fayaz report on challenges associated with sepn of hcl-water azeotrope 04.08 (7)

8/18/2019 Fayaz Report on Challenges Associated With Sepn of Hcl-water Azeotrope 04.08 (7)

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PROJECT INTERNSHIP REPORT

CHALLENGES ASSOCIATED WITHSEPARATION OF HCl-WATER AZEOTROPE

IN COPPER CHLORINE

THERMOCHEMICAL HYDROGEN

GENERATION CYCLE(A CASE STUDY)

24 th Jul 2!"#

SUBMITTED BY,

MOHAMMED FAYAZUDDIN.

1



Project Internship eportOn

CHALLENGES ASSOCIATED WITH SEPARATION OF HCl-WATER

AZEOTROPE IN COPPER - CHLORINE THERMOCHEMICAL

HYDROGEN GENERATION CYCLE - A CASE STUDY

$

Moh!""e# F!$!%&##in

B.Tech ' r# $e!r ()he"ic!* En+ineerin+ ,

!ji- !n#hi Instit&te o/ Petro*e&" Techno*o+$,

!e B!re*i (0&*$ 213

U%&' th' u*' +, , % .

Dr. D P!r-!t!*&,

Project "!n!+er, H$#ro+en project,OE), p!n-e*.

In /&*/i*"ent o/ re4&ire"ent o/ project intern /or ' r# $e!r B.Tech in )he"ic!* en+ineerin+ !t

IPT,

!e5!re*i(U.P



)E TIFI)ATE

I here5$ certi/$ th!t the project internship report tit*e# 6 Ch/ll'%0' A 1,/t'& ,th

S'*/ /t, % . HCl - W/t' A3' t *' ,% C **' -Chl ,%' Th' 1h' ,1/l H & 0'%G'%' /t, % C 1l' 5 A C/ ' Stu& 7 h!s 5een c!rrie# o&t s&ccess/&* 5$ hi" in the ON )

Ener+$ )entre, P!n-e*. Mr. Moh!""e# F!$!%&##in h!s 8or9e# on this topic !s S&""er

Internship tr!inee &n#er "$ +&i#!nce /ro" 1: th M!$ 213 to ; th 0&*$ 213.

Si+n!t&re <

ese!rch S&per-isor < Dr. D. P!r-!t!*&, Project M!n!+er, H$#ro+en Project, OE), P!n-e*

A//i*i!tion < ON ) ENE Y )ENT E, P!n-e*, M!h!r!shtr!, In#i!.

D!te <

'



A16% l'&0' '%t

It h!s 5een !n i""ense p*e!s&re !n# tr&*$ enrichin+ e=perience #oin+ "$ -oc!tion!* tr!inin+

!t ON ) Ener+$ )enter, P!n-e*, N!-i M&"5!i in their H$#ro+en Project.

I 8o&*# /irst *i9e to th!n9 Dr. B. Bh!r+!-!, Director ener!*, ON ) Ener+$ )entre, Mr. ).

T!n#i, ED>HOI>IEOT, P!n-e* !n# Mr. P&neet ?ishore, M(P > He!#>T U, OE) /or

!**o8in+ "e to p&rs&e "$ s&""er tr!inin+ !t OE), P!n-e*. I t!9e this opport&nit$ 8ith

"&ch p*e!s&re to th!n9 !** the peop*e 8ho h!-e he*pe# "e thro&+h the co&rse o/ "$ jo&rne$

!s !n intern

I t!9e this opport&nit$ to e=press "$ pro/o&n# +r!tit&#e !n# #eep re+!r#s to "$ +&i#e !n#

"entor Dr. D. P!r-!t!*& Project M!n!+er, H$#ro+en project, OE), P!n-e* /or his e=e"p*!r$

+&i#!nce, "onitorin+ !n# const!nt enco&r!+e"ent thro&+ho&t the co&rse o/ this thesis. He

h!s 5een the #ri-in+ /orce 5ehin# the co"p*etion o/ this project. I e=press "$ +r!tit&#e to Dr.

S. B!nerjee /or his -!*&!5*e +&i#!nce !n# technic!* !#-ice #&rin+ the co&rse o/ "$ 8or9.

I 8o&*# *i9e to e=press "$ +r!tit&#e to Mrs. Bin! Pr!s!#, He!# ASU, OE) /or +i-in+ "e this

opport&nit$ to &n#ert!9e this s&""er internship.

I 8o&*# *i9e to th!n9 Ms. ?!"ini Si-!9&"!r, Sr. Project Fe**o8, OE), P!n-e* /or her

!ssist!nce. I 8o&*# *i9e to th!n9 OE) /or this opport&nit$ to 8or9 8ith the" !n# +i-in+ "e

! /irst>h!n# e=perience o/ sep!r!tion techni4&es !n# so/t8!re !pp*ic!tions in-o*-e# in

H$#ro+en pro#&ction thro&+h ther"oche"ic!* c$c*es.

;



INDE7

1.2 INT ODU)TION @

.2 OB0E)TI E

'.2 APP OA)H

;.2 MA0O SEPA ATION ISSUES ECATED TO )U>)* )Y)CE :

3.2 SEPA ATION TE)HNI UES FO AZEOT OPE MI TU E

@.2 ESIDUE GDISTICCATION )U E ANACYSIS OF SYSTEMS FO MIN

AZEOT OPE

.2 SEPA ATION OF H (+ GH)*(+ ASEOUS MI TU E 1;

:.2 P ESSU E S IN DISTICCATION 13

.2 SIMUCATIONS )A IED OUT TO DETE MINE PHASE BEHA IOU

AND AZEOT OPI) )OMPOSITION OF H)C> ATE 1@

12.2 SIMUCATIONS )A IED OUT TO DETE MINE PHASE BEHA IOU

AND AZEOT OPI) )OMPOSITION OF H)C> ATE 1

12.1 )ASE STUDY 1 < APPCI)ATION OF P ESSU E S IN

DISTICCATION TO H)C ATE SYSTEM 1

12. )ASE STUDY> < SIMUCATION STUDY OF P ESSU E S IN '

11.2 DISTICCATION )OCUMNS OPE ATIN AT 2.21ATM AND 12 ATM @

1 .2 )ON)CUSION

1;.2 BIBICO APHY

"8 INTRODUCTION <

3



H$#ro+en is c*e!n ener+$ c!rrier !n# pro"isin+ !*tern!ti-e to the con-ention!* /ossi* /&e*. It

h!s ! hi+hest ener+$ per &nit "!ss o/ 1 2M0G9+ .To o5t!in si"i*!r !"o&nt o/ ener+$ 8o&*#

re4&ire .3 9+ o/ n!t&r!* +!s, . 39+ o/ oi* !n# '. >;.39+ o/ co!*. The "ost 8i#e*$ &se#

"etho# /or pro#&ction o/ h$#ro+en is ste!" "eth!ne re/or"in+ process, pro#&ces )O !n#

)O 8hich !re +reenho&se +!ses. Other s&st!in!5*e !n# +reen "etho#s h!-e 5een #e-e*ope#

in the ne!r p!st, one o/ 8hich is pro#&ction o/ H 5$ ther"oche"ic!* 8!ter sp*ittin+ c$c*es.

These c$c*es !re pro"isin+ 8!ter sp*ittin+ !*tern!ti-es th!t c!n 5e *in9e# 8ith So*!r or

n&c*e!r he!t so&rce to ther"!**$ #eco"pose H O thro&+h ! series o/ inter"e#i!te re!ctions

!n# h!-e the potenti!* /or *!r+e sc!*e h$#ro+en +ener!tion. Se-er!* ther"oche"ic!* c$c*es !re

reporte# in the p!st 5&t -er$ /e8 h!-e 5een p&rs&e# in -ie8 o/ their "erits !s !ppe!r

pro"isin+ to #e-e*op in ne!r /&t&re. Io#ine>S&*/&r c$c*e !n# )opper )h*orine c$c*es !re the

5est e=!"p*es. These !re 5ein+ #e-e*ope# 5$ ON ) Ener+$ )entre in co**!5or!tion 8ith

se-er!* n!tion!* D instit&tions o/ rep&te. One o/ the "ost pro"isin+ ther"oche"ic!*

c$c*e is the )opper J )h*orine ()&>)* c$c*e !n# h!-e 5een 8i#e*$ rese!rche# 8or*#8i#e.

The )&>)* ther"oche"ic!* c$c*e< The )opperJ)h*orine c$c*e ()&J)* c$c*e is

ther"oche"ic!* c$c*e (Fi+&re 1 /or the pro#&ction o/ h$#ro+en. The )&J)* c$c*e is !

h$5ri# process th!t e"p*o$s 5oth ther"oche"ic!* !n# e*ectro*$sis steps. It h!s ! "!=i"&"

te"per!t&re re4&ire"ent o/ !5o&t 3'2 o ).

The )&J)* c$c*e in-o*-es che"ic!* re!ctions /or 8!ter sp*ittin+, 8hose net re!ction

#eco"poses 8!ter into h$#ro+en !n# o=$+en. A** other che"ic!*s !re rec$c*e#. The )&J)*

process c!n 5e *in9e# 8ith n&c*e!r p*!nts or other he!t so&rces s&ch !s so*!r !n# in#&stri!*

8!ste he!t to potenti!**$ !chie-e hi+her e//iciencies, *o8er en-iron"ent!* i"p!ct !n# *o8er

costs o/ h$#ro+en pro#&ction th!n !n$ other con-ention!* techno*o+$ (Orh!n et !*., 212 .

A#-!nt!+es o/ the )opperJ)h*orine c$c*e inc*&#e *o8er oper!tin+ te"per!t&re, the !5i*it$ to

&se *o8>+r!#e 8!ste he!t to i"pro-e ener+$ e//icienc$, !n# potenti!**$ *o8er cost "!teri!*s.

In co"p!rison 8ith other ther"oche"ic!* c$c*es, the )&J)* process re4&ires re*!ti-e*$ *o8

te"per!t&res o/ &p to 3'2K). Another si+ni/ic!nt "erit o/ this c$c*e is ! re*!ti-e*$ *o8

-o*t!+e (th&s *o8 e*ectric!* ener+$ e=pen#it&re th!t is re4&ire# /or the e*ectroche"ic!* step

(2.@ to 1.2 . The o-er!** e//icienc$ o/ the )&J)* c$c*e h!s 5een esti"!te# to 5e j&st o-er

;'L, e=c*&#in+ the !##ition!* potenti!* +!ins o/ &ti*i%in+ 8!ste he!t in the c$c*e.

@



F,0u ' "8 F u t/0' Cu-Cl 1 1l'

D&rin+ h$#ro*$sis re!ction step o/ the )&>)* ther"oche"ic!* c$c*e /or h$#ro+en +ener!tion,

e=cess ste!" is re4&ire# /or "!=i"&" con-ersion o/ )&pric )h*ori#e. The &nre!cte# ste!"

!n# pro#&ct H)* /or"s !n !%eotropic "i=t&re !t the pro#&ct en#. Here co"p*ete sep!r!tion

o/ H)* !n# 8!ter is not possi5*e 5$ con-ention!* #isti**!tion !*one 5ec!&se o/ /or"!tion o/

H)*G8!ter !%eotrope. The present 8or9 !i"s to /in# ! /e!si5*e so*&tion to this i"port!nt

pro5*e".

28 O9JECTI:EThe "!in o5jecti-e o/ the 8or9 8!s to per/or" Si"&*!tion St&#ies &ti*isin+ )HEM)AD

si"&*!tion so/t8!re /or sep!r!tion o/ H)*>8!ter !%eotrope in the h$#ro*$sis re!ction step o/

the )opper )h*orine c$c*e.

;8 APPROACH

Si"&*!tion st&#ies 5$ !pp*ic!tion o/ press&re s8in+ #isti**!tion &sin+ 6)HEM)AD7

Si"&*!tion So/t8!re /or sep!r!tion o/ H)* !n# 8!ter /ro" H)*G8!ter !%eotrope pro#&ce# in

the h$#ro*$sis step o/ the )&>)* c$c*e.



48 MAJOR SEPARATION ISSUES RELATED TO CU-Cl CYCLE <• H$#ro+en +ener!tion re!ction< The sep!r!tion o/ "i=t&re o/ pro#&ct H (+ !n# &nre!cte#

H)* (+ .• Disproportion!tion e!ction< D&rin+ e*ectro*$sis re!ction there is /or"!tion o/ c&pper

po8#er. These copper po8#er nee# to 5e sep!r!te# /ro" e*ectro*$tic so*&tion.• H$#ro*$sis e!ction< D&rin+ h$#ro*$sis re!ction e=cess ste!" is re4&ire# /or "!=i"&"

con-ersion o/ c&pric ch*ori#e. The &nre!cte# ste!" !n# pro#&ct H)* /or"in+ the

!%eotropic "i=t&re !t the pro#&ct en#. The co"p*ete sep!r!tion o/ H)*G8!ter is not

possi5*e 5$ con-ention!* #isti**!tion !*one 5ec!&se o/ !%eotrope. Press&re s8in+

#isti**!tion "!$ so*-e this sep!r!tion pro5*e".

48" H 2O<HCl /3' t *' '*/ /t, %= !ter !n# H)* /or" ! "!=i"&" 5oi*in+ !%eotrope !t 1 !t"press&re !s sho8n in H OGH)*

ph!se #i!+r!" (Fi+&re . This "e!ns th!t the 5oi*in+ point o/ !%eotrope is hi+her th!n 5oth

8!ter !n# H)*. M!=i"&" 5oi*in+ !%eotrope !re 4&ite &nco""on in n!t&re. The$ h!-e

ne+!ti-e #e-i!tions /ro" i#e!* 5eh!-io&r8hich "e!ns th!t its !cti-it$ coe//icient i is

ne+!ti-e. The re!son /or this non i#e!*it$ is th!t the h$#ro+en 5on#in+ inter!ction !ssoci!te#

8ith the H O !n# H)*.is #epicte# 5e*o8.

:



Fi+&re .H OGH)* A%eotrope sep!r!tion 8ith te"per!t&re

#8! SEPARATION TECHNI>UES FOR AZEOTROPE MI7TURE=

#8" E?t /1t,+' &, t,ll/t, %=

Here ! *!r+e !"o&nt o/ re*!ti-e*$ hi+h5oi*in+ so*-ent is &se# to !*ter *i4&i# ph!se !cti-it$

coe//icients so th!t re*!ti-e -o*!ti*it$ o/ 9e$ co"ponents 5eco"es "ore /!-o&r!5*e /or

sep!r!tion. So*-ent enters the co*&"n ! /e8 tr!$s 5e*o8 the top, !n# e=its /ro" the 5otto"

8itho&t /or"in+ !%eotrope. I/ the )o*&"n /ee# is !n !%eotrope, the so*-ent 5re!9s it.

#82 S/lt &, t,ll/t, % <

It s ! -!ri!tion o/ e=tr!cti-e #isti**!tion in 8hich re*!ti-e -o*!ti*it$ o/ 9e$ co"ponents is

!*tere# 5$ !##in+ to the top re/*&= !s&it!5*e, non>-o*!ti*e ionic s!*t 8hich st!$s in the *i4&i#

ph!se !s it sep!r!tes !s it p!sses #o8n the co*&"n.

#8; P ' u ' S ,%0 D, t,ll/t, % <

It sep!r!tes ! "i=t&re th!t /or"s ! press&re sensiti-e !%eotrope, 5$ &ti*i%in+ t8o co*&"ns !t

#i//erent press&res. B$ ch!n+in+ the press&re the ph!se #i!+r!", !n# the !%eotropic

co"position ch!n+es 8hich he*ps in crossin+ the initi!* !%eotropic co"position /or o5t!inin+

hi+her p&rit$.The press&re -!ri!tion is osci**!tor$, "e!nin+ 8e incre!se,#ecre!se !n# !+!in

incre!se so on.

#84 H 0'% u A3' t *,1 D, t,ll/t, %=

It s ! "etho# o/ sep!r!tin+ ! "i=t&re 5$ !##in+ !n entr!iner th!t /or"s ! ho"o+eno&s

"ini"&" or "!=i"&" 5oi*in+ !%eotrope 8ith /ee co"ponent(s . here the entr!iner !##e#

#epen#s on 8hether the !%eotrope is re"o-e# /ro" top or 5otto" o/ the co*&"n.

#8# H't' 0'%' u A3' t *,1 D, t,ll/t, %=

A "ini"&" 5oi*in+ !%eotrope is /or"e# 5$ the entr!iner. The !%eotrope sp*its into *i4&i#

ph!ses inthe o-er he!# con#enser. One *i4&i# ph!se is sent 5!c9 !s re/*&= the other is sent to

!nother sep!r!tion step or is ! pro#&ct.

#8@ R'/1t,+' D, t,ll/t, % <

A che"ic!* th!t re!cts se*ecti-e*$ 8ith one or "ore /ee# constit&ents is !##e#, !n# the

re!ction pro#&ct is then #isti**e# /ro" the non>re!ctin+ co"ponents. This re!ction is *!ter

re-erse# to reco-er the sep!r!tin+ !+ent !n# re!ctin+ co"ponent. e!cti-e #isti**!tion !*so

re/ers to che"ic!* re!ction !n# #isti**!tion con#&cte# si"&*t!neo&s*$ in the s!"e !pp!r!t&s.

@8! RESIDUE < DISTILLATION CUR:E ANALYSIS OF SYSTEMS FORMING

AZEOTROPE=

For or#in!r$ "&*tico"ponent #isti**!tion,the #eter"in!tion o/ /e!si5*e #isti**!tion se4&ences,#esi+n o/ #isti**!tion co*&"n is prett$ str!i+ht/or8!r#, 8here!s enh!nce# "etho#s o/



sep!r!tion /or !%eotropes !re /!ir*$ co"p*ic!te# !n# the #eter"in!tion o/ /e!si5*e #isti**!tion

#esi+n !n# co*&"n #esi+n is s&5st!nti!**$ "ore #i//ic&*t. M!n$ ! ti"e ri+oro&s c!*c&*!tions

/!i* 5ec!&se o/ non i#e!*ities o/ *i4&i# so*&tion. For "!9in+ the !n!*$sis si"p*e ! -er$

i"port!nt too* is o/ +r!phic!* techni4&es #e-e*ope# 5$ Dohert$ !n# co>8or9ers (Dohert$ et

!*,. !n# 5$ Stich"*!ir !n# co>8or9ers. These +r!phic!* techni4&es !re #escri5e# !s /o**o8s.

@8" R' ,&u' Cu +' <

hen !n entr!iner is !##e# to ! 5in!r$ "i=t&re /or"in+ !n !%eotrope the res&*t is ! tern!r$

"i=t&re, so it is -er$ i"port!nt to consi#er the ph!se e4&i*i5ri&" /or pre#ictin+ the possi5*e

o-erhe!# !n# 5otto"s co"position. Tri!n+&*!r #i!+r!"s !re o/ten &se# to #escri5e

e4&i*i5ri&" /or tern!r$ "i=t&res. One o/ the "ost i"port!nt !spects o/ tern!r$ #i!+r!"s is the

resi#&e c&r-es (Fi+&re '>3 . These c&r-es represent *i4&i# resi#&e co"position !s ! /&nction

o/ ti"e !s ! res&*t o/ ! si"p*e 5!tch #isti**!tion o/ ! tern!r$ "i=t&re. The$ !re #eri-e#

"!the"!tic!**$ !s ! res&*t o/ co"ponent "!ss 5!*!nce #one !ro&n# the sti**, !ss&"in+ th!t

the *i4&i# is per/ect*$ "i=e# !n# is !t its 5&55*e point. The e4&!tion (1 +o-ernin+ the resi#&e

c&r-e is !s /o**o8s.

( ii i

dx dw y x

dt Wdt = −

.......... (1here, = i< "o*e /r!ction o/ ! co"ponent

i < "o*es o/ ! per/ect*$ "i=e# *i4&i# resi#&e in the sti**

$i< "o*e /r!ction o/ co"ponent i in the -!po&r *e!-in+ the sti** inst!nt!neo&s*$ 8hich

is in e4&i*i5ri&" 8ith = i.

The res&*ts o/ this e4&!tion 8hen p*otte# on ! tri!n+&*!r +r!ph /or" resi#&e c&r-es 5ec!&se

the p*ot /o**o8s 8ith ti"e the *i4&i# resi#&e co"position in the sti**. Note th!t 8e !re not

p*ottin+ -!po&r co"position in the p*ottin+ o/ resi#&e c&r-e. A co**ection o/ the resi#&e

c&r-es !t ! /i=e# press&re is c!**e# ! resi#&e c&r-e "!p. P*ottin+ the resi#&e c&r-e 5$ h!n# is

! te#io&s !n# ! *!5orio&s t!s9 8hich re4&ires ! *ot o/ ti"e. esi#&e c&r-e c!n 5e #r!8 e!si*$

5$ &sin+ process si"&*!tors s&ch !s !spen p*&s or )HEM)AD..

A resi#&e c&r-e "!p h!s the /o**o8in+ ch!r!cteristics<

(1 . The #irection in 8hich the !rro8 points st!rts in#ic!tes the initi!* co"position in the

sti** to the /in!* co"position !s ti"e pro+resses.Arro8 st!rts /ro" ! *o8 5oi*in+

co"ponent or !n !%eotropeto the hi+her 5oi*in+ co"ponent or !n !%eotrope.

12



( There c!n 5e #isti**!tion 5o&n#!ries in so"e c!ses 8hich ! resi#&e c&r-e c!nnot cross.

The #isti**!tion 5o&n#!r$ itse*/ is ! resi#&e c&r-e #i-i#in+ the tern!r$ p*ot into

re+ions. These 5o&n#!ries !re ther"o#$n!"ic in n!t&re

S ' , * t/%t t' ,% l 0 ,% ' ,&u' 1u +' /%/l , =

N &'= esi#&e c&r-es 5e+in !n# en# !t no#es.

St/$l' % &'= The co"ponent or !%eotrope 8ith the hi+hest 5oi*in+ point in the re+ion. A** the

resi#&e c&r-es in the re+ion point to (ter"in!te !t this point.

U% t/$l' % &'= The co"ponent or !%eotrope 8ith the *o8est 5oi*in+ point in the re+ion

S/&&l' esi#&e c&r-es "o-e to8!r# !n# then !8!$ /ro" s!##*es. P&re co"ponents !n#

!%eotrope 8hich h!-e ! 5oi*in+ point 5et8een thest!5*e !n# &nst!5*e no#es !re s!##*es

F,0u ' ;

11



F,0u ' 4

F,0u ' #

1



@82 D, t,ll/t, % Cu +' =

An !*tern!ti-e represent!tion /or #isti**!tion on ! tern!r$ #i!+r!" is ! #isti**!tion c&r-e /or

contin&o&s, r!ther th!n 5!tch, #isti**!tion. The c&r-e is "ost re!#i*$ #eter"ine# /or tot!*

re/*&=. The se4&ence o/ *i4&i#>ph!se co"positions, 8hich correspon#s to the oper!tin+ *ine !t

tot!*re/*&=, is p*otte# on ! tri!n+&*!r #i!+r!" (Fi+&re @ . Disti**!tion c&r-e "!ps c!n 5e

!r5itr!ri*$ #irecte# to incre!sin+ or #ecre!sin+ te"per!t&res. Inthe /or"er c!se, the$ c*ose*$

!ppro=i"!te resi#&e c&r-e "!ps.The "!the"!tic!* +o-ernin+ re*!tions /or #isti**!tion c&r-e

!re

, 1 ,i j i j x y+ =

...............(

this is the e4&!tion o/ the oper!tin+ *ine in ! #isti**!tion co*&"n (5oth recti/ic!tion !n#

strippin+ section !t tot!* re/*&=.

, , ,i j i j i j y K x=

..................('

this is the e4&i*i5ri&" re*!tionship 5et8een the -!po&r !n# *i4&i# *e!-in+ ! tr!$. To so*-e

these e4&!tions !n initi!* !ss&"tion o/ = i,1 is "!#e !n# 5$ &sin+ !5o-e e4&!tions in s&ccesion

=i, , =i,' ... etc c!n 5e #eter"ine# . P*ottin+ ! #isti**!tion c&r-e !*so is ! *!5orio&s t!s9 5&t

t!9es *esser e//ort !n# ti"e 8hen co"p!re# to resi#&e c&r-e.

1'



F,0u ' @8Ttri!n+&*!r #i!+r!"

It is /o&n# th!t resi#&e c&r-e "!ps !n# #isti**!tion c&r-e "!p o/ ! tern!r$ s$ste" !re

!ppro=i"!te*$ coinci#ent, so one c!n 5e &se# in p*!ce o/ !nother (interch!n+e!5*$ .

8! PRODUCT OF COMPOSITION REGIONS AND FEASI9LITY ANALYSIS=

esi#&e>c&r-e "!ps !n# #isti**!tion>c&r-e "!ps !re &se# to "!9e pre*i"in!r$ esti"!tes o/

re+ions o/ /e!si5*e pro#&ct co"positions /or #isti**!tion o/ non>i#e!* tern!r$ "i=t&res. The

pro#&ct re+ions !re #eter"ine# 5$ s&peri"posin+ ! co*&"n "!teri!* 5!*!nce *ine on the c&r-e

"!p #i!+r!".I/ ! str!i+ht *ine is #r!8n th!t connects #isti**!te !n# 5otto"s co"positions, th!t*ine "&st p!ss thro&+h the /ee# co"position !t so"e inter"e#i!te point to s!tis/$ o-er!** !n#

co"ponent"!teri!* 5!*!nces. For s&ch ! "!teri!* 5!*!nce *ine, the #isti**!te !n# 5otto"s

co"positions "&st *ie on the s!"e #isti**!tion (resi#&e c&r-e.

For !%eotropic s$ste"s, 8here #isti**!tion 5o&n#!ries !re present, ! /e!si5*e pro#&ct re+ion

c!n5e /o&n# /or e!ch #isti**!tion re+ion.

B8! SEPARATION OF H 2(0) <HCl(0)GASEOUS MI7TURE=

1;



The "ost co""on "etho# /or sep!r!tin+ ! "i=t&re o/ +!s is 5$ !5sorption or !#sorption

either in tr!$ to8ers or p!c9e# to8ers.The other "etho#s !*so inc*&#e "e"5r!ne sep!r!tion

!n# &se o/ "o*ec&*!r sie-es.

B8" S'*/ /t, % $ A$ *t, % 'th & =

A5sorption "etho#s(ph$sic!* !n# che"ic!* < A5sorption "etho#s !re +!s>*i4&i# sep!r!tions

8here !5sor5ents ( !ter !re &se# to re"o-e so*&5*e (H)* +!s co"ponents /ro" H GH)*

"i=t&re. The e4&ip"ent consists o/ !n !#sorption co*&"n in 8hich so*&5*e co"ponents !re

tr!ppe# in !n !5sor5ent in 8hich the !5sor5e# co"ponents !re re*e!se# !t ! *o8er press&re or

hi+h te"per!t&re. There !re t8o t$pes o/ !5sorption "!in*$ ph$sic!* !n# che"ic!*.

(1 Ph$sic!* !5sorption< In this process the so*&5i*it$ o/ +!seo&s co"ponents +ener!**$ o5e$s

Henr$ s *!8, !re "ost*$ !pp*ie# to sep!r!tions o/ H /ro" /ee# +!s. The !#-!nt!+e o/ this

is th!t re+ener!tion o/ !5sor5ents is -er$ e!s$ !n# pro#&ct h$#ro+en o/ this *e!-in+ the

!5sorption co*&"n is ne!r the /ee# press&re.

( )he"ic!* !5sorption< This process is s&it!5*e /or co"p*ete re"o-!* o/ speci/ic i"p&rities

/ro" cr&#e h$#ro+en !n# reco-er$ o/ H /ro" th!t !t its re*!ti-e*$ *o8 press&re or *o8

concentr!tion in co"p!rison 8ith Ph$sic!* !5sorption. This che"ic!* !5sorption "etho#

is &se# "!in*$ /or sep!r!tion o/ !ci#ic s&5st!nces s&ch !s H S,H)N,c!r5on$* s&*phi#e,

H)* /ro" r!8 H +!s. Hot !*9!*ine or !"ine so*&tions !re &se# !s the !5sor5in+ !+ents to

re"o-e the !ci#ic i"p&rities.

B82 S'*/ /t, % $ A& *t, % 'th & =

A#sorption sep!r!tion "etho#s &ti*i%e the pre/erenti!* !#sorption o/ so"e constit&ent species

other th!n h$#ro+en "!in*$ #&e to #i//erence in !#sorption e4&i*i5ri&". epresent!ti-e

!#sor5ents !re si*ic! +e*, !cti-!te# c!r5on, !cti-!te# !*&"ini&" !n# "o*ec&*!r sie-es. Most

sep!r!tion &nits !re oper!te# in #&!* "o#e !n# "o*ec&*!r sie-es. Most sep!r!tion &nits !re

oper!te# in #&!* "o#e o/ !#sorption 5$ p!ssin+ the /ee# h$#ro+en +!s !n# re+ener!tion 5$

"e!ns o/ he!tin+, press&re re#&ction, +!s p&r+e or ! co"5in!tion o/ these "etho#s. In 1 @2 s

! ne8 sep!r!tion techno*o+$, the so c!**e# Qpress&re s8in+ !#sorption PSA processQ (Sirc!r et

!* 8!s #e-e*ope#. A PSA &nit consists o/ ;>1 co*&"ns cont!inin+ speci/ic !#sor5ents. The

co*&"ns !re connecte# thro&+h -!*-es in or#er to per/or" press&ris!tion !n# #epress&ris!tion

5$ sophistic!te# ch!r+e !n# #isch!r+e o/ H +!ses. E!ch co*&"n is oper!te# in se4&enti!*

c$c*e ,8hich consists o/ !#sorption o/ i"p&rities, e4&i*i5ri!tion o/ press&res ,#esorption o/

i"p&rities, p&r+e o/ i"p&rities !n# press&ris!tion.PSA o//ers se-er!* /e!t&res in H in !

pro#&ct +!s !n# other constit&ents in ! p&r+e +!s, sep!r!tion to hi+h*$ p&re h$#ro+en !t !"o#er!te h$#ro+en reco-er$, pro#&ct h$#ro+en press&re is ne!r the /ee# press&re , "inor

13



in/*&ence on the #esi+n o/ the sep!r!tion &nit !n# the p&rit$ !n# reco-er$ o/ pro#&ct H 5$

-!ri!tions in co"p!rison in /ee# h$#ro+en !n# *o8 oper!tin+ cost. O8in+ to these !#-!nt!+es

PSA process o/ -!rio&s t$pes !re 8i#espre!# /or reco-er$ o/ H .

B8; S'*/ /t, % $ ' $ /%' '*/ /t, % * 1' <

Here ! "e"5r!ne !cts !s ! se"i>per"e!5*e 5!rrier !n# sep!r!tion occ&rs 5$ the "e"5r!ne

contro**in+ the r!te o/ "o-e"ent o/ -!rio&s "o*ec&*es 5et8een t8o *i4&i# ph!ses, t8o +!s

ph!ses or *i4&i# !n# ! +!s ph!se. The t8o /*&i# ph!ses !re &s&!**$ "isci5*e !n# the "e"5r!ne

5!rrier pre-ents !ct&!*, or#in!r$ h$#ro#$n!"ic /*o8.

Me"5r!ne process /or H GH)* is +!s #i//&sion 8here the r!tes o/ +!s #i//&sion #epen# on the

pore si%es !n# the "o*ec&*!r 8ei+hts. e "!$ h!-e "o*ec&*!r,tr!nsition !n# ?n&#sen

#i//&sion re+ion #epen#in+ on the re*!ti-e pore !n# +!s "o*ec&*e. The t$pe o/ "e"5r!ne

&se# /or +!s sep!r!tion is /*!t "e"5r!nes !n# spir!* 8o&n# "e"5r!nes.

8! PRESSURE SWING DISTILLATION <

I/ ! 5in!r$ !%eotrope #is!ppe!rs !t so"e press&re, or ch!n+es co"position 5$ 3 "o*L or

"ore o-er ! "o#er!te r!n+e o/ press&re, consi#er!tion sho&*# 5e +i-en to &sin+ t8o or#in!r$

#isti**!tion co*&"ns oper!tin+ in series !t #i//erent press&res. This process is re/erre# to !s

press&re>s8in+ #isti**!tion. ?n!pp !n# Dohert$ *ist press&re>sensiti-e, 5in!r$ !%eotropes,

"!in*$ /ro" the co"pi*!tion o/ Hors*e$. The e//ect o/ press&re on te"per!t&re !n#

co"position o/ t8o "ini"&">5oi*in+ !%eotropes is sho8n in Fi+&re 12.The "o*e /r!ction o/

eth!no* in the eth!no*J8!ter !%eotrope incre!ses /ro" 2.: ;' !t @2 torr to "ore th!n 2. :'3

!t 2 torr. Not sho8n in Fi+&re 5 is th!t the !%eotrope #is!ppe!rs !t 5e*o8 2 torr. A "ore

#r!"!tic ch!n+e in co"position 8ith press&re is seen in /or the eth!no*J5en%ene s$ste",

8hich /or"s ! "ini"&">5oi*in+ !%eotrope !t ;;.: "o*L eth!no* !n# 1 !t". App*ic!tions o/

press&res 8in+ #isti**!tion, /irst note# 5$ Ce8is in ! 1 : p!tent, inc*&#e sep!r!tions o/ the

"ini"&">5oi*in+ !%eotrope o/ tetr!h$#ro/&r!nJ8!ter !n# "!=i"&">5oi*in+ !%eotropes o/

h$#roch*oric !ci#J8!ter !n# /or"ic !ci#J8!ter. !n in9*e #escri5es ! "ini"&">5oi*in+

!%eotrope /or A !n# B, 8ith the TJ$J= c&r-es sho8n in Fi+&re .As the press&re #ecre!ses

/ro" P to P1, the !%eotropic co"position "o-es to8!r# ! s"!**er percent!+e o/ A. An

oper!5*e press&re>s8in+ se4&ence is sho8n in Fi+&re 5. The tot!* /ee#, F1, to )o*&"n 1,

oper!tin+ !t *o8er press&reP1, is the s&" o/ /resh /ee#, F, 8hich is richer in A th!n the

!%eotrope, !n# rec$c*e# #isti**!te, D , 8hose co"position is c*ose to th!t o/ the !%eotrope !t

press&re P . D !n#, conse4&ent*$,F1 !re 5oth richer in A th!n the !%eotrope !t P1. The 5otto"s, B1, *e!-in+ )o*&"n 1 is !*"ost p&re A. Disti**!te,D1, 8hich is s*i+ht*$ richer in A

1@



th!n the !%eotrope 5&t *ess rich in A th!n the !%eotrope !t P , is /e# to )o*&"n , 8here the

5otto"s, B , is !*"ost p&re B. o5inson !n# i**i*!n# #isc&ss the sep!r!tion o/ eth!no* !n#

8!ter, 8here the /resh /ee# is *ess rich in eth!no* th!n the !%eotrope. For th!t c!se, pro#&cts

!re sti** re"o-e# !s 5otto"s, 5&t ne!r*$ p&re B is t!9en /ro" the /irst co*&"n !n# A /ro" the

secon#. Press&re>s8in+ #isti**!tion c!n !*so 5e &se# to sep!r!te *ess>co""on "!=i"&">

5oi*in+ 5in!r$ !%eotropes. A se4&ence is sho8n in Fi+&re12c, 8here 5oth pro#&cts !re

8ith#r!8n !s #isti**!tes, r!ther th!n !s 5otto"s. In this c!se, the !%eotrope 5eco"es richer in

A !s press&re is #ecre!se#.

F,0u ' 8 D,..' '%t 'th & . /3' t *,1 * ' u ' ,%0 *' /t, %

"!8! SIMULATIONS CARRIED OUT TO DETERMINE PHASE 9EHA:IOUR

AND AZEOTROPIC COMPOSITION OF HCL-WATER

"!8" C/ ' Stu& "= A**l,1/t, % . * ' u ' ,%0 &, t,ll/t, % t HCl /t' t'

A/ter so"e tri!*s o/ 5in!r$ ph!se #i!+r!" o/ H)C>8!ter s$ste" !t #i//erent press&res, it 8!s

/o&n# th!t the s$ste" is press&re sensiti-e, so 8e c!n c!rr$ o&t press&re s8in+ #isti**!tion /or

sep!r!tion o/ the "i=t&re. As cite# in *iter!t&re (Se!#erhen*e$ th!t /or econo"ic /e!si5i*it$ o/

press&re s8in+ #isti**!tion the co*&"ns sho&*# 5e oper!te# !t press&res s&ch th!t there is !t

1



*e!st ;>3 "o*L shi/t in !%eotropic co"position. S&ch possi5*e -!*&es o/ press&res 8ere

esti"!te# 5$ "!n$ tri!*s on )HEM)AD@.'so/t8!re !n# it /o&n# th!t 1!t" !n# 2!t" !re

s&ch press&re -!*&es. Another set o/ -!*&es 8ere 2.21!t" !n# 12!t". The ph!se #i!+r!"s

p*otte# 5$ the so/t8!re !re sho8n 5e*o8 /or 1!t" !n# 2!t" &sin+ ther"o#$n!"ic settin+ (?

-!*&e !s PPA .

As 8e c!n see th!t !t 1!t" the !%eotropic co"position is 2.11 !n# it ch!n+es 5$ 2.2; (;"o*

L to 2.2 !t 2!t", th&s no8 it s possi5*e to #esi+n the press&re s8in+ #isti**!tion oper!tion

/or s&ch press&re -!*&es. An !tte"pt to #esi+n press&re s8in+ #isti**!tion 8!s "!#e on the

process si"&*!tor che"c!#@.' !n# 8!s c!rrie# o&t s&ccess/&**$, the /*o8 sheet !n# screen

shots 8ere t!9en /or re/erence.

Fi+&re : !ri!tion o/ "o*e /r!ction o/ H)*G8!ter 8ith te"per!t&re !t 1 !t"

1:



00.10.20.3

0.40.50.60.70.80.9

1

H & 0'% Chl ,&' L, u,& M l' F /1t, %

H & 0'% Chl ,&' :/* M l' F /1t, %

Fi+&re . E4&i*i5ri&" c&r-e /or H)*G8!ter !t 2.21 !t"

Fi+&re 12. !ri!tion o/ "o*e /r!ction o/ H)*G8!ter 8ith te"per!t&re !t 2 !t"

1



Fi+&re 11. E4&i*i5ri&" c&r-e /or H)*G8!ter !t 2 !t"

S' u'%1,%0 . th' P ' u '-S ,%0 D, t,ll/t, % P 1' $ , ul/t, %=

Fi+&re 1 sho8s the press&re>s8in+ se4&ence /or the sep!r!tion o/ H)* /ro" 8!ter. The /ee#

enters the *o8 press&re #isti**!tion co*&"n !t 1 !t" !n# the #isti**!te o/ this co*&"n h!s !co"position th!t !ppro!ches the !%eotropic concentr!tion. This #isti**!te is the /ee# stre!" to

the hi+h press&re co*&"n !t 2 !t". ener!**$ the #isti**!te o/ secon# co*&"n h!s !

co"position th!t is si"i*!r to the /ee# co"position !n# it is rec$c*e# to "i= 8ith the /ee# to

/irst co*&"n. Hi+h p&rit$ H)* is pro#&ce# !s ! #isti**!te stre!" /ro" the secon# co*&"n.

The n&"5er o/ st!+es is -er$ te"per!t&re sensiti-e /or !%eotropic #isti**!tion. For /irst

co*&"n (!s sho8n in Fi+&re1' .it is -er$ sensiti-e !t !ro&n# 12@ K). For secon# co*&"n !s

sho8n inFi+&re 1; it is sensiti-e !t 1 : K)

2



Fi+&re 1 .H)*G8!ter press&re s8in+ !%eotropic !t1 !n# 2!t" /or H)*G8!ter s$ste"

Fi+&re 1'. !ri!tion o/ st!+es 8ith te"per!t&re !t 1 !t" /or H)*G8!ter s$ste"

1



Fi+&re 1;. !ri!tion o/ st!+es 8ith te"per!t&re !t 2 !t" /or H)*G8!ter s$ste"

D&rin+ si"&*!tion /or sep!r!tion o/ H)*G8!ter !%eotrope, /irst co*&"n 8!s 9ept !t 1 !t"

8hi*e secon#s !t 2!t" press&re. The other speci/ic!tions o/ in#i-i#&!* stre!" !re sho8n

5e*o8 in T!5*e No .

Stre!"

No

Te"per!t&re

(R)

Press&re

(!t"

Tot!* F*o8 !te

(9"o*Ghr

t. /r!ction

o/ H)*

t. /r!ction

o/ H)*1 12 1 122 2.23 2. 3

12 .@ 1 3 .:2 2.2@ 2.

' 12@. @ 1 ;2.1 2.11; 2.::

; '2.:; 2 2.2; 1 2

3 22. 3 2 ;2.13 2.11 2.:

T!5*e No. Stre!" speci/ic!tions /or H)*G8!ter press&re s8in+ isotropic !t1 !n# 2!t"

It 8!s o5ser-e# /ro" T!5*e th!t the 5otto" o&t*et o/ the /irst stre!" !chie-e the

!%eotropic co"position !n# in secon# co*&"n it +et sep!r!te#. For /irst co*&"n the '2 st!+es



8ere &se# 8ith 1; th p*!te !s /ee# p*!te 8hi*e /or secon# co*&"n the '2 st!+es 8ere &se# 8ithth st!+e !s /ee# st!+e.

"!82 C/ ' Stu& -2= S, ul/t, % tu& . * ' u ' ,%0 &, t,ll/t, % 1 lu % *' /t,%0

/t !8!"/t /%& "! /t

The re!son /or #oin+ this si"&*!tion 8!s th!t the e!r*ier si"&*!tion the -!*&e &se# /or the n#

#isti**!tion co*&"n &se# ! -!*&e o/ 2 !t" 8hich is on the hi+her si#e !n# s&ch -!*&e "!$ not

5e e!si*$ !chie-e# so ! re!son!5*e !"o&nt o/ 12 !t" 8!s chosen !n# to cre!te ! #i//erence o/

3 "o*L in the !%eotropic co"position the -!*&e o/press&re /or the 1 stco*&"n 8!s /o&n#

s&it!5*e 8!s 2.21 !t". Si"i*!r to the e!r*ier c!se st&#$ si"&*!tions 8!s c!rrie# o&t /or "!n$

inp&t speci/ic!tions !n# the /o**o8in+ res&*ts !re /or the c!se in 8hich the si"&*!tion

con-er+e#.

Fi+&re 13H)*G8!ter press&re s8in+ !%eotropic !t2.1 !n# 12!t" /or H)*G8!ter s$ste"

'



Fi+&re 1@. !ri!tion o/ "o*e /r!ction o/ H)*G8!ter 8ith te"per!t&re !t 2.21 !t"

Fi+&re 1 . E4&i*i5ri&" c&r-e /or H)*G8!ter !t 2.21 !t"

;



Fi+&re 1:. !ri!tion o/ "o*e /r!ction o/ H)*G8!ter 8ith te"per!t&re !t 12 !t"

Fi+&re 1 . E4&i*i5ri&" c&r-e /or H)*G8!ter !t 12 !t"

Stre!"

No

Te"per!t&re

(R)

Press&re

(!t"

Tot!* F*o8 !te

(9"o*Ghr

t. /r!ction

o/ H)*

t. /r!ction

o/ H)*1 1 .22 2.21 122 2.23 2. 3

.;2 2.21 @1. ' 2 1

' 1@.@ 2.21 ':. 2.1' 2.:

; > @.2 12 2.2': 1 2

3 1 .@1 12 ':. ' 2.1' 2.:

T!5*e No. '. Stre!" speci/ic!tions /or H)*G8!ter press&re s8in+ !%eotropic !t 2.1 !n# 12!t"

3



""8! COST ESTIMATION FOR THE PRESSURE SWING SEPARATION=

)ost esti"!tion 5$ consi#erin+ tr!$ co*&"n o/ c!r5on stee* "!teri!*. )o*&"n #i!"eter !n#

hei+ht 8ere consi#ere# !t 1. 3 " !n# 12 " respecti-e*$. Thic9ness o/ the co*&"n !t top !n#

5otto" 8!s /i=e# !t 2.13: c" !n# 2. ' c" respecti-e*$. The tre$ sp!cin+ 8!s /i=e# !t 2.@1 ".

The Fi=e# he!# c!r5on stee* con#enser !n# re5oi*er h!-in+ . 1 " !n# ;1. 3" s&r/!ce

!re! respecti-e*$, #esi+ne# /or 3 !t" press&re &se#. The tot!* p&rch!se cost is esti"!te# to 5e

1@ ;3:.1 ( '2.; /or #isti**!tion co*&"n 2 . /or con#enser !n# re5oi*er

"28! CONCLUSION=

A*tho&+h there !re "!n$ techni4&es !re reporte# /or c!rr$in+ o&t sep!r!tion o/ !%eotropes,

#esi+nin+ o/ !** o/ the" is not e!s$ 8ith the he*p o/ ! process si"&*!tor especi!**$ those

techni4&es 8hich in-o*-e !##ition o/ thir# co"ponent !s c!*c&*!tions 5eco"e te#io&s !n# the

si"&*!tor ()HEM)AD 8!s &n!5*e to con-er+e e-en !/ter se-er!* tri!*s, so press&re s8in+

#isti**!tion o/ H)C>8!ter 8!s chosen !n# !n !tte"pt 8!s "!#e to #esi+n !n# c!rr$ o&t cost

esti"!tion o/ 5oth the #isti**!tion co*&"ns.

The hi+h*i+ht o/ &sin+ press&re s8in+ #isti**!tion /or the sep!r!tion o/ H)C>8!ter !%eotrope

8!s th!t there 8!s no 'r# co"ponent (entr!iner &se# #&e to 8hich the !##ition!* cost o/

entr!iner 8!s !-oi#e# !n# !*so the si"&*!tions 8ere !5*e to con-er+e in the c!se o/ press&re

s8in+ #isti**!tion !s !##ition o/ ! 'r# co"ponent co"p*ic!tes the "!the"!tics !n#

!tt!in!5i*it$ o/ ! con-er+in+ so*&tion.

In the present st&#$, it 8!s /o&n# th!t #isti**!tion co*&"ns oper!tin+ !t 1!t" !n# 2!t" !*on+

8ith !5o-e sho8n speci/ic!tions "!#e the c!*c&*!tions con-er+e !n# H)* !n# 8!ter 8ere

o5t!ine# !s !*"ost p&re pro#&cts. In the secon# c!se st&#$ the press&res chosen 8ere 2.21!t"

!n# 12!t" !n# the top pro#&cts 8ere p&re H)* !n# 8!ter.

hi*e:2.;L o/ H)* 8!s reco-ere# in the c!se 1 o/ 1!t" !n# 2!t" , in c!se !t 2.1!t" !n#

12!t" it 8!s /o&n# to 5e @.@L. So 8e c!n see th!t the /r!ction o/ H)* reco-ere# is s*i+ht*$

hi+her in c!se 1.

The cost o/ 1st #isti**!tion 8!s /o&n# to 5e 2 !n# n# co*&"n 8!s /o&n# to 5e '2.;

!n# the speci/ic!tions /or hei+ht, #i!"eter etc., 8ere t!9en 8hich 8ere "ost co""on*$ &se#

in !n$ che"ic!* in#&str$.

@



";8! 9I9ILOGRAPHY=

1. Dohert$, M. F., !n# M!*one, M. F. ( 221 , )oncept&!* Desi+n o/ Disti**!tion S$ste". Ne8

Yor9< Mc r!8>Hi**, Inc.. Sirc!r, S., !n# o*#en, T.). ( 222 , P&ri/ic!tion o/ h$#ro+en 5$ press&re s8in+ !#sorption,

Sep!r!tion Science !n# Techno*o+$, '3(3 , @@ .'. Se!#er, 0. D., !n# Hen*e$, Ernest 0. (1 : , Sep!r!tion Process Princip*es. Ne8 Yor9<

i*e$.;. Pro+ress o/ Intern!tion!* Pro+r!" on H$#ro+en Pro#&ction 8ith the )opper )h*orine

c$c*e3. N!terer .F., S&ppi!h S., Sto*5er+ C., Ce8is M., !n+ Z., osen M.A., Dincer I., !5rie*

?., O#&9o$! A., Secni9 E,. E!ston E.B., !n# P!p!n+e*!9is . ( 213 , Pro+ress in

ther"oche"ic!* h$#ro+en pro#&ction 8ith the )opperJ)h*orine c$c*e, I0HE, ;2 (1 ,

@ :'J@ 3.@. )HEMSTATIONS 8e5site.

. Tre$5!* (1 :2 . M!ss>Tr!ns/er Oper!tions ('r# E#ition e#. . Mc r!8>Hi**.:. Perr$, o5ert H., !n# reen, Don . (1 :; , Perr$ s )he"ic!* En+ineers H!n#5oo9 (@th

E#ition e#. . Mc r!8>Hi**. Se*ectin+ Entr!iners /or A%eotropic Disti**!tion, i-e9j&*9!, M!#h&r! )hi*p&n9!r, Cione*

O Yo&n+, )*e!r !ter B!$ Techno*o+$ IN).

fayaz report on challenges associated with sepn of hcl-water azeotrope 04.08 (7)

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