,ery of
the reaction heat" A reaction pressure is preferably <"< MPa or hi.her,
more preferably <"5 MPa or hi.her, particularly preferably B MPa or
hi.her" (y controllin. a reaction pressure within the abo,e ran.e,
propane andKor butane can be produced with a hi.her con,ersion and a
hi.her yield, and the deterioration with time of the catalyst can be
reduced further, so that propane andKor butane can be produced for a
further lon.er period with a hi.her con,ersion and a hi.her yield" In
particular, by controllin. a reaction pressure to be B MPa or hi.her,
propane andKor butane can be produced with a suJciently hi.h
con,ersion and a suJciently hi.h yield"
@n the other hand, a reaction pressure is preferably 76 MPa or lower,
more preferably C MPa or lower, in the li.ht of economical eJciency"
A .as space ,elocity is preferably 566 hr
[7
or more, more preferably
7566 hr
[7
or more, in the li.ht of economical eJciency" In addition, a .as
space ,elocity is preferably 76666 hr
[7
or less, more preferably 5666 hr
[7
or less, in order that each of a Pd-based methanol synthesis catalyst
41
component and a \-Aeolite catalyst component may .i,e a contact time
achie,in. a further suJcient con,ersion" A
concentration of carbon mono:ide in a .as fed into a reactor is
preferably <6 mol ? or more, more preferably <5 mol ? or more, in the
li.ht of ensurin. a pressure Fpartial pressureG of carbon mono:ide
re;uired for the reaction in a .as fed into the reactor, and impro,in. a
speci9c producti,ity of the materials" In addition, a concentration of
carbon mono:ide in a .as fed into a reactor is preferably 35 mol ? or
less, more preferably 36 mol ? or less, in the li.ht of a further
suJciently hi.h con,ersion of carbon mono:ide"
A concentration of hydro.en in a
.as fed into a reactor is preferably 7"< moles or more, more preferably
7"5 moles or more per one mole of carbon mono:ide, in order that
carbon mono:ide may react more suJciently" In addition, a
concentration of hydro.en in a .as fed into a reactor is preferably B
moles or less, more preferably <"5 moles or less per one mole of carbon
mono:ide, in the li.ht of economical eJciency" In some cases,
preferably, a concentration of hydro.en in a .as fed into a reactor may
be reduced to about 6"5 moles per one mole of carbon mono:ide" A .as
fed into a reactor may contain carbon dio:ide in addition to carbon
mono:ide and hydro.en, which are startin. materials of the reaction" (y
recyclin. carbon dio:ide dischar.ed from the reactor, or by addin. the
correspondin. amount of carbon dio:ide, formation of carbon dio:ide
from carbon mono:ide by a shift reaction in the reactor can be
substantially reduced or be eliminated"
A .as fed into a reactor can contain water ,apor" And a .as fed into a
reactor can contain an inert .as" A .as fed into a reactor can be
di,idedly fed to the reactor so as to control a reaction temperature" )he
reaction can be conducted in a 9:ed bed, a Tuid bed, a mo,in. bed or
the lie, and can be preferably selected, tain. both of control of a
reaction temperature and a re.eneration method of the catalyst into
account" /or e:ample, a 9:ed bed may include a ;uench type reactor
such as an internal multista.e ;uench type, a multi tubular type reactor,
a multista.e type reactor ha,in. a plurality of internal heat e:chan.ers
or the lie, a multista.e coolin. radial Tow type, a double pipe heat
e:chan.e type, an internal coolin. coil type, a mi:ed Tow type, and
other types of reactors"
-hen used, a catalyst for producin. a li;ue9ed petroleum .as accordin.
to the present in,ention can be diluted with silica, alumina or an inert
and stable heat conductor for controllin. a temperature" In addition,
when used, a catalyst for producin. a li;ue9ed petroleum .as accordin.
to the present in,ention can be applied to the surface of a heat
e:chan.er for controllin. a temperature"
42
Process for Producin. a Li;ue9ed Petroleum Gas from a Earbon-
Eontainin. &tartin. Material"In this in,ention, a synthesis .as can be
used as a startin. .as for producin. a li;ue9ed petroleum .as FLPGG"
#e:t, there will be described an embodiment of a process for producin.
LPG accordin. to this in,ention, comprisin. the steps of producin. a
synthesis .as from a carbon-containin. startin. material Fsynthesis .as
production processG and then producin. LPG from the obtained synthesis
.as usin. a catalyst of this in,ention Fli;ue9ed petroleum .as production
processG"
S4%t'e5i5 G#5 Pro98ctio% Proce55
In a synthesis .as production process, a synthesis .as is produced from
a carbon-containin. startin. material and at least one selected from the
.roup consistin. of H
<
@, @
<
and E@
<
"A carbon-containin. substance
which can react with at least one selected from the .roup consistin. of
H
<
@, @
<
and E@
<
to form H
<
and E@, can be used as a carbon-containin.
startin. material" A substance nown as a raw material for a synthesis
.as can be used as a carbon-containin. startin. materialM for e:ample,
lower hydrocarbons such as methane and ethane, a natural .as, a
naphtha, a coal, and the lie can be used"
&ince a catalyst is .enerally used in a synthesis .as production process
and a li;ue9ed petroleum .as production process in this in,ention, a
carbon-containin. startin. material Fa natural .as, a naphtha, a coal and
so onG preferably contains less catalyst poisonin. components such as
sulfur and a sulfur compound" -hen a carbon-containin. startin.
material contains a catalyst poisonin. component, a step of remo,in.
the catalyst poisonin. component such as de,ocaliAation can be
conducted before a synthesis .as production process, if necessary"
A synthesis .as can be produced by reactin. the abo,e carbon-
containin. startin. material with at least one selected from the .roup
consistin. of H
<
@, @
<
and E@
<
in the presence of a catalyst for producin.
a synthesis .as Freformin. catalystG"A synthesis .as can be produced by
a nown method" -hen a natural .as FmethaneG is used as a startin.
material, for e:ample, a synthesis .as can be produced by a water-,apor
reformin. method, an auto thermal reformin. method or the lie" In
these methods, water ,apor re;uired for a water-,apor reformin.,
o:y.en re;uired for an auto thermal reformin., or the lie can be fed, if
43
necessary" -hen a coal is used as a startin. material, a synthesis .as
can be produced usin. an aeratin. .asi9cation furnace"
/or e:ample, a shift reactor may be placed downstream of a reformer,
which is a reactor for producin. a synthesis .as from the abo,e startin.
materials, so that a synthesis .as composition can be ad2usted by a shift
reaction FE@VH
<
@XE@
<
VH
<
G"In this in,ention, a preferable composition
of a synthesis .as produced in a synthesis .as production process is a
molar ratio of H
<
KE@ is CKB]<"B in terms of the stoichiometry for a lower
paraJn production, and a ratio
of hydro.en to carbon mono:ide FH
<
KE@M by moleG in a synthesis .as
produced is preferably 7"< to B" A ratio of hydro.en to carbon mono:ide
FH
<
KE@M by moleG in a synthesis .as is preferably 7"< or more, more
preferably 7"5 or more, in order that carbon mono:ide may react
suitably, since hydro.en is .enerated by a shift reaction caused by water
.enerated in a con,ersion reaction from a synthesis .as to LPG" It is only
necessary to feed hydro.en in such an amount that carbon mono:ide
can react suitably to form a li;ue9ed petroleum .as comprisin. propane
or butane as a main component, and e:cessi,e hydro.en may increase
the total pressure of a startin. .as unnecessarily, leadin. to a lower
economical eJciency" )hus, a ratio of hydro.en to carbon mono:ide
FH
<
KE@M by moleG in a synthesis .as is preferably B or less, more
preferably <"5 or less"
A
concentration of carbon mono:ide in a synthesis .as produced is
preferably <6 mol ? or more, more preferably <5 mol ? or more, in the
li.ht of ensurin. a pressure Fpartial pressureG of carbon mono:ide
suitable for a con,ersion reaction from a synthesis .as to LPG, and
impro,in. a speci9c producti,ity of the materials" In addition, a
concentration of carbon mono:ide in a synthesis .as produced is
preferably 35 mol ? or less, more preferably 36 mol ? or less, in the
li.ht of a further suJciently hi.h con,ersion of carbon mono:ide in a
con,ersion reaction from a synthesis .as to LPG"A synthesis .as ha,in.
the abo,e composition can be produced by appropriately selectin.
reaction conditions such as a feedin. ratio of a carbon-containin.
startin. material and at least one material selected from the .roup
consistin. of steam FwaterG, o:y.en and carbon dio:ide, a ind of a
catalyst for producin. a synthesis .as used, and others"

/or e:ample, a synthesis .as can be produced usin. a .as whose
composition is steamKmethane Fmolar ratioG of 7 and carbon
dio:ideKmethane Fmolar ratioG of 6"3 as a startin. .as under the
operation conditions of a reaction temperature Fan outlet temperature of
a catalyst layerG of 466 to 866O E", a reaction pressure of 7 to 3 MPa, a
44
.as space ,elocity FGH&IG of <6666 hr
[7
, in an e:ternal heatin. multi
tubular tubular reactor type apparatus 9lled with a catalyst, a Ru or RhKa
ma.nesia made the surface area smaller by sinterin." -hen usin. steam
for reformin. in a synthesis .as production, a ratio of steamKraw material
carbon F&KEG is preferably 7"5 or less, more preferably 6"4 to 7"<, in the
li.ht of an ener.y eJciency" (ut such a low &KE ,alue may lead to the
considerable possibility of carbon precipitation formation"
%:amples of the metal o:ide in this catalyst include those containin. at
least one metal such as M., Ea, (a, Zn, Al, Zr and La" An e:ample of
such a metal o:ide is ma.nesia FM.@G"
In a process in which methane and steam are reacted Fsteam reformin.G,
the reaction is represented by the followin. formula FiGN
EH
3
VH
<
@^BH
<
VE @ FiG
In a process in which methane and carbon dio:ide are reacted FE@
<
reformin.G, the reaction is represented by the followin. formula FiiGN
EH
3
VE@
<
^<H
<
V< E@ FiiG
In a process in which methane, steam and carbon dio:ide are reacted
FsteamKE@
<
mi:ed reformin.G, the reaction is represented by the
followin. formula FiiiGN
BEH
3
V<H
<
@VE@
<
_`4H
<
V3E@ FiiiG
/or steam reformin. usin. the abo,e catalyst, a reaction temperature is
preferably >66 to 7<66O E", more preferably >66 to 7666O E", and a
reaction pressure is preferably 6"684 MPaG to B"8 MPaG, more preferably
6"38 MPaG to <"8 MPaG FG indicates that a ,alue is a .au.e pressureG"
-hen the steam reformin. is conducted with a 9:ed bed, a .as space
,elocity FGH&IG is preferably 7,666 to 76,666 hr
[7
, more preferably <,666
to 4,666 hr
[7
" A rate of steam to a carbon-containin. startin. material is
preferably 6"5 to < moles, more preferably 6"5 to 7"5 moles, further
preferably 6"4 to 7"< moles of steam FH
<
@G per one mole of carbon in the
carbon-containin. startin. material Fe:cludin. E@
<
G"In a li;ue9ed
petroleum .as production process, a lower-paraJn-containin. .as, which
comprises propane or butane as a main component of the hydrocarbon
contained therein, is produced from the synthesis .as obtained in the
abo,e synthesis .as production process, by usin. a catalyst for
producin. a li;ue9ed petroleum .as accordin. to the present in,ention"
And then, water is separated from the lower-paraJn-containin. .as
produced, as necessary, and subse;uently a low-boilin. component
ha,in. a lower boilin. point or a lower sublimation point than the boilin.
point of propane Funreacted startin. materials, hydro.en and carbon
45
mono:ideM by-products, carbon dio:ide, ethane, ethylene and methaneM
and so onG and a hi.h-boilin. component ha,in. a hi.her boilin. point
than the boilin. point of butane Fby-products, hi.h-boilin. paraJn
.asesG are, if necessary, separated from the lower-paraJn-containin.
.as, so as to obtain a li;ue9ed petroleum .as FLPGG comprisin. propane
or butane as a main component" If necessary, the .as may be
pressuriAed andKor cooled so as to obtain a li;ue9ed petroleum .as"
In a li;ue9ed petroleum .as production process, carbon mono:ide and
hydro.en are reacted in the presence of the abo,e catalyst for producin.
a li;ue9ed petroleum .as of this in,ention, to produce a paraJn
comprisin. propane or butane as a main component, preferably a
paraJn comprisin. propane as a main component"In this case, a .as fed
into a reactor is the synthesis .as produced in the abo,e synthesis .as
production process" )he .as fed into a reactor may contain, in
addition to carbon mono:ide and hydro.en, other components such as
carbon dio:ide, water, methane, ethane, ethylene and an inert .as" )he
.as fed into a reactor may be a .as obtained by addin. carbon
mono:ide, hydro.en or other components, if necessary, to the synthesis
.as produced in the abo,e synthesis .as production process" And the
.as fed into a reactor may be a .as obtained by separatin. a certain
component, as necessary, from the synthesis .as produced in the abo,e
synthesis .as production process"
A .as fed
into a reactor may comprise carbon dio:ide, in addition to carbon
mono:ide and hydro.en, which are startin. materials for producin. a
lower paraJn" As the carbon dio:ide, by recyclin. carbon dio:ide
dischar.ed from the reactor, or by usin. the correspondin. amount of
carbon dio:ide, formation of carbon dio:ide from carbon mono:ide by a
shift reaction in the reactor can be substantially reduced or be
eliminated"
A .as fed into a reactor may comprise water ,apor"
A reaction temperature is preferably B66O E" or hi.her, more preferably
B<6O E" or hi.her, particularly preferably B36O E" or hi.her" @n the other
hand, as described abo,e, a reaction temperature is preferably 3<6O E"
or lower, more preferably 366O E" or lower"
A reaction pressure is preferably <"< MPa or hi.her,
more preferably <"5 MPa or hi.her, particularly preferably B MPa or
hi.her" @n the other hand, as described abo,e, a reaction pressure is
preferably 76 MPa or lower, more preferably C MPa or lower"
46
A .as space ,elocity is
preferably 566 hr
[7
or more, more preferably 7566 hr
[7
or more" @n the
other hand, as described abo,e, a .as space ,elocity is preferably 76666
hr
[7
or less, more preferably 5666 hr
[7
or less"
A .as fed into a reactor can be di,idedly fed to the reactor so
as to control a reaction temperature" )he reaction can be conducted in a
9:ed bed, a Tuid bed, a mo,in. bed or the lie, and can be preferably
selected, tain. both of control of a reaction temperature and a
re.eneration method of the catalyst into account" /or e:ample, a 9:ed
bed may include a ;uench type reactor such as an internal multista.e
;uench type, a multi tubular type reactor, a multista.e type reactor
ha,in. a plurality of internal heat e:chan.ers or the lie, a multista.e
coolin. radial Tow type, a double pipe heat e:chan.e type, an internal
coolin. coil type, a mi:ed Tow type, and other types of reactors"
-hen used, a catalyst
for producin. a li;ue9ed petroleum .as accordin. to the present
in,ention can be diluted with
silica, alumina or an inert and stable heat conductor for controllin. a
temperature" In addition, when used, a catalyst for producin. a li;ue9ed
petroleum .as accordin. to the present in,ention can be applied to the
surface of a heat e:chan.er for controllin. a temperature"
A lower-paraJn-
containin. .as produced in the li;ue9ed petroleum .as production
process comprises a hydrocarbon containin. propane or butane as a
main component" In the li.ht of li;uefaction properties, it is preferable
that the total content of propane and butane is hi.her in a lower-
paraJn-containin. .as" Accordin. to this in,ention, there can be
obtained a lower-paraJn-containin. .as ha,in. a content of propane
and butane of 56 mol ? or more, preferably >6 mol ? or more, more
preferably C6 mol ? or more Fincludin. 766 mol ?G to the hydrocarbon
contained therein, in total" /urthermore, a lower-paraJn-containin. .as
produced in the li;ue9ed petroleum .as production process preferably
contains more propane in comparison with butane, in the li.ht of
inTammability and ,apor pressure properties"
)hus, water, a low-boilin. component and a hi.h-boilin.
component are, as necessary, separated from a lower-paraJn-
containin. .as produced, so as to obtain a li;ue9ed petroleum .as FLPGG
comprisin. propane or butane as a main component" &eparation of
water, a low-boilin. component or a hi.h-boilin. component can be
conducted in accordance with a nown method"
-ater can be separated by, for e:ample, li;uid-li;uid separation"
47
A low-boilin. component can be separated by, for e:ample, .as-li;uid
separation, absorption separation or distillationM more speci9cally, .as-
li;uid separation at an ambient temperature under increased pressure,
absorption separation at an ambient temperature under increased
pressure, .as-li;uid separation with coolin., absorption separation with
coolin., or combination thereof" Alternati,ely, for this purpose,
membrane separation or adsorption separation can be conducted, or
these in combination with .as-li;uid separation, absorption separation or
distillation can be conducted" A .as reco,ery process commonly
employed in an oil factory Fdescribed in @il Re9nin. ProcessesW, applied
to separation of a low-boilin. component"A preferable method of
separation of a low-boilin. component is an absorption process where a
li;ue9ed petroleum .as comprisin. propane or butane as a main
component is absorbed into an absorbent li;uid such as a hi.h-boilin.
paraJn .as ha,in. a hi.her boilin. point than butane, and a .asoline"A
hi.h-boilin. component can be separated by, for e:ample, .as-li;uid
separation, absorption separation or distillation"
/or consumer use, it is preferable that a content of a low-boilin.
component in the LPG is reduced to 5 mol ? or less Fincludin. 6 mol ?G
by separation, for e:ample, in the li.ht of safety in use")he total content
of propane and butane in the LPG
thus produced may be 86 mol ? or more, more preferably 85 mol ? or
more Fincludin. 766 mol ?G" And a content of propane in the LPG
produced may be 56 mol ? or more, more preferably >6 mol ? or more
Fincludin. 766 mol ?G" )hus, accordin. to this in,ention, LPG ha,in. a
composition suitable for a propane .as, which is widely used as a fuel for
household and business use, can be produced"
In this in,ention, a low-boilin. component separated from the lower-
paraJn-containin. .as can be recycled as a startin. material for the
synthesis .as production process"A low-boilin. component separated
from the lower-paraJn-containin. .as includes substances which can be
recycled as startin. materials for a synthesis .as production processM for
e:ample, methane, ethane, ethylene and so on" And carbon dio:ide in
the low-boilin. component can be bac to a synthesis .as by a E@
<
reformin. reaction" In addition, a low-boilin. component includes
unreacted startin. materials such as hydro.en and carbon mono:ide"
)herefore, the low-boilin. component separated from the lower-paraJn-
containin. .as may be recycled as a startin. material for a synthesis .as
production process, leadin. to reduce a speci9c producti,ity of the
materials"
)he whole low-boilin. components separated from a lower-paraJn-
containin. .as can be recycled to a synthesis .as production process"
Alternati,ely, part of the low-boilin. components may be remo,ed
48
outside the system, while the rest of low-boilin. components may be
recycled to a synthesis .as production process" Low-boilin. components
can be recycled to a synthesis .as production process after separatin.
only desired components"
In a synthesis .as production process, a content of a low-boilin.
component in a .as fed into a reformer, which is a reactorM in other
words, a content of a recycled material may be determined as
appropriate, and it may be, for e:ample, 36 to C5 mol ?"
/or the purpose of recyclin. a low-boilin. component, a nown
techni;ue, e".", appropriately pro,idin. a recycle line with a
pressuriAation means can be employed"
I%985tri#( A""(ic#7i(it4
As described abo,e, a catalyst for producin. a li;ue9ed petroleum .as
accordin. to the present in,ention is a less deteriorati,e catalyst with a
lon.er catalyst life, which can produce a hydrocarbon containin.
propane or butane as a main component, i"e", a li;ue9ed petroleum .as
FLPGG, by reactin. carbon mono:ide and hydro.en, with hi.h acti,ity,
hi.h selecti,ity and hi.h yield" )herefore, by usin. the catalyst of this
in,ention, propane andKor butane can be stably produced for a
lon. period with hi.h acti,ity, hi.h selecti,ity and hi.h yield, from a
carbon-containin. startin. material such as a natural .as or a synthesis
.as" In other words, by usin. the catalyst of this in,ention, a li;ue9ed
petroleum .as with a hi.h concentration of propane andKor butane can
be stably produced for a lon. period with hi.h yield, from a carbon-
containin. startin. material such as a natural .as or a synthesis .as"
49
C'#"ter DK
50
G#5 )#5 e=c'#%)er
Introduction
-ithin the contact section of an LPG reco,ery plant
heat is .enerated from the e:othermic reaction of LPG"
)he multi-sta.e nature of the process re;uires that this
heat is remo,ed from the process .as in order to
obtain the hi.hest possible con,ersion eJciency" In a
.as condensate plant much of this e:cess heat is used
to .enerate hi.h pressure steam" &ome of the heat is
also used to reheat the process .ases, such the .as
returnin. from the intermediate absorption system" In
a metallur.ical acid plant most of the heat is use to
reheat either the cold .as comin. from the .as
cleanin. system or reheatin. the .as from the
intermediate absorption system"
)he transfer of heat from one process .as to another .as is done in a
.as-to-.as heat e:chan.er, so called because .as is Towin. on both the
shell and tube side of the heat e:chan.er" A .as-to-.as heat e:chan.er
usually taes the form of a ,ertical shell and tube heat e:chan.er"
Iariations of the standard desi.n are horiAontal units, plate type heat
e:chan.ers and heat e:chan.ers that are located inside the con,erter
,essel"
51
Eon,entional Gas-to-Gas Heat %:chan.ers
)he con,entional .as-to-.as heat e:chan.er is ,ertical shell and
tube heat e:chan.er with sin.le se.mental baaes" )hese e:chan.ers
are typically o,er desi.ned for the intended duty because of the
followin.N
&in.le se.mental baaes create a dead Aones in the shell side Tow
path
#oAAle orientations are restricted due to the sin.le se.mental
baaes
Gas enterin. the shell side impin.es only one side of the tube
bundle
Hi.h thermal stresses are induced by the cross Tow arran.ement
Lar.e tube bundles maes it more diJcult to obtain uniform Tow
on the shell and tube side
Hi.h shell side pressure drops re;uired to obtain acceptable heat
transfer coeJcients
#on-uniform and non-symmetrical temperature pro9les occur on
the shell side
In a heat e:chan.er with sin.le se.mental baaes, .as will Tow across
the tube bundle 9rst and then parallel to the tubes before encounterin.
the ne:t baae
which forces the .as bac across the tubes" )he di0erent Tow patterns
on the shell side maes it diJcult to desi.n and predict heat transfer
coeJcients"
)he non-uniform temperature pro9le across the tube bundle leads to
thermal stresses which can lead to tube sheet warp a.es and tube-to-
tube sheet 2oint failures"
An impro,ement on the sin.le se.mental baae is the double
se.mental baae" )he .as is introduced to the two bundle at two points
746O apart" )he .as Tows across the tube towards the centre of the
tube bundle by two baaes" At the centre of the tube bundle the space
between the baaes allows the .as to Tow alon. tubes into the ne:t
baae section" A sin.le baae located in the centre of the tube bundle
forces the .as bac out across the tube bundle towards the shell" )his
pattern of Tow is repeated until the desired thermal characteristics are
achie,ed" )he ad,anta.e of the double se.mental baae is that the Tow
is split in two inside the tube bundle such that only half the .as Tow is
crossin. the bundle" )his means that the pressure drop will be less than
52
the sin.le se.mental baae arran.ement, e,erythin. else bein. e;ual"
Howe,er, there are still a mi:ture of cross and lon.itudinal Tow within
the tube bundle" $ouble se.mental heat e:chan.ers re;uire lar.e
bustles to distribute the .as to points 746O apart on the shell" )he
Te:ibility of shell side noAAle placement is impro,ed but the inlet and
outlets must still be in-line with each other"
A
further impro,ement is the so-called no-tubes-in-window desi.n which
omits all the tubes within the baae window" )he Tow of .as is now
essentially always across the tube bundle which maes predictin. shell
side heat transfer coeJcients easier" )he disad,anta.e is that the shell
of the e:chan.er is .enerally lar.er to accommodate all the tubes within
the o,erlap of the baaes and to minimiAe o,erall pressure drop"
Radial /low Heat
%:chan.ers
)he principal behind the
radial Tow heat e:chan.ers is
the use of disc and dount
baaes" )he dount baae
forces the .as to Tow from
the outside to the inside and
throu.h the hole in the middle
of the baae while the disc
baae does the opposite"
Placin. the tubes within the
o,erlappin. area
of the disc and donut baaes means the all the .as Tow will be
essentially across the tubes only" )he disc and donut baaes are
symmetrical around their centre so it does not matter where the .as
enters or e:its the shell side of the heat e:chan.er" )his allows the
ma:imum freedom to place shell side noAAles"
)he symmetrical layout of the
tubes means that the temperature pro9le across the tube sheet will also
be symmetrical" )he stresses occurrin. in the tube sheet will be more
uniform and hence there will be less chance of failures of the tube sheet
or tube-to-tube sheet 2oints"

Many di0erent tube layouts can be used with a disc and donut baae
arran.ement" )he simplest is to utiliAe a standard B6O or >6O tube
layout and remo,e all the tubes that fall in the baae windows" )he tube
53
layout will not be perfectly symmetrical but with enou.h tube =rows=
across the Tow path the unsymmetrical layout becomes less of a factor"
Plate )ype Heat %:chan.ers
Plate type heat e:chan.ers are relati,ely
new to the industry" )he principal of plate
heat e:chan.ers is similar to the plate
heat e:chan.ers used in acid coolin.
ser,ice" )he coolin. and heatin. streams
Tow on either side of a thin plate throu.h
which heat transfer occurs"
)he heat e:chan.er is modular in
construction allowin. it to be fully shop
fabricated and e:panded easily" $i0erent
materials of construction can be used for
the modules tain. ad,anta.e of better
corrosion resistance or hi.h temperature
stren.th"
)he MonPle: desi.n uses a Toatin. plate
pac contained within a ri.id housin." )he
desi.n allows for thermal e:pansion and contraction with minimal stress
on the components" )he .as passa.es are easily accessible on both
sides of the e:chan.er unlie a shell and tube unit where the tube side is
easily inspected and cleaned while the shell side is near impossible to
access"
Hot %:chan.ers
Hot %:chan.ers are .enerally cool the hot .ases lea,in. the 9rst catalyst
pass before enterin. the second catalyst pass" )he coolin. medium is
.enerally the partially heated .as enterin. the plant .oin. to the 9rst
catalyst pass" Hot e:chan.ers are e:posed to the hi.hest .as
temperatures e:it (ed 7 of the con,erter" Ma:imum temperatures can
reach as hi.h as ><5
O
E dependin. on .as stren.th""
Eold %:chan.ers
Eold e:chan.ers are .enerally the 9rst heatin. sta.e for the incomin.
.as and the 9nal coolin. sta.e for the .as enterin. the 9nal absorbin.
54
tower" /or hi.h .as stren.ths where e:cess heat is .enerated the cold
e:chan.er maybe followed by an &@
B
cooler or economiAer" @ld
e:chan.ers are .enerally constructed of carbon steel since the operatin.
temperatures are not as in hot e:chan.ers" )he problem that cold
e:chan.ers must contend with that hot e:chan.er do not, is the
possibility of .as condensation" /rom a corrosion point of ,iew, carbon
steel is not the best choice of materials"

T8r7oe="#%9er
55
/i.ure N&chematic dia.ram of a turboe:pander dri,in. a compressor"
A turboe:pander, also referred to as a turbo-e:pander or an e:pansion
turbine, is a centrifu.al or a:ial Tow turbine throu.h which a hi.h
pressure .as is e:panded to produce wor that is often used to dri,e a
compressor"
(ecause wor is e:tracted from the e:pandin. hi.h pressure .as, the
e:pansion is an isentropic process Fi"e", a constant entropy processG and
the low pressure e:haust .as from the turbine is at a ,ery low
temperature, sometimes as low as [86 OE or less"
)urboe:panders are ,ery widely used as sources of refri.eration in
industrial processes such as the e:traction of ethane and natural .as
li;uids F#GLsG from natural .as, the li;uefaction of .ases Fsuch as
o:y.en, nitro.en, helium, ar.on and ryptonG
R5SR>S
and other low-
temperature processes"
)urboe:panders currently in operation ran.e in siAe from about C56 - to
about C"5 M- F7 hp to about 76,666 hpG"
A""(ic#tio%5
Althou.h turboe:panders are ,ery commonly used in low-temperature
processes, they are used in many other applications as well" )his section
discusses one of the low temperature processes as well as some of the
other applications"
56
E=tr#cti%) '49roc#r7o% (iH8i95 &ro$ %#t8r#( )#5
/i.ure NA schematic dia.ram of a demethaniAer e:tractin. hydrocarbon
li;uids from natural .as"
Raw natural .as consists primarily of methane FEH
3
G, the shortest and
li.htest hydrocarbon molecule, as well as ,arious amounts of hea,ier
hydrocarbon .ases such as ethane FE
<
H
>
G, propane FE
B
H
4
G, normal butane
Fn-E
3
H
76
G, isobutane Fi-E
3
H
76
G, pentanes and e,en hi.her molecular
wei.ht hydrocarbons" )he raw .as also contains ,arious amounts of acid
.ases such as carbon dio:ide FE@
<
G, hydro.en sul9de FH
<
&G and
mercaptans such as methanethiol FEH
B
&HG and ethanethiol FE
<
H
5
&HG"
-hen processed into 9nished by-products Fsee #atural .as processin.G,
these hea,ier hydrocarbons are collecti,ely referred to as #GL Fnatural
.as li;uidsG" )he e:traction of the #GL often in,ol,es a turboe:pander
and a low-temperature distillation column Fcalled a demethaniAerG as
shown in /i.ure <" )he inlet .as to the demethaniAer is 9rst cooled to
about [57 OE in a heat e:chan.er Freferred to as a cold bo:G which
partially condenses the inlet .as" )he resultant .as-li;uid mi:ture is then
separated into a .as stream and a li;uid stream"
)he li;uid stream from the .as-li;uid separator Tows throu.h a ,al,e
and under.oes a throttlin. e:pansion from an absolute pressure of ><
57
bar to <7 bar F>"< to <"7 MPaG, which is an enthalpic process Fi"e", a
constant enthalpy processG that
results in lowerin. the temperature of the stream from about [57 OE to
about [47 OE as the stream enters the demethaniAer"
)he .as stream from the .as-li;uid separator enters the turboe:pander
where it under.oes an isentropic e:pansion from an absolute pressure of
>< bar to <7 bar F>"< to <"7 MPaG that lowers the .as stream temperature
from about [57 OE to about [87 OE as it enters the demethaniAer to
ser,e as distillation reTu:"
Li;uid from the top tray of the demethaniAer Fat about [86 OEG is routed
throu.h the cold bo: where it is warmed to about 6 OE as it cools the
inlet .as, and is then returned to the lower section of the demethaniAer"
Another li;uid stream from the lower section of the demethaniAer Fat
about < OEG is routed throu.h the cold bo: and returned to the
demethaniAer at about 7< OE" In e0ect, the inlet .as pro,ides the heat
re;uired to !reboil! the bottom of the demethaniAer and the
turboe:pander remo,es the heat re;uired to pro,ide reTu: in the top of
the demethaniAer"
)he o,erhead .as product from the demethaniAer at about [86 OE is
processed natural .as that is of suitable ;uality for distribution to end-
use consumers by pipeline" It is routed throu.h the cold bo: where it is
warmed as it cools the inlet .as" It is then compressed in the .as
compressor which is dri,en by the turbo e:pander and further
compressed in a second-sta.e .as compressor dri,en by an electrical
motor before enterin. the distribution pipeline"
)he bottom product from the demethaniAer is also warmed in the cold
bo:, as it cools the inlet .as, before it lea,es the system as #GL"
PoIer )e%er#tio%
58
/i.ure N&chematic dia.ram of power .eneration system usin. a
turboe:pander"
/i.ure B depicts a electric power .eneration system that uses a heat
source, a coolin. medium Fair, water or otherG, a circulatin. worin. Tuid
and a turboe:pander" )he system can accommodate a wide ,ariety of
heat sources such
asN
Geothermal hot water
%:haust .as from internal combustion en.ines burnin. a ,ariety of
fuels Fnatural .as, land9ll .as, diesel oil, or fuel oilG
A ,ariety of waste heat sources Fin the form of either .as or li;uidG
Referrin. to /i.ure B, the circulatin. worin. Tuid is pumped to a hi.h
pressure and then ,aporiAed in the e,aporator by heat e:chan.e with
the a,ailable heat source" )he resultin. hi.h-pressure ,apor Tows to the
turboe:pander where it under.oes an isentropic e:pansion and e:its as
a ,apor-li;uid mi:ture which is then condensed into a li;uid by heat
e:chan.e with the a,ailable coolin. medium" )he condensed li;uid is
pumped bac to the e,aporator to complete the cycle"
)he system in /i.ure B is a
Ranine cycle as is used in fossil fuel power plants where water is the
worin. Tuid and the heat source is deri,ed from the combustion of
natural .as, fuel oil or coal used to .enerate hi.h-pressure steam" )he
hi.h-pressure steam then under.oes an isentropic e:pansion in a
con,entional steam turbine" )he steam turbine e:haust steam is ne:t
condensed into li;uid water which is then pumped bac to steam
.enerator to complete the cycle"
-hen an or.anic worin. Tuid such as R-7B3a is used in the Ranine
cycle, the cycle is sometimes referred to as an @r.anic Ranine Eycle
F@REG"
59
Re&ri)er#tio% 545te$
/i.ure N &chematic dia.ram of a refri.eration system usin. a
turboe:pander, compressor and a motor"
/i.ure depicts a refri.eration system with a capacity of about 766 to
7666 tons of refri.eration Fi"e", B5< to B,5<6 -G" )he system utiliAes a
compressor, a turboe:pander and an electric motor"
$ependin. on the operatin. conditions, the turboe:pander reduces the
load on the electric motor by some > to 75? as compared to a
con,entional ,apor-compression refri.eration system that uses a
throttlin. e:pansion ,al,e rather than a turboe:pander"
)he system employs a hi.h-pressure refri.erant Fi"e", one with a low
normal boilin. pointG such asN
EhlorodiTuoromethane FEHEl/
<
G nown as R-<<, with a normal
boilin. point of [3C OE
7,7,7,< )etraTuoroethane FE
<
H
<
/
3
G nown as R-7B3a, with a normal
boilin. point of [<> OE"
As shown in /i.ure 3, refri.erant ,apor is compressed to a hi.her
pressure resultin. in a hi.her temperature as well" )he hot, compressed
,apor is then condensed into a li;uid" )he condenser is where heat is
e:pelled from the circulatin. refri.erant and is carried away by whate,er
coolin. medium is used in the condenser Fair, water, etc"G"
60
The refrigerant liquid flows through the turboexpander where it is vaporized and the vapor
undergoes an isentropic expansion which results in a low-temperature mixture of vapor and
liquid. The vapor-liquid mixture is then routed through the evaporator where it is vaporized
by heat absorbed from the space being cooled. The vaporized refrigerant flows to the
compressor inlet to complete the cycle.

S(8) c#tc'er
)he scope of the slu. catcher is the separation of a
two-phase Tow"
)he two-phase stream Tow from the pipeline enters
the slu. catcher section at about 77"5 m ele,ation
from .round"
)he last part of the pipeline is also Tan.ed pieces of pipe sli.htly sloped
downward to permit the li;uid to accumulate and be separated"
-hen the Tow comes to the separator inlet, the 9rst separation occurs
between the .as that Tows in the separator and the li;uids that .oes
strai.ht to the end section of the pipeline where it is dischar.ed by a
le,el control ,al,e"
)he .as phase Tows throu.h the separator and the demisters where the
remainin. entrained li;uids are separated to the bottom of the ,essel
and returned into the pipeline section Fli;uid sectionG"
Any e:cess .as retained in the li;uid section is returned to the separator
with the e;ualiAer line"
)he demister space can be di,ided into multi e;ui,alent sections with
separate .as outlets and washin. de,ices"
If salt or pipeline solids plu. the demisters, it is possible to wash one
section at a time, while the other sections continue to wor" If the
amount of li;uid phase increases, it is possible to add a Tan.ed piece of
pipe at the end of the pipeline to accommodate the une:pected Tow
increase"
)o sum up the main features of our proprietary slu. catcher are the
followin.N
If the li;uid Tow increases it is possible to handle the une:pected
li;uid stream simply by addin. Tan.ed pieces of pipe as neededM
)he plu..in. of the demister will not stop the operation"
61
Li;uid slu.s can e:ist in a re.ion between the super9cial li;uid ,elocities
of 7 to 3 mKs and a super9cial .as ,elocity of 3 to <6 mKs" )hese li;uid
slu.s tra,el at the same ,elocity as the .as throu.h a pipeline and can
cause si.ni9cant dama.e to, or operational problems for, .as processin.
e;uipment" Gas pipelines ha,e typically used !&lu. Eatchers! to
dissipate the ener.y of the li;uid slu.s that intermittently propa.ate
throu.h a .as pipeline"
Eurrent !&lu. Eatcher! desi.ns are based on reducin. Tuid ,elocities to
promote a !strati9ed! Tow re.ime and subse;uent .ra,ity separation" )o
attain this the slu. catcher must control and dissipate the ener.y of the
incomin. .as stream as it enters the slu. catcher to minimiAe turbulence
and ensure that the .as and li;uid Tow rates are low enou.h so that
.ra,ity se.re.ation can occur" Ielocity reduction is achie,ed by
enlar.in. the pipe n" diameter" A rule of thumb is that the .as ,elocity
cannot e:ceed 7"5 mKs F5 fKsG for li;uid remo,al to occur" )he current
slu. catcher desi.n must not only promote strati9cation, but must also
be capable of handlin. the lar.est slu. ,olume without permittin. slu.
formation in the slu. catcher" )hus, selectin. slu. catcher len.th is an
important part of the slu. catcher desi.n" )o conser,e on land area, it is
common to use !9n.er stora.e! which is essentially a mesh of
interconnected slu. catchers
B#5ic O"er#tio%
In its simplest form, the &lu. &tabiliAer &ystem consists of a branch
connection, a slu. stabiliAin. loop, a bypass loop, and another branch
connection" In normal operation the .as Tow enters the &lu. &tabiliAer
&ystem and di,ides at the 9rst branch connection between the slu.
catchin. loop and the bypass loop before recombinin. at the second
branch connection and continuin. alon. the pipeline" )he branch
connections will normally be a tee and can be oriented from horiAontal
trou.h to ,ertical position" )he branch positions and siAes can be
optimiAed to meet indi,idual .asKli;uid pipeline Tow characteristics and
minimiAe the ,olume of li;uid enterin. the branch connection while still
allowin. suJcient .as Tow to bypass ahead of the li;uid slu."
62
Incomin. li;uid slu.s enter the &lu. &tabiliAer &ystem and the ma2ority
of the slu. is propelled past the 9rst branch connection" Most of the
li;uid will continue past the branch connection and into the slu.-
stabiliAin. loop due to the li;uid=s momentum ener.y and its resistance
to chan.e Tow direction" )he li;uid slu. will continue passin. the branch
connection Fwith some li;uids enterin. the branchG until the .as behind
the slu. reaches the same branch connection" )he .as pressure behind
the li;uid slu. is normally hi.her Fto o,ercome the slu.=s friction losses
and pro,ide the li;uid momentum ener.yG than the pressure in the slu.
stabiliAin. loop and the bypass pipin." -hen the hi.her .as pressure
pushin. the slu. reaches the branch connection the .as will bypass into
the branch, as the .as pressure is lower in the branch connection" As the
.as Tows into the bypass branch the pressure will increase in the branch
connection and decrease in the pipin. behind the li;uid slu."
)he branch by-pass pipin. directs the hi.h-pressure .as from behind the
li;uid slu. to the other end of the slu.-stabiliAin. loop where the second
branch connection is located" )he .as will di,ide with most of the .as
continuin. down the pipeline with some .as enterin. the slu. stabiliAin.
loop and increasin. the pressure in front of the li;uid slu." )he second
branch connection can also be desi.ned such that most of the li;uids
that entered the bypass branch Fwhile the slu. was passin. the 9rst
branch connectionG will be carried past the second branch connection
into the slu. stabiliAin. loop" -ith the .as pressure increasin. in front of
the slu. and the .as pressure reducin. behind the slu. Fdue to .as
bypassin. around the slu.G the momentum of the slu. will be reduced
until the pressure stabiliAes and e0ecti,ely reduces the slu. ,elocity to
63
nil" )he preferred .as Tow is now throu.h the bypass pipin. and the
trapped li;uid slu. alon. with
the bypass li;uids are essentially suspended in the slu.-stabiliAin. loop"
)he siAe, len.th and orientation of the slu. stabiliAin. loop can be
optimiAed for the ma:imum slu. e:pected and the applicable .as Tow
rates and pressures"
)he slu.-stabiliAin. loop can be desi.ned with a .rade to collect the
trapped li;uids and dischar.e throu.h a drain" An alternati,e would be
to .rade the slu.-stabiliAin. loop to allow a strati9ed Tow reintroduction
of li;uids into the primary .as stream" )he li;uids can then be remo,ed
with downstream e;uipment that only has to be desi.ned for strati9ed
Tow and siAed for a li;uids withdrawal rate e;ui,alent to the re-
introduction li;uid Tow rate" In e0ect, the slu. stabiliAer system allows
downstream separation e;uipment to ha,e li;uid capacity desi.n in line
with the re-introduction rate which can occur o,er an hour or lon.er
instead of ha,in. to separate the li;uid slu. in a minute or less" )his is a
ma2or impro,ement o,er the desi.n criterion of e:istin. slu. catchers
which rely on .as ,elocity reduction to enable li;uid separation in the
short time a,ailable that the slu. tra,els throu.h the con,entionally
desi.ned slu. catcher"
&lu.catcher is the name of a unit in the .as re9nery or petroleum
industry in which slu.s at the outlet of pipelines are collected or
=cau.ht=" A slu. is a lar.e ;uantity of .as or li;uid that e:its the pipeline"
S(8)5
Pipelines that transport both .as and li;uids to.ether, nown as )wo-
phase Tow, can operate in a Tow re.ime nown as slu..in. Tow or slu.
Tow" 'nder the inTuence of .ra,ity li;uids will tend to settle on the
bottom of the pipeline, while the .asses occupy the top section of the
pipeline" 'nder certain operatin. conditions .as and li;uid are not
e,enly distributed throu.hout the pipeline, but tra,el as lar.e plu.s with
mostly li;uids or mostly .asses throu.h the pipeline" )hese lar.e plu.s
are called slu.s"
&lu.s e:itin. the pipeline can o,erload the .asKli;uid handlin. capacity
of the plant at the pipeline outlet, as they are often produced at a much
lar.er rate than the e;uipment is desi.ned for"
&lu.s can be .enerated by di0erent mechanisms in a pipelineN
)errain slu..in. is caused by the ele,ations in the pipeline, which
follows the .round ele,ation or the sea bed" Li;uid can accumulate
64
at a low point of the pipeline until suJcient pressure builds up
behind it" @nce the li;uid is pushed out of the low point, it can
form a slu."
Hydrodynamic slu..in. is caused by .as Towin. at a fast rate o,er
a slower Towin. li;uid phase" )he .as will form wa,es on the li;uid
surface, which
may .row to brid.e the whole cross-section of the line" )his
creates a bloca.e on the .as Tow, which tra,els as a slu. throu.h
the line"
Riser-based slu..in., also nown as se,ere slu..in., is associated
with the pipeline risers often found in o0shore oil production
facilties" Li;uids accumulate at the bottom of the riser until
suJcient pressure is .enerated behind it to push the li;uids o,er
the top of the riser, o,ercomin. the static head" (ehind this slu. of
li;uid follows a slu. of .as, until suJcient li;uids ha,e
accumulated at the bottom to form a new li;uid slu."
Pi..in. slu.s are caused by Pi..in. operations in the pipeline" )he
pi. is desi.ned to push all or most of the li;uids contents of the
pipeline to the outlet" )his intentionally creates a li;uid slu."
&lu.s formed by terrain slu..in., hydrodynamic slu..in. or riser-based
slu..in. are periodical in nature" -hether a slu. is able to reach the
outlet of the pipeline depends on the rate at which li;uids are added to
the slu. at the front Fi"e" in the direction of TowG and the rate at which
li;uids lea,e the slu. at the bac" &ome slu.s will .row as they tra,el
the pipeline, while others are dampened and disappear before reachin.
the outlet of the pipeline"
P8r"o5e o& t'e 5(8) c#tc'er
A slu. catcher is a ,essel with suJcient bu0er ,olume to store the
lar.est slu.s e:pected from the upstream system" )he slu. catcher is
located between the outlet of the pipeline and the processin.
e;uipment" )he bu0ered li;uids can be drained to the processin.
e;uipment at a much slower rate to pre,ent o,erloadin. the system" As
slu.s are a periodical phenomenon, the slu. catcher should be emptied
before the ne:t slu. arri,es"
&lu. catchers can be used continuously or on-demand" A slu. catcher
permanently connected to the pipeline will bu0er all production,
includin. the slu.s, before it is sent to the .as and li;uid handlin.
facilities" )his is used for diJcult to predict slu..in. beha,iour found in
terrain slu..in., hydrodynamic slu..in. or riser-based slu..in."
Alternati,ely, the slu. catcher can bypassed in normal operation and be
brou.ht online when a slu. is e:pected, usually durin. pi..in.
65
operations" An ad,anta.e of this set-up is that inspection and
maintenance on the slu. catcher can be done without interruptin. the
normal operation"
S(8) c#tc'er 9e5i)%
&lu. catchers are desi.ned in di0erent formsN
A ,essel type slu. catcher is essentially a con,entional ,essel" )his
type is simple in desi.n and maintenance"
A 9n.er type slu. catcher consists of se,eral lon. pieces of pipe
F=9n.ers=G, which to.ether form the bu0er ,olume" )he ad,anta.e
of this type of slu. catcher is that pipe se.ments are simpler to
desi.n for hi.h pressures, which are often encountered in pipeline
systems, than a lar.e ,essel" A disad,anta.e is that its footprint
can become e:cessi,ely lar.e" An e:ample of a lar.e 9n.er-type
slu. catcher can be seen in $en Helder, )he #etherlands, usin.
Goo.le Maps"
A basic slu. catcher desi.n contains the bu0er ,olume for .as and
li;uid" A control system is used for controlled outTow of .as and li;uid to
the downstream processin. facilities" )he inlet section is desi.ned to
promote the separation of .as and li;uid"
Mo(ec8(#r Sie3e5
Molecular sie,e adsorbents were de,eloped to remo,e water from li;uids
and .ases more eJciently than the older silica .el and alumina
desiccants" Molecular sie,es, because of their crystalline composition,
will yield ,irtually water-free products" )his feature maes molecular
66
sie,es particularly useful in cryo.enic operations where li;uefaction of
.ases is re;uired and water must be eliminated to a,oid freeAin."
Molecular sie,es o0er adsorption selecti,ity based on molecular siAe,
molecular aJnity for the sie,e crystal surface, and shape of the
molecule" Molecular sie,e systems are e:tremely simple to use for
reducin. contaminants to nearly undetectable le,els compared to other
technolo.ies such as li;uid separation systems" )his, alon. with the
hi.her eJciency compared to other adsorption systems, has made
molecular sie,e systems a popular en.ineerin. choice"
Less than B6-B5?RH, these are e0ecti,e"
'sin. a dry pur.e .as at an inlet temperature of <66-B56OE and a
pressure of 6"B b
6"5 .Kcmc, heat the molecular sie,e bed" As the temperature in outlet
reaches 756 b 746OE, let the bed cool o0"
Handlin. and &tora.eN Product must be stored in a dry location Frelati,e
67
humidity d 86?G to pre,ent re-adsorption of water" @pened paca.es
should be resealed to pre,ent contamination of the product" -hene,er
possible, rotate stoc to use oldest material 9rst"
T4"e5 o& t'e Mo(ec8(er 5ie3e5 7e95
EJL Mo(ec8(#r Sie3e K=0
ApplicationsN Multi-purpose" 'sed for the dehydration and puri9cation of
,arious hydrocarbon and non-hydrocarbon .as and li;uid streams"
EJL Mo(ec8(#r
Sie3e 0=E*
ApplicationsN Multi-purpose" 'sed for the dehydration and puri9cation of
,arious hydrocarbon and non-hydrocarbon .as and li;uid streams"
S"eci;c#tio%5
Si:e M8#(i;c#tio% e 85"6?
/#ter A95or"tio% e <5"5 m.K.
CO* A95or"tio% e 74"6 m.K.
Co$"re55i3e Stre%)t' e <5"6 n
B8(F De%5it4 e 6">3 .Kml
/e#r R#te f 6"B6? wei.ht
P#cF#)e> Re5i98#(
Moi5t8re
f 7"5? wei.ht
Co8%tr4 o& Ori)i% Ehina
P#cF#)i%) 736 . steel drum
F&upersacs A,ailableG
S"eci;c#tio%5
Si:e M8#(i;c#tio% e 85"6?
/#ter A95or"tio% e <5"5 m.K.
CO* A95or"tio% e 74"6 m.K.
Co$"re55i3e Stre%)t' e <5"6 n
B8(F De%5it4 e 6">3 .Kml
/e#r R#te f 6"B6? wei.ht
P#cF#)e> Re5i98#(
Moi5t8re
f 7"5? wei.ht
Co8%tr4 o& Ori)i% Ehina
P#cF#)i%) 736 . steel drum
F&upersacs A,ailableG
68
EJL Mo(ec8(#r Sie3e APG
ApplicationN 7Bg Molecular &ie,e APG is used commercially for air plant
feed puri9cation Fsimultaneous remo,al of H<@ and E@< G and .eneral
.as dryin."
Pro"ertie
5
Me#58
re U%it
S"'eric#( C4(i%9ric
#(
Di#$eter mm 7">-<"5 B-5 7"> B"<
St#tic
/#ter
A95or"ti
o%
e m.K. <C6 <C6 <C6 <C6
CO*
A95or"ti
o%
e m.K. 746 746 746 746
B8(F
De%5it4
.Kml 6">Ch6"
6<
6">>h6"
6<
6"><h6"
6<
6"><h6"
6<
Cr85'
Stre%)t'
e # B6 46 B6 >5
/e#r
R#te
f ?wt 6"7 6"7 6"< 6"7
P#cF#)e
Moi5t8re
f ?wt 7"6 7"6 7"6 7"5
EJL Mo(ec8(#r Sie3e HP
ApplicationN 7Bg Molecular &ie,e HP is used commercially for air plant
feed puri9cation and P&A o:y.en .eneration process"
Pro"ertie5 Me#58re$
e%t U%it
S"'eric#(
Di#$eter mm 6"5-7"6 7">-<"5
St#tic /#ter
A95or"tio%
e m.K. <45 <45
CO*
A95or"tio%
e m.K. 786 785
B8(F De%5it4 .Kml 6">3h6"
6<
6"><h6"
6<
Cr85'
Stre%)t'
e # <6
/e#r R#te f ?wt 7"6 7"6
69
P#cF#)e
Moi5t8re
f ?wt 7"6 7"6
EJL Mo(ec8(#r Sie3e PG
ApplicationN 7Bg Molecular &ie,e PG is used commercially for
desulfuriAation of li;ue9ed petroleum .as"It is also used for dehydration
of .ases and li;uids"
Pro"ertie
5
Me#58re$
e%t U%it
S"'eric#( C4(i%9ric#(
Di#$eter mm 7">-<"5 B-5 5-4 7"> B"<
St#tic
/#ter
A95or"ti
o%
e m.K. <>6 <>6 <>6 <>6 <>6
CO*
A95or"ti
o%
e m.K. 7C5 7C5 7C5 7C5 7C5
B8(F
De%5it4
.Kml 6">Ch6"
6<
6">>h6"
6<
6">3h6"
6<
6"><h6"
6<
6">6h6"
6<
Cr85'
Stre%)t'
e # <5 46 7<6 <5 >3
/e#r
R#te
f ?wt 6"7 6"7 6"7 6"< 6"<
P#cF#)e
Moi5t8re
f ?wt 7"6 7"6 7"6 7"5 7"5
EJL Acti3#te9 PoI9er
ApplicationN 7Bg Acti,ated Powder is a,ailable for dehydration in coatin.
industry and paint industry"
Pro"ertie5 Me#58re$e%t
U%it
S"eci;c#ti
o%
For$ Powder
Pore Di#$eter g 7B
/'ite%e55 e ? 86
P#rtic(e
Di#$eter
i m 7-3
70
St#tic /#ter
A95or"tio%
e ?wt <>6
PH f 77"5
Gr#3it4 e.Kml "BB
P#cF#)e
Moi5t8re
f? -t B"6
Molecular sie,es are Alumino &ilicates, which ha,e a uniform, crystalline
structure" It is this structure, which is used to !9lter! out molecules of
contaminants" )he sie,es are produced in pellets of di0erent shapes
and siAes to suit the application and bed wei.ht"
Re)e%er#tio% ?#cti3#tio%@
Re.eneration in typical cyclic systems constitutes remo,al of the
adsorbate from the molecular sie,e bed by heatin. and pur.in. with a
carrier .as" &uJcient heat must be applied to raise the temperature of
the adsorbate, the adsorbent and the ,essel to ,aporiAe the li;uid and
o0set the heat of wettin. the molecular-sie,e surface" )he bed
temperature is critical in re.eneration" (ed temperatures in the 7C5-
<>6O ran.e are usually employed for type BA" )his lower ran.e
minimiAes polymeriAation of ole9ns on the molecular sie,e surfaces
when such materials are present in the .as" &low heat up is
recommended since most ole9nic materials will be remo,ed at minimum
temperaturesM 3A, 5A and 7Bg sie,es re;uire temperatures in the <66-
B75 OE ran.e"
After re.eneration, a coolin. period is necessary to reduce the
molecular sie,e temperature to within 75O of the temperature of the
stream to be processed" )his is most con,eniently done by usin. the
same .as stream as for heatin., but with no heat input" /or optimum
re.eneration, .as Tow should be countercurrent to adsorption durin. the
heat up cycle, and concurrent Frelati,e to the process streamG durin.
71
coolin." Alternati,ely, small ;uantities of molecular sie,es may be dried
in the absence of a pur.e .as by o,en heatin. followed by slow coolin.
in a closed system, such as a desiccator"
Molecular &ie,es are crystalline Aeolites that ha,e been acti,ated for
adsorption by remo,in. their water of hydration" $urin. this
dehydration, hi.hly porous adsorbents are formed that ha,e stron.
aJnity for water and certain other .ases and li;uids"
)he pores of any particular type of Molecular &ie,e are precisely uniform
in siAe and of molecular dimensions" $ependin. on the siAe of these
pores, molecules may be readily adsorbed , slowly adsorbed or
completely e:cluded"
Molecular &ie,es ha,e been used in many commercial and industrial
systems for
dryin. and purifyin. li;uids and .ases" Also, these adsorbents ha,e
made possible the de,elopment of lar.e scale separation processes used
to reco,er normal paraJns from branched chain and cyclic
hydrocarbons"
Mo(ec8(#r Sie3e5 c#% 7e 85e9 i% t'e &o((oIi%) t4"e5 o&
#95or"tio% 545te$5>
M8(ti"(e-Be9 A95or"tio%. )his method can be used for the ma2ority of
commercial lar.e scale Tuid puri9cation operations" Eon,entional 9:ed
bed, heat re.enerated adsorption systems are .enerally utiliAed" A
typical dual-bed installation places one bed on-stream purifyin. the Tuid
while the other is bein. heated, pur.ed and cooled"
Si%)(e-Be9 A95or"tio%. -hen interrupted product Tow can be
tolerated, it is sometimes con,enient to use a sin.le adsorption bed"
-hen the adsorption capacity of the bed is reached, it can be
re.enerated for further use or discarded, dependin. on process
economics"
St#tic A95or"tio%. -hen formed into wafers or other shapes,
Molecular &ie,es can be used as static desiccants in closed .as or li;uid
systems"
)he basic types of Molecular &ie,es are the BA, 3A, 5A and 7Bg sie,es"
%ach of these are a,ailable in the form of beads of 3 : 4 F< mmG and 4 :
72
7< F3 mmG mesh siAes"
De-et'#%i:er
An inte.rated deethaniAer and ethylene fractionation column and
process for separatin. a feed stream comprisin. ethylene, ethane and
E
B
V is disclosed" A sin.le shell houses a reTu:ed upper portion and a
lower portion of the column" A .enerally ,ertical wall partitions the lower
portion of the column into a deethaniAer section and an ethylene
stripper section" )he upper column portion is used as the absorption
section of the ethylene fractionator" )he feed is supplied to an
intermediate sta.e in the deethaniAer, and the deethaniAer is operated
at a lower pressure Fand correspondin.ly lower temperatureG matchin.
that of the ethylene fractionation" )he desi.n allows the use of one
73
sli.htly lar.er column in place of the two lar.e columns pre,iously used
for separate deethaniAation and ethylene fractionation"
)he present in,ention relates to an apparatus and method for the
deethaniAation and ethylene fractionation in an ole9n plant processin.
propane and hea,ier feedstocs, and particularly to the use of an
inte.rated column which combines both the deethaniAer and ethylene
fractionator into a sin.le column"
A typical process for the separation and reco,ery of ole9ns from
pyrolysis furnaces operated with feedstocs hea,ier than ethane, is
nown as the front end depropaniAer and front end acetylene
hydro.enation scheme" A brief re,iew of the typical front end
depropaniAer process is in order"
there are three sta.es of con,entional compression to raise the pressure
of the process .as from 2ust abo,e atmospheric to a pressure of about
75 bars F<76 psiaG" Eondensed li;uids, i"e" hydrocarbons and water, are
separated"
)he .as is then treated in a con,entional two or three sta.e caustic
wash tower 76 for the remo,al of carbon dio:ide and hydro.en sul9de"
)he .as is cooled and mildly chilled before enterin. the dryers" -ater is
remo,ed completely"
)he .as is then further chilled in propylene refri.erant e:chan.er, and
enters the hi.h pressure depropaniAer which does not really operate at
hi.h pressure but is only called that because there is also a low pressure
depropaniAer" )he hi.h pressure depropaniAer typically operates at a
pressure of 7< bars F7C6 psiaG, and the low pressure depropaniAer <6 at
a pressure of 4"5 bars F7<6 psiaG"
)he o,erhead of the hi.h pressure depropaniAer is usually compressed
in compressor to a pressure of B4 bars F556 psiaG and is then sent to the
acetylene hydro.enation system which typically consists of two or three
adiabatic reactors in series with inter-cooler for the remo,al of the heat
of reaction" )he reactor eauent is cooled in coolin. water e:chan.er <>
and partially condensed in propylene refri.erant e:chan.er" A portion of
the condensate is used as reTu: ,ia line for the hi.h pressure
depropaniAer" )he rest is sent to the demethaniAer stripper ,ia line"
In the strippin. section of the hi.h pressure depropaniAer only ethane
and li.hter components are remo,ed, resultin. in a fairly low bottoms
temperature of 5>O E" F7BBO /"G" )he bottoms product is sent ,ia line to
the low pressure depropaniAer where it is separated into E
B
=s and E
3
V"
)he E
B
is used as reTu: in the hi.h pressure depropaniAer ,ia line, while
the E
3
V is sent to the debutaniAer Fnot shownG ,ia line" $ue to the low
74
operatin. pressure, the bottoms temperatures in the depropaniAers are
;uite low, namely 5>O E" F7BBO /"G and C7O E" F7>6O /"G" )herefore, there
is no foulin. in either tower or their respecti,e reboilers"
)he acetylene hydro.enation unit is hi.hly eJcient and selecti,e" )he
acetylene remo,al easily results in acetylene concentrations of less than
7 ppm in the 9nal ethylene product while the ethylene .ain amounts to
56? or more of the acetylene" $ue to the hi.h hydro.en content of the
feed .as, no carbonaceous material is deposited on the catalyst" )he
catalyst needs no re.eneration and thus the reactors need no spares"
Green oil formation is miniscule"
In the acetylene hydro.enation reactor about 46? of the methyl-
acetylene and <6? of the propadiene are con,erted to propylene" If the
ole9ns plant produces polymer .rade propylene the remainin. E
B
H
3
can
be easily fractionated into the propane productM the hi.h con,ersion of
methyl-acetylene and propadiene in the acetylene hydro.enation
reactors ob,iates the need for an additional separate E
B
H
3
hydro.enation system"
)he operational stability of the acetylene hydro.enation reactor is
enhanced by its location in the .ross o,erhead loop of the depropaniAer
and in the minimum Tow recycle circuit of the fourth sta.e of
compression" )hese factors reduce the acetylene concentration in the
inlet to the reactor and stabiliAe the Tow rate irrespecti,e of the furnace
throu.hput"
)he ,apor and li;uid from the reTu: accumulator of the hi.h pressure
depropaniAer Tow to the chillin. and demethaniAation sectionG" )he
li;uid plus the condensate formed at -BCO E" F-B5O /"G is sent ,ia
respecti,e lines and to the demethaniAer stripper " )he o,erhead ,apor
from the demethaniAer stripper plus the li;uids formed at lower
temperatures are sent to the main demethaniAer ,ia respecti,e lines
and " )he tower is reboiled by reboiler with condensin. propylene
refri.erant, and reTu: is condensed in heat e:chan.er with low
temperature ethylene refri.erant"
)he respecti,e bottoms products of the two demethaniAers , after some
heat e:chan.e which is not shown, enter the prior art deethaniAer " )he
tower reco,ers appro:imately 36 percent of the ethylene contained in
the two feeds as hi.h purity product" &i:ty percent of the ethylene and
all the ethane lea,e the tower as a side stream and proceed to the low
pressure ethylene fractionator " )he deethaniAer is reboiled by reboiler
with ;uench water and reTu: is condensed in e:chan.er with -36O
propylene refri.erant" )he bottoms product of the deethaniAer is a
75
stream containin. propylene, propane and the remainin. E
B
H
3
" It Tows
to a con,entional propylene fractionator (ecause of the ethylene
fractionation in its top section , the deethaniAer has 9fty more trays
than a con,entional deethaniAer which produces a mi:ed ethylene and
ethane o,erhead product in line "
)he ethylene fractionator is a relati,ely low pressure tower typically
operatin. at 3 bars F>6 psiaG with appro:imately 766 trays" It uses an
open heat pump" %thylene refri.erant is condensed in the reboiler and is
then used as reTu: ,ia line " %0ecti,ely, the reboiler also ser,es as the
reTu: condenser" )here are no reTu: pumps and there is no reTu: drum"
)he present in,ention combines the deethaniAer and ethylene
fractionator of the prior art into a sin.le fractionation column, reduces
the pressure of the deethaniAer to that of the ethylene fractionator and
locates the deethaniAer and the strippin. section of the ethylene
fractionator in the bottom portion of a sin.le distillation column di,ided
by a ,ertical wall" Locatin. the deethaniAer and the strippin. sections of
the ethylene fractionator in the bottom section of a sin.le distillation
column di,ided by a ,ertical wall has the capital cost sa,in.s of
replacin. two lar.e columns with a sli.htly lar.er columnM eliminates the
deethaniAer reTu: condenser, drum and pumpsM and employs a much
smaller deethaniAer reboiler"
In one aspect, the present in,ention pro,ides an inte.rated deethaniAer
and ethylene fractionation column for separatin. a feed stream
comprisin. ethylene, ethane and E
B
V into an ethylene stream, an
ethane stream and a E
B
V stream" )he inte.rated column is made of a
sin.le shell housin. a reTu:ed upper portion and a lower portion" %ach of
the inte.rated column portions comprise multiple ,apor-li;uid contactin.
elements" A .enerally ,ertical wall partitions the lower portion into a
deethaniAer section and an ethylene stripper section" A feed line
supplies at
least one feed stream to at least one feed sta.e of the deethaniAer
section of the lower portion of the column, between a plurality of
absorption sta.es abo,e the feed sta.e and a plurality of strippin.
sta.es below the feed sta.e, for producin. an o,erhead ,apor stream
from the deethaniAer section consistin. essentially of ethylene and
ethane and a bottoms stream consistin. essentially of E
B
and hea,ier
components" A distribution pan with ,apor chimneyFsG at the lower end
of the upper portion of the column facilitates passa.e of ,apors from the
deethaniAer and ethylene stripper sections into the upper column
portion, and collects li;uid for passa.e from the upper portion of the
column into the upper sta.e of the deethaniAer section and into the
ethylene strippin. section"
76
)he inte.rated column can ha,e a deethaniAer section comprisin. from
<6 to >6 trays" )he upper and lower portions of the inte.rated column
preferably ha,e the same cross-sectional diameter" )he inte.rated
column can also include a reboiler for the deethaniAer section heated
with hi.h pressure depropaniAer .ross o,erhead or some other suitable
heatin. medium" )he inte.rated column can also include a reboiler for
the ethylene stripper section, heated by ethylene condensed at a
relati,ely hi.her pressure than the inte.rated column" )he inte.rated
column preferably includes a line for reTu:in. the upper portion of the
column with the ethylene condensed in the ethylene stripper section
reboiler" )he inte.rated column can include a compressor for
compressin. o,erhead ,apor from the upper portion of the column to
the pressure of the ethylene stripper section reboiler" )he inte.rated
column preferably comprises respecti,e li;uid lines from the distribution
pan to the tops of the dethaniAer section and the ethylene stripper
section" )he line from the distribution pan to the top of the deethaniAer
section can include a ,al,e for controllin. the amount of li;uid supplied
to the deethaniAer section" )he inte.rated column preferably has an
operatin. pressure of from < to <6 bars FB6 to <86 psiaG"
De-78t#%i:er
77
Proce55 De5cri"tio%
)he debutaniAer column considered in this study "the LPG can be
produced with hi.h -
LPG
,alues Fup to 75
o
EG and sent to the /EE unit to
be reprocessed" $ependin. on the adopted operatin. strate.y,
completely di0erent process conditions are obtained and conse;uently
the system follows di0erent models" )hen, a robustness problem is
created and the control system must deal with it" )he schematic
representation of the debutaniAer is shown in /i."B" )he feed stream
comes from the top of the crude pre-Tash column at a temperature of
36
o
E and pressure of 4 .fKcm
<
" It is pre-heated in the heat e:chan.er %-
67 where the hot Tuid is the stabiliAed .asoline that lea,es the bottom of
the debutaniAer at appro:imately 7>B
o
E" At the e:it of %-67 the
temperature of the feedstream is appro:imately 7B>
o
E and it is >?
,aporiAed" )he feed is introduced in the debutaniAer column F)-67G at
sta.e 7C" )he column has B6 sta.es with a Murphree eJciency of
appro:imately C5?" Measured points of the temperature pro9le are the
top Fabout 53
o
EG, bottom Fabout 7>B
o
EG and sta.e 5 Fabout >C
o
EG" )he
top condenser has a heat duty of appro:imately 7"6 MMcalKh that
corresponds to a distillate Tow of about 764 m
B
Kd and a reTu: Tow of
about 366 m
B
Kd" A small Tow of fuel .as is also produced"

78

In the control scheme adopted in this study the manipulated
,ariables are the reboiler heat duty Fj
R%(
G and the reTu: Tow
rate FI
R)
G which operatin. window is represented in /i."3" )his
operatin. window results from se,eral process constraints that
are de9ned in )able 7"

79


80
C'#"ter D ,
PLANT LOCATION B SELECTION
&electin. a plant side is critical to 9nancial success of a plant" &e,eral
81
factors must be considered in selectin. a .eneral plant location"
SITTING FACTORS
)he primary sittin. factors, which inTuence the selection of a plant
location, are as follows"
%n,ironmental consideration
Labor a,ailability and producti,ity
Raw material a,ailability
Pro:imity to maret
Property cost
)a: incenti,es
%lectric power a,ailability and cost"
%#IIR@#M%#)AL E@#&I$%RA)I@#
%n,ironmental consideration is the most important factor in selection
of location"
LABOR AVAILABILITY AND PRODUCTIVITY
It is prefer to ha,e access to a wor force with de,eloped sills that -can
be readily con,erted to suit the special re;uirement of a new business"
LIVING CONDITION
Li,in. conditions such as house a,ailability, cost, safety, school, health
care, ma2or
82
hospitals and local doctors, musical place, are considered ,ery important
for ;uality of life"
RA/ MATERIAL AVAILABILITY
/or many industries such as the petroleum and petrochemical industries,
a,ailability of raw materials is most important factor in selectin. a plant
site"
ACCESSIBILITY TO TRANSPORTATION
)he cost of transportation is important factor in plant side selection" )he
plant needs to be located close to the maret the cost of shippin. by
taner is lowest"
PROPERTY COST
Land cost is the most important factor in side selection" Plants tend to
locate away from areas where residential homes dri,e up the property
cost"
TAL
-hen considerin. ta:es, all types needed to be considered, initial fees,
capital ,alue, corporate rate, personal income ta:, sales ta:, property
ta: and unemployment, insurance"
SPECIFIC PLANT SITE CONSIDERATION
@nce a .eneral plant location has been established, a speci9c plant site
location to be determined" @ne approach is to use the kcorn 9eldl
method of plant site assessment, the purpose of which is to de,elop an
ideal list of speci9cation that de9ne what would be re;uired to put the
plant in any corn 9eld"
CONCLUSION
83
Heepin. in ,iew the abo,e factors and on the assumption, we ha,e
decided to construct the GA& PR@E%&&I#G PLA#) in the rural areas of
SINDH"
84
C'#"ter D 1
Eost estimation
An acceptable plant desi.n must present a process that is capable of
operatin. under conditions, which will yield a pro9t" It is necessary the
85
chemical en.ineer be aware of many di0erent types of costs in,ol,e in
the manufacturin. process" Eapital must be allocated for direct plant
e:penses, such as those for raw material, labor and e;uipment" (esides
direct plant e:penses, many other indirect e:penses are included if a
complete analysis of the total cost is to be obtained" )he total capital
in,estment for any process consists of /Ig%$ EAPI)AL I#I%&)M%#) for
physical e;uipment and facilities in the plant plus -@RHI#G EAPI)AL"
I#I%&)M%#) 1 /Ig%$ EAPI)AL I#I%&)M%#)
/orFi%) C#"it#( I%3e5t$e%t
)he capital, which is necessary for the operation of the plant, is called
worin. capital in,estment"
Fi=e9 C#"it#( I%3e5t$e%t
)he capital needed to supply the necessary manufacturin. and
production is called worin. 9:ed in,estment" It is di,ided in to two-sub
di,ision"
Direct Co5t
)he direct cost items are incurred in the construction of the plant in
addition to the cost of e;uipment"
Purchased %;uipment"
Purchased %;uipment Installation"
Instrumentation and Eontrol"
Pipin."
86
%lectrical %;uipment and Materials"
(uilidin.
*ard Impro,ement
ser,ice /acilities
Land
I%9irect Co5t
$esi.n 1 %n.ineerin."
Eontractor=s %:penses"
Eontractor=s /ee"
Eontin.ency"
/AE)@R& A//%E)I#G I#I%&)M%#) A#$ PR@$'E)I@# E@&)&
-hen a chemical en.ineer determines costs for any type o commercial
process, these costs should be of suJcient accuracy to pro,ide reliable
decisions" )o accomplish this" )he en.ineer must ha,e complete
understandin. of the factors that can a0ect cost" &ome important factors
are"
&ources of %;uipment"
87
Price /luctuations"
Eompany Policies"
@peratin. )ime 1 Rate of Production"
Go,ernment Policies"
TYPES OF CAPITAL COST ESTIMATE
An estimate of capital in,estment for a process may ,ary from pre-
desi.ned estimate based on little information e:cept the siAe of the
proposed pro2ect to a detailed estimate prepared from complete
drawin.s and speci9cation" (etween these two e:tremes of capital
in,estment estimates, which ,ary in accuracy dependin. upon the sta.e
of de,elopment of pro2ect"
/ollowin. 9,e cate.ories are used for desi.n purpose"
@rder of Ma.nitude %stimateN (ased on similar-pre,ious cost data
probable accuracy of estimate o,er V B6?"
&tudy %stimateN (ased on nowled.e of ma2or items of e;uipment,
probable accuracy of estimate up to VB6?"
Preliminary %stimateN (ased on suJcient data to permit the estimate to
be bud.eted" probable accuracy of estimate with in V <6?"
$e9niti,e %stimateN (ased on complete data but before completion of
drawin.s and speci9cation probable accuracy of estimate within V7@?"
$etailed %stimateN (ased on complete en.ineerin. drawin.s,
88
speci9cation and side sur,ey probable accuracy of estimate with in
V5?"
E@&) I#$%g%&
A cost inde: in merrily an inde: ,alue for a .i,en point in time showin.
the cost at that time relati,e to a certain base time if the cost at same
tie in the past is nown the e;uipment and the present time can be
determine by multiplyin. the ori.inal cost by the ratio of the present
Inde: ,alue to the inde: ,alue when the ori.inal cost was obtained"
)hese inde:es show accurate estimates if the time period in,ol,ed is
less than 76 years" )he most common inde:es areN
Marshall and &wift All Industry 1 Process Industry e;uipment
inde:es"
%n.ineerin. #ews Record Eonstruction Inde:"
#elson-/arrar Re9ner Eonstruction Inde:"
Ehemical %n.ineerin. Plant Eost Inde:"
M%)H@$ /@R %&)IMA)I#G EAPI)AL I#I%&)M%#)
Iarious methods can be employed for estimatin. capital in,estment the
choice of any method depends upon the amount of the detailed
information a,ailable and the accuracy desired"
$etailed Item %stimate"
89
'nit Eost %stimate"
Percenta.e of $eli,ered %;uipment Eost"
Land factor for Appro:imation of Eapital In,estment"
Power /actor Applied to Plant Eapacity Ratio"
In,estment Eost per 'nit of Eapacity"
)urn @,er Ratios"
-e ha,e estimated the total in,estment for our pro2ect by usin.
percenta.e of deli,ered cost"
$%L%II%R%$ %j'IPM%#) E@&)
Inde: 'sedN Marshall and &wift Installed %;uipment Inde: Ffor process
industryG Inde: ,alue in 7886P8<3
Inde: ,alue in 9rst ;uarter <66< P 7768"8 FReferenceN-/rom-Ehemical
%n.ineerin. Ma.aAine March <66<G
Eost of %;uipment in <66< P Eost of %;uipment in 7886 : inde: ,alue in
<66<Kinde: ,alue in 7886"
90
COST ESTIMATION
Eost of slu. catcher P 7,66,66
Eost of /in /an Eooler P 3B666D
P
86,666D
P
4<6,666D
PC6,666D
P
736,
666
P
56,666D
P
34,666D
P
>6,666D
P
7>,7,8><D
P
<6,666D
Eost of )rim Eooler
Eost of inlet
separator
Eost of /eed Gas
Eooler
Eost of &chreiber
Eost of /ilter
-alescer
Eost of &uper heater
Eost of Guard (ed
/ilter
Eost of particle /ilter
Eost of Membrane
91
P
>6C566D
92
Eost of H
<
& polishin. towers P 366,666D
Present cost P ori.inal cost : inde: ,alue at present
Inde: ,alue at ori.inal time"
PBBC63>< : 7768"8 P
365<85B"7>4D
8<3
Direct Purchased Cost Equipment Cost = E 4052953.168$
Components %AgeofE Cost$
Purchased Equipment Installation 47%E 1904887.989
Instrumentation (installed) 81%E 729531.5702 .
Piping installed 66%E 2674949.091
Electrical (installed 11%E 445824.8485
Building (including services) 18%E 729531.5702
Yard improvement Service Facilities 10%E 405295.3168
Service Facilities 70%E 2837067.218
Lard 6%E 243177.1901
Direct Cost (D) 9970264.794
INDIRECT COST
%n.ineerin. 1 &uper,ision BB?% D7BBC3C3"535
Eonstruction %:penses 37?% D7>>7C76"C88
)otal indirect Eost D<888745"B33
Eonstruction=s /ee 5? F$VlG: DB5<>6>"8<5>
Eontin.ency 76?F$V7G DC65<7B"B457<
/i:ed Eapital In,estment /P$V:VCP4768858"<48D
-orin. Eapital In,estment 75? of total capital in,estment P <
)otalEapital
In,estment
PAPZV/
PA P6"75AV/P85377<4"5C5D
PA P)PRs5"C<5 (illions
DIR!T "R#D$!TI#% !#&T
@peratin. Labor P6"75:) PRs"454C5666
$irect &uper,isin. and electrical labor P6"74:6
PRs"7535C566
'tilities P6"7 :) Rs"5C<56666
Patent 1 royalties P6"6B:) PRs"7C7C5666
$irect production cost PRs" <C>C<>38>"<PRs" <"CC: 764
Maintenance and
repair
@peratin. &upplies
P6"65:/
P6"66C5
:/
P<6<"4CC"Rs"
PRs"C<848>B
B">
PR@E%&&I#G E@&)
Processin. Eost P $irect Production wst V 9:ed char.es V plant
o,erhead cost
/Ig%$ EHARG%&
Patent 1"
royalties
$uplication
Local )a:es
Insurance
/i:ed Ehar.es
Plant o,er head
cost
Processin. Eost
P6"6B:
) P6"7
:/
P6"6<5
:/
P6"66C
:/
P6"7
:)
PRs"7C7C5666
Rs"
P34>58C55"CB
Rs"
P7<7>38B4"8B
Rs"
PB36>74<"867
Rs"
P>3<B64CC"5C
PRs"5C<56666
PRs"B84<6CBC
6"4
G%#%RAL %gP%#&%&
Admit Eost P 6"63:) P Rs" <<866666
PR
)otal product costKyear P processin. cost V General e:penses P Rs"
<"6C3:764
$istribution 1 sellin. cost P 6"77
:)
R 1 $ Eost
/inancin.
General
%:penses
P6"65:
)
P6"65:
)
As capacity is 766
MM&E/$ &ellin.
PriceKMM&E/
)otal .as sold
Pro9tKyear
PRs"<"C8B:7
68
P66 : B66 P6"666MM&E/
$ PRs"
766,666
PRs"B:764
PB:768-<"6C3:764
)urn o,er ratio is .i,en byN
PGross annual sales K/EI
PB:768K34>5C55"B
P>"7C
C'#"ter D 2
I%5tr8$e%t#tio% #%9 co%tro( "roce55
)he important common to all processes is that a process is ne,er in
a state of static e;uilibrium e:cept for a ,ery short period of time
and process is a dynamicentity sub2ect to continual upsets or
disturbances which tend to dri,e it away from the desired state of
e;uilibrium" If a process is to operate eJciency, disturbances and
the process must be controlled"
A process desi.ned for a particular
ob2ect and is then found" &ome time by trial and error and some
time by re0erin. from the pre,ious e:perience that control of a
particular ,ariable associated with some sta.es of the process are
necessary to achie,e the desired eJciency" Process may be
controlled more precisely to .i,e more uniform and hi.h ;uality
products by the application of automatic control, often leadin. to
hi.h pro9ts" Additionally, process which response too rapidly to be
controlled by human operator can be controlled automatically"
Automatic control is also bene9cial in certain remote, haAards or
routine operations" After a period e:perimentation, computer are
bein. used to operate automatically control" Processin. systems,
which may too lar.e and too comple: for e0ecti,e direct human
control"

Fee9 7#cF co%tro(
-hen a controller corrects a ,ariable, it does so in response to a
si.nal send from the measurin. de,ice" )his si.nal de,ice is called
called feedbac"
N#)#ti3e &ee9 7#cF co%tro(
#e.ati,e feed bac ensures that the di0erence between )r Fset
pointG and )m Fmeasured ,alueG is used to ad2ust the control
element in order to reduce the error"
Po5iti3e &ee9 7#cF co%tro(
If the si.nal to the comparator will be obtained by addin. )r and )m,
we would ha,e a positi,e feed bac system, which is unstable" %rror
si.nal F%G is obtained as,
% P )r V )m
Co$"o%e%t5 o& t'e co%tro( 545te$
Proce55
Any operation or series of operation that produces desired 9nal
results is a process" In this discussion the process is the puri9cation
of natural .as"
Me#58ri%) e(e$e%t5
As all he parts of the control system, measurin. elements is
perhaps the most important" If the measurements are not made
properly the remainder of the system can not operate satisfactorily"
)he measured ,ariable is chosen to represent the desired conditions
in the process"
A%#(45i5 o& t'e $e#58re$e%t 3#ri#7(e5 to 7e
$e#58re9
Iariables to be measured
Pressure measurement
)emperature measurement
/low rate measurement
Le,el measurement
V#ri#7(e5 to 7e recor9e9
Indicated temperature, composition , pressure ,etc"
Co%tro((er
)he controller is the mechanism that responds to any error
indicated by the error deductin. mechanism,"
@utput of the controller is the some predetermined function of the
error " )here are three types of the controller" Proportional action ,
which mo,es the control ,al,e indirect proportion to the ma.nitude
of the error "
Inte.ral action which mo,es the control ,al,e based on the time
inte.ral of the error and the purpose of the inte.ral action is to dri,e
the process that to its set point when it has been disturbed"
Ideal deri,ati,e action Fpre actsG and its purpose is to anticipate
where the process is headin. by cooin. at the time a rate of
chan.e of error"
Fi%#( co%tro( e(e$e%t
)he 9nal control element recei,es the si.nal from the
controller and by some pre determined relationship chan.es the
ener.y input to the process"
C'#r#cteri5tic5 o& t'e co%tro((er
In .eneral the process controller can be classi9ed as
Pneumatic controllers
%lectronic controllers
Hydraulic controllers
In the puri9cations of .as condensate the controller and 9nal control
element may be pneumatically operated due to the followin.
reasons""
)he pneumatic controller is ,ery ru..ed and almost free of
maintenance "
)he maintenance men need no suJcient trainin."
Pneumatic control appears to be safer in a potentially e:plosi,es
atmosphere which is often present in the petrochemical industry"
Mo9e5 o& t'e co%tro(
)he ,arious types of controls are called =modes= and then determine
the type response obtained" In other words these describe the
action if controller that is the relationship of output si.nal to the
input or error si.nal"
It must be noted that it is error that acti,ates the controller" )he
four basic mode of control areN
@0-on control"
Inte.ral control"
Proportional control"
Rate of deri,ati,e control"
In industry purely inte.ral, proportional or deri,ati,e modes seldom
occur alone in the control system"
)he o0-on control, with the ,ery hi.h .ain" In this case the error
si.nal at once o0 the ,al,e or any other parameter upon which it
sits or completely sets the systems"
F(oI co%tro((er
)hese are used to control the feed rate into a process unit" @ri9ce
plates are the most used as the Tow rate sensor" #ormally ori9ce
plates are desi.ned to .i,e a pressure drop in the ran.e of <6 to
<66 inch of water" Ientury tubes, and turbine are also used"
Te$"er#t8re co%tro((er
)hermocouples are the most used temperature sensin. de,ice" )he
two dissimilar wires pro,ide a milli ,olt emf that ,aries with the =hot-
function= temperature" Iron constrict any thermocouple are
commonly used o,er the 7B66 / temperature ran.e"
Pre558re co%tro((er
(orden tubes, bellows and diaphra.ms are used to sense pressure
and di0erential pressure" e"." in a mechanical system the process
forse is balance by the mo,ement of sprin." )he sprin. position can
be related to process pressure"
Le3e( co%tro((er
Li;uid le,els are indicated in the ,ariety of ways" )he three most
common are M
7" )he followin. position of the Toat that is li.hter than the Tuid"
<" Measurin. are apparent wei.ht of a hea,y cylinder as it is
buoyed up more or less by the li;uidFthey are called displacement
metersG"
B" Measurin. the di0erence in static pressure between two 9:ed
ele,ations, one is the ,apour abo,e the li;uid and the other under
the li;uid surface" )he di0erential pressure between the two le,el
taps is directly related to the li;uid le,el in the ,essel"
Tr#%5$itter5
)he transmitter is the interface between the process and its control
system" )he 2ob of the transmitter is to con,ert the sensor si.nal
Fmill ,olts, mechanical mo,ement, pressure di0erence, etc"G into a
control si.nal B to 75 psi. air pressure si.nal, 7 to 5 or 76 to 566
milli ampere electrical si.nal etc"
Co%tro( 3#(3e5
)he interface in the process are the other end of the control loop is
made by the 9nal control element in an automatic control ,al,es"
)he Tow of steam that open or closes ori9ce openin. as the steam
is raised or lowered" )he steam is attached to the diaphra.m that is
dri,en by chan.in. air pressure abo,e the diaphra.ms" )he fore for
the air pressure is opposed by a sprin."
I%5tr8$e%t#tio% #%9 co%tro( o76ecti3e5
)he main ob2ecti,es are as followsN
&afe plant operation"
)o eep the process ,ariable within nown safe operatin.
limit"
)o detect dan.erous situations as they de,elop and to pro,ide
an alarm and automatic shut down systems"
Pro98ctio% R#te> )o achie,e the desi.n product output"
Pro98ct M8#(it4> )o maintained the product composition with in
the speci9c ;uality standards"
Co5t> )o operate at the lowest production cost"
In a typical chemical processin. plant these ob2ecti,es are achie,ed
by combination of automatic control, manual monitorin. and
laboratory analysis"
Pro)r#$$#7(e (o)ic co%tro( ?PLCS@
)hese were de,eloped in the early 78C6s and represent the earliest
and most successful application of computers in process control"
)oday, PLE& are one of the most hi.hly de,eloped and one of the
most rapidly e,ol,in. e:amples of computers in the process control"
)he term pro.rammable means that e;uipments beha,iour is
de9ned by instructions FsoftwareG, not by its manufacturin.
speci9cation" PLE was the name .i,en to the ori.inal e;uipment,
which performed only Lo.ic operations" )oday=s units are called
simply pro.rammable controllers FPEsG and many be part of
inte.rated control"
)he 9rst PLE was small computers desi.ned primarily to ser,e as
pilot relay replacements"
PLE=s are widely used today as inputKoutput FIK@G counts of B666 or
more are common" )he IK@ modules are ser,iced o,er a networ by
a separate processor unit located for the con,enience of the user"
)he lar.e IK@ counts also made the PLE a rich source of data"
I%te)r#te9 co%tro( 545te$
Many de,elopment are occurrin. simultaneously" PLE=s ha,e
ac;uired loop control capabilities in addition, the lo.ic capabilities of
control systen are bein. enhanced, and $E& is enterin. the
traditionally discrete control 9eld of the PLE=s"
C'#"ter D 0
T'e #93#%t#)e5 o& LPG i%c(89e
/ollowin. are the ma2or ad,anta.es
(ecause LPG ,aporiAes when released from the tan and is not
water soluble, LPG does not pollute under.round water sources"
Propane has a hi.h octane ratin. of 763, in-between Eompressed
#atural Gas FE#GG F7B6G and re.ular unleaded .asoline F4CG"
Refuelin. a propane ,ehicle is similar to 9llin. a .as .rill tanM
the time it taes is comparable with that needed to 9ll a E#G,
.asoline or diesel fuel tan"
Its hi.h octane ratin. enables it to mi: better with air and to burn
more completely than does .asoline, .eneratin. less carbon"
-ith less carbon buildup, spar plu.s often last lon.er and oil
chan.es are needed less fre;uently"
(ecause it burns in the en.ine in the .aseous phase, propane
results in less corrosion and en.ine wear than does .asoline"
(oth Propane and (utane are easily li;ue9ed and stored in
pressure containers" )hese properties mae the fuel hi.hly
portable, and hence, can be easily transported in cylinders or
tans to end-users"
LPG is a .ood substitute for petrol in spar i.nition en.ines" Its
clean burnin. properties, in a properly tuned en.ine, .i,e
reduced e:haust emissions, and e:tended lubricant and spar
plu. life"
As a replacement for aerosol propellants and refri.erants, LPG
pro,ides alternati,es to Tuorocarbons which are nown to cause
deterioration of the earth=s oAone layer"
)he clean burnin. properties and portability of LPG pro,ide a
substitute for indi.enous fuels such as wood, coal, and other
or.anic matter" )his pro,ides a solution to de-forestation and the
reduction of particulate matter in the atmosphere FhaAeG, caused
by burnin. the indi.enous fuels"
)his is called =sweatin.=, and is caused by the process of LPG
chan.in. from its li;uid state to a ,apour state" LPG in a stable
state consists of both li;uid and ,apour" -hen ,apour is drawn
from the cylinder the ,apour pressure in the cylinder is reduced
and alters this stability between the ,apour pressure and the
pressure re;uired maintainin. the LPG as a li;uid" In this
condition, the li;uid LPG boils releasin. ,apour which stabiliAes
the pressure within the cylinder" In order for LPG to boil, it must
draw in heat throu.h the cylinder wall" As this happens the wall
of the cylinder is cooled and moisture in the air condenses on the
wall of the cylinder" In e:treme cases, the cylinder may ha,e ice
formin. on the surface of the cylinder" Interestin.ly, the top ed.e
of the sweatin. or ice, re,eals the le,el of the LPG remainin. in
the cylinder"
Li;ue9ed petroleum .as FLPGG is a fully-Ted.ed fuel for internal
combustion en.ines" Gas has been uni,ersally reco.niAed as a
cheap, ecolo.ical fuel, which is superior to petrol in se,eral
aspects" It is also important to now that there is no need to
redesi.n a ,ehicle in order to use LPG, which results in the
opportunity to use both petrol and LPG as a fuel"
(ecause of its relati,ely fewer components, it is easy to achie,e
the correct fuel to air mi: ratio that allows the complete
combustion of the product" )his .i,es LPG its clean burnin.
characteristics"

%Jcient and economical hydrocarbon reco,eryN typically >6? to


86? reco,ery of feed LPG

LPG reco,ery as an easy to handle li;uid

Reduces Tarin. and corrects re9nery fuel balance

Reco,ery of puri9ed hydro.en can be an added bene9t

Pro,en performanceN doAens of references for both hydrocarbon


and hydro.en membranes"

Lon. membrane lifeN typical membrane lifetime is 3 to 5 years or


more"

&imple, reliable, Te:ible unitM easy to install and operate

@perates at moderate temperatures and pressures

&imple installation and operation with compact sid-mounted


construction

Re;uires no additional chemicalsM produces no wastes



T'e 9r#I7#cF5 o& LPG i%c(89e
/ollowin.s are the ma2or disad,anta.es
In cold conditions, below B< de.rees /ahrenheit, startin. could
be a problem because of the low ,apor pressure of propane at
low temperatures"
@ne .allon of LPG contains less ener.y than a .allon of .asoline"
)he dri,in. ran.e of a propane ,ehicle is about 73 percent lower
than a comparable .asoline-powered ,ehicle"
LPG is .enerally hi.her priced than other fuel alternati,es such
as E#G and .asoline"
)here are o,er 3,666 LPG refuelin. sites in the '&, more than all
of the other alternati,e fuels combined" Most of these stations,
howe,er, are not readily a,ailable to consumers on a <3KC basis"
)his is one of the reasons why most on-road applications are bi-
fuel ,ehicles, which burn LPG and .asoline"
LPG is used as a fuel for domestic, industrial, horticultural,
a.ricultural, cooin., heatin. and dryin. processes" LPG can be
used as an automoti,e fuel or as a propellant for aerosols, in
addition to other specialist applications" LPG can also be used to
pro,ide li.htin. throu.h the use of pressure lanterns"
Tr#%5"ort#tio%
)here are a number of ways to chec thisN
/irstly, a cylinder can be wei.hed to chec how much product is
left in the cylinder" )he wei.ht of the LPG remainin. in the
cylinder is total wei.ht of the cylinder plus the LPG, less the
empty wei.ht or tare wei.ht, of the cylinder" F)he re.ulator and
any other 9ttin.s should be remo,ed prior to wei.hin. the
cylinderG"
&econdly, some cylinders ha,e .au.es which show the amount
of LPG contained within the cylinder"
)hirdly, li;uid crystal .au.es, which stic to the outer surface of
the LPG cylinder, are a,ailable, and these show the le,el of the
li;uid LPG within the cylinder by indicatin. a colour chan.e at
the interface between the li;uid and ,apour le,els caused by the
temperature ,ariation"
/ourthly, if the cylinder is bein. used, then it may be possible to
see the le,el of the LPG in the cylinder by obser,in. the le,el of
the sweatin. on the cylinder wall"
Lastly, it is possible to see the le,el of the LPG li;uid within a
cylinder by pourin. boilin. water down the side of the LPG
cylinder" )he li;uid le,el is re,ealed where a condensate or frost
line occurs"
Recent de,elopments and trends in transportation of LP .as areN
'se of lar.e multipurpose FLP .as and ammoniaG railroad tan
cars" )an cars with a >6,666 .al capacity ha,e been introduced"
$e,elopment of lar.e refri.erated ocean taners capable of
transportin. millions of .allons of LP .as at atmospheric
pressure"
A""(ic#tio% Are#5
Re9nery fuelKTare .as

Eatalytic reformer net .as

Pressure swin. adsorption FP&AG tail .as

/luidiAed catalytically craced F/EEG main column o,erhead .as

Aromatics plant pur.e and ,ent .ases

&team methane reformer feed .as

H
<
membrane tail .as
/ractionation is also used to remo,e water from LP .as" )he
water-rich o,erhead ,apor from the dryin. fractionator is
condensed, resultin. in two li;uid phases" )hese are allowed to
separate" )he hydrocarbon-rich phase is returned to the
fractionators as reTu:" )he water-rich phase is discardedM it may
be stripped to remo,e dissol,ed hydrocarbons before discardin."
A dry hydrocarbon product is produced as ettle product from the
dryin. column" /ractionation can produce e:ceptionally dry
products"
LP .as also used for
Includes home space heatin., cooin., water heatin., clothes
dryin., etc"
used as a fuel for domestic Fcooin.G, industrial, horticultural,
a.ricultural, heatin. and dryin. processes" LPG can be used as
an automoti,e fuel or as a propellant for aerosols, in addition to
other specialist applications" LPG can also be used to pro,ide
li.htin. throu.h the use of pressure lanterns" -hile butane and
propane are di0erent chemical compounds, their properties are
similar enou.h to be useful in mi:tures" (utane and Propane are
both saturated hydrocarbons" )hey do not react with other"
(utane is less ,olatile and boils at 6"> de. E" Propane is more
,olatile and boils at - 3< de. E" (oth products are li;uids at
atmospheric pressure when cooled to temperatures lower than
their boilin. points" IaporiAation is rapid at temperatures abo,e
the boilin. points" )he calori9c FheatG ,alues of both are almost
e;ual" (oth are thus mi:ed to.ether to attain the ,apor pressure
that is re;uired by the end user and dependin. on the ambient
conditions" If the ambient temperature is ,ery low propane is
preferred to achie,e hi.her ,apor pressure at the .i,en
temperature"
Stor#)e
Lar.e ,olumes of LP .as are stored to meet the pea demand durin.
the winter months" /our basic types of stora.e are usedN
F7G hi.h-pressure stora.e abo,e .roundM
F<G low-pressure refri.erated stora.e abo,e .roundM
FBG froAen-earth stora.eM
F3G under.round ca,ern stora.e"
)he capacity of the stora.e units ,aries from a one-;uart pressure
cylinder to a 56-million .al under.round stora.e ca,ern"
%conomic factors determine the proper stora.e for any .i,en
re;uirementN
Abo,e-.round hi.h-pressure stora.e tans are usually desi.ned
for a <56-psi. worin. pressure for propane and 7<5 psi. for
butane"
F<G Refri.erated abo,e-.round stora.e tans usually are
desi.ned for a few pounds per s;uare inch .a.e"
FBG In froAen-earth stora.e, the walls and bottom of a pit in the
.round are froAen" A dome is constructed o,er the pit" )he
pressure in the stora.e ca,ity is maintained at a near-
atmospheric pressure" Heat leas into the ca,ity ,aporiAe some
propane which is withdrawn, compressed, condensed, and
returned to the ca,ity as a li;uid" (ecause this stora.e method
must operate considerably below B</ and at atmospheric
pressure, it is not for butane stora.e"
F3G 'nder.round stora.e ca,erns, operatin. at appro:imately
formation temperatures and correspondin. LP-.as ,apor
pressures, may be mined under.round-stora.e ca,ities or
ca,ities that ha,e been produced in salt formations by solution
minin." )he under.round ca,erns must be of suJcient depth to
pro,ide o,erburden pressure .reater than the ,apor pressure of
the stored li;uid" Mined stora.e ca,erns are usually <66-566ft
deep while ca,erns in salt formation may be B56-5666 ft deep"
'nder.round stora.e is much more economical for stora.e of
lar.e ,olumes Fabo,e appro: 7 million .alG of LP .as than abo,e-
.round stora.e" If suitable salt formations e:it, the washed-out
salt ca,erns cost only one-tenth to one-half as much as typical
mined ca,ern stora.e" About 86? of the total stora.e ,olume is
under.round and of this appro: 86? in salt formations"
Lar.e ,olumes of LP .as are transported from the producin. plants to
centers of consumption by se,eral methods" )he pro.ress of LP .as
utiliAation has been closely related to the pro.ress in the
transportation methods" )ransportation costs are a ma2or factor in the
cost of LP .as to the consumer" )he two ma2or transportation methods
for LP .as are railroad tan cars and truc transports" (oth of these
methods use hi.h-pressure tans which are desi.ned for ambient-
temperature operation" -hen lar.e ,olumes of LP .as are transported,
hi.h-pressure pipelines usually supply the most economical method"
)he use of pipelines for transportin. LP .as is .rowin. rapidly, resultin.
lar.ely in decreased use of railroad tan cars" )he use of taners and
bar.es for transportin. LP .as to %urope and for transportin. LP .as on
waterways in the 'nited &tates is also .rowin. rapidly" )he taners and
bar.es are desi.ned for both hi.h-pressure, ambient temperature, and
for low-pressure, refri.erated transportation" /or lar.e ,olumes and
lon. distances, low pressure, refri.erated transportation is often more
economical than hi.h-pressure pipelinesM howe,er, for small ;uantities
of ethane, multi tube truc trailers are often used"
SALES AND USES
)he sales of LP .as due to e:clusi,e of LP .as used in the
production of .asoline ha,e increased from 366,666 .al to 7B
billion"
)he yearly increase in sales o,er the past ten years was about
4? a year" )he o,erall supply and demand for LP .as has been
essentially in balance the past one or two years"
Althou.h the total ,olumes of both butane propane in Lp .as
sales ha,e continued to increase o,er this period, propane sales
ha,e increased more rapidly than butane sales" As a result, the
trend shows a lar.er percenta.e of sales represented by propane
and a correspondin. decrease for butane, partially a result of the
increased re9nery demand for butane in motor fuel" /urthermore,
the supplies of LP .as propane ha,e increased more rapidly than
those of butane" )he older natural .as processin. plants
reco,ered only nominal ;uantities of propane" the process
impro,ements in e:traction of LP .as ha,e increased the
reco,ery of propane up to about 86?"
As propane reco,eries are increased, ethane reco,eries are also
substantially increased" In the future, process re,isions to
increase reco,ery are liely to pro,ide .reater increase in
production for ethane than for propane" %thane is used lar.ely
for the production of ethylene" )hermal cracin. of ethane
pro,ides hi.h yields of ethylene because fewer by-products are
produced than with other feed stocs such as propane, butane,
or hea,ier hydrocarbons" )he demand for ethane as a raw for
petrochemical manufacture should continue to e:pand rapidly"
Residential and commercial demands represent nearly half of the
LP .as sales, Home heatin. is the leader in this demand" @ther
domestic uses also represent si.ni9cant ,olumes of LP .as" )he
second lar.est use of LP .as is in the manufacture of
petrochemical and polymer intermediates" Plastic polymers are
the lar.est consumer of intermediates deri,ed from LP .as" )he
manufacture of polyethylene, polypropylene, and poly,inyl
chloride, three lar.e ,olume and rapidly .rowin. plastic resin
products, re;uires lar.e ,olumes of ethylene and propylene
which are produced by thermal cracin. of propane, butane, and
ethane"
)he use of propylene for the manufacture of synthetic deter.ents
will be substantially reduced because in the new biode.radable
deter.ents a normal in main. the alylate" )he e:pected .ains
for propylene in polypropylene plastic and ethylene-propylene
rubbers will tend to o0set the decrease in propylene"
References
1.International Energy Glossary (a page from the website of the
Energy Information Administration)
2.Natural gas processing (a page from the website of the Energy
Information Administration)
3.Natural Gas Condensate Marathon Oil Company MSDS
4.Natural Gas Condensate Phillips Petroleum Company MSDS
5.Condensate (Alaska) ConocoPhillips of Alaska MSDS
6.Natural Gas Condensate Amerada Hess Corporation MSDS
7.Chemical process control George stephenpolous
8.Encyclopedia for the chemical technology. Kirk Orthomer, 4
th

edition
9.Natural gas engineering, Donald. E. Katz
10. Chemical engineering handbook Robert H. Perry & Don
Green, 8
th
edition