American Journal of Chemical Engineering

2013; 1(3): 59-64 Published online November 30, 2013 (htt :!!"""#s$ien$e ublishin%%rou #$om!&!'&$he) doi: 10#1164(!&#'&$he#20130103#11

Simulation of ammonia synthesis

M. R. Amin, S. Sharear, N. Siddique, Shaidul Islam
)hemi$'l *n%ineerin% +e 'rtment, ,-*., +h'/', ,'n%l'desh

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1# 2# 3min, 4# 4h're'r, N# 4iddi5ue, 4h'idul 6sl'm# 4imul'tion o7 3mmoni' 48nthesis# American Journal of Chemical Engineering# 9ol# 1, No# 3, 2013, # 59-64# doi: 10#1164(!&#'&$he#20130103#11

Abstract: 3mmoni' is rodeu$ed to %ive ' 7in'l rodu$t n'med ure' "hi$h is ' ver8 im ort'nt 7ertili:er 7or hi%her
nitro%en $ontent#4ever'l ro$esses h's been invented 7or o timum rodu$tion o7 'mmoni'# No"-'-d'8s, 3mmoni' rodu$tion is m'inl8 done b8 ;'ber ro$ess in "hi$h nitro%en 'ndh8dro%en re'$t in the resen$e o7 'n iron $'t'l8st to 7orm 'mmoni'# .he h8dro%en is 7ormedb8 re'$tin% n'tur'l %'s 'nd ste'm 't hi%h tem er'tures 'nd the nitro%en is su lied 7rom the'ir# <ther %'ses (su$h 's "'ter 'nd $'rbon dio=ide) 're removed 7rom the %'s stre'm 'ndthe nitro%en 'nd h8dro%en 'ssed over 'n iron $'t'l8st 't hi%h tem er'ture 'nd ressure to7orm the 'mmoni'# 6n our "or/, simul'tion o7 'mmoni' s8nthesis ro$ess is done on 3s en ;8s8s >#1# ,8 usin% 1#0>e?005/mole!hr meth'ne, 2#(e?005/mole!hr h8dro%en, 1#02e?005/mole!hr nitro%en, "e h've rodu$ed4#6e?004 /mole!hr 'mmoni'#6t h's 'lso been 7ound th't 'mmoni' rodu$tion in$re'ses "ith the rise o7 ressure o7 7resh 7eed#

Keywords: 3mmoni', 4imul'tion, ;eber, @ertili:er, 2e7ormer

. Introduction
3mmoni' is ' $om ound o7 nitro%en 'nd h8dro%en "ith the 7ormul' N;3# 6t is ' $olorless %'s "ith '$h'r'$teristi$ un%ent smell# 3mmoni' A1B $ontributes si%ni7i$'ntl8 to the nutrition'l needs o7 terrestri'l or%'nisms b8servin% 's ' re$ursor to 7ood 'nd7ertili:ers A5Bindustr8 A(B# 3mmoni', both dire$tl8 or indire$tl8, is 'lso ' buildin%-blo$/ 7or thes8nthesis o7 m'n8 h'rm'$euti$'ls 'nd is used in m'n8 $ommer$i'l $le'nin% rodu$ts# 3lthou%h in "ide use,'mmoni' is both $'usti$ 'nd h':'rdous# .he%lob'l rodu$tion o7 'mmoni' 7or 2012 is 'nti$i 'ted to be 19( milliontons, ' 35C in$re'se over the estim'ted 2006 %lob'l out ut o7 146#5 million tones# 3mmoni', 's used $ommer$i'll8, is o7ten $'lled 'nh8drous A2B 'mmoni'# .his term em h'si:es the 'bsen$e o7 "'ter inthe m'teri'l# ,e$'use N;3 boils 't D33#34 E) (D2(#012 E@) 't ' ressure o7 1 'tmos here, the li5uid must be storedunder hi%h ressure A3B or 't lo" tem er'ture# F;ousehold 'mmoni'F or F'mmonium h8dro=ideF is ' solution o7 N;3 in"'ter# .he $on$entr'tion o7 su$h solutions is me'sured in units o7 the ,'umGs$'le (densit8), "ith 26 de%rees,'umG ('bout 30C "!" 'mmoni' 't 15#5 E)) bein% the t8 i$'l hi%h-$on$entr'tion $ommer$i'l rodu$t# ;ousehold'mmoni' r'n%es in $on$entr'tion 7rom 5 to 10 "ei%ht er$ent 'mmoni'# 6n this e= eriment ' det'iled stud8 is er7ormed 'bout
A11B

the ro$ess b8 me'ns o7 simul'tion in 3s en ;8s8sv>#1 #4in$e ;'ber ro$ess is "idel8 used 7or m'=imum rodu$tion o7 'mmoni', "e h've simul'ted the ro$ess th't is b'sed on ;'ber A10B ro$ess# .hou%h simul'tion does not %ive the re'l "orld er7orm'n$e or the re'l li7e rodu$tion environment but i7 the b'si$ ro$ess is /no"n 'nd rel'ted d't' 're 'v'il'ble, it surel8 is the best "'8 b8 "hi$h 'n individu'l $'n %et ide's o7 'n industri'l ro$ess "ithout $ondu$tin% 'n8 e= eriment#

!. Methodolo"y
.he ro$ess o7 rodu$in% 'mmoni' is simul'ted in 4imul'tion so7t"'re 3s en ;8s8s>#1# 3s en ;H4H4 ro$ess simul'tor is ' $ore element o7 3s en.e$hIs3s en<N*Jen%ineerin% ' li$'tions# 6t rovides 5uite '$$ur'te results "hi$h m'/es it 'n e77i$ient simul'tor# 6t rovides $om rehensive thermod8n'mi$s b'sis 7or '$$ur'te determin'tion o7 h8si$'l ro erties, tr'ns ort ro erties, 'nd h'se beh'vior# 3s en ;H4H4 $'n be used to determine outlet ro$ess $onditions i7 the inlet $onditions li/e tem er'ture, ressure, 'nd $om osition 're s e$i7ied# 6n this simul'tion "e used Pen%-2obinson model 7its best to e5uilibrium ro$ess#

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1# 2# 3min et al.: 4imul'tion o7 3mmoni' 48nthesis

2.1. Process Description

.he sim li7ied blo$/ di'%r'm o7'mmoni' s8nthesis is %iven belo"#

Figure 01. block diagram of ammonia synthesis.

Figure 02. Hysys Process flow diagram of ammonia synthesis.

2.1. Reaction Involved 6n h8dro%en rodu$tion ste , 7our re'$tions 're involved#Khi$h 'reLn< ? ;24M Ln4 ? ;2< this re'$tion is done to $'rried out 'll sul her $om ounds 7rom n'tur'l %'s# @ollo"in% re'$tions o$$ur in re7ormer-

);4 ? ;2< M 3;2 ? )< );4 ? 2;2< M 4;2 ? )<2 )< ? ;2< M ;2 ? )<2 .his %'seous mi=ture is /no"n 's s8nthesis %'s# 6n nitro%en 'ddition ste , s8nthesis %'ses 're mi=ed "ith 'ir in the se$ond'r8 re7ormer# .he re'$tions 're)< ? ;2< M )<2 ? ;2

3meri$'n Nourn'l o7 )hemi$'l *n%ineerin% 2013; 1(3): 59-64

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<2 ? 2);4M 2)< ? 4;2 <2 ? );4 M)<2 ? 2;2 2<2 ? );4M 2;2< ? )<2 6n $'rbon mono=ide remov'l ste , $'rbon mono=ide is removed b8 "'ter %'s shi7t re'$tion# )< ? ;2<M )<2 ? ;2 6n 2emov'l o7 $'rbon o=ides ste , 'll $'rbon o=ides 're $onverted to meth'ne b8 7ollo"in% re'$tions)< ? 3;2M );4 ? ;2< )<2 ? 4;2M );4 ? 2;2< 6n 'mmoni' s8nthesis ste , 7o"lloin% re'$tion rovides 7in'l rodu$t 'mmoni'N2 ? 3;2M 2N;3 2.1.1. Hydrogen Production ;8dro%en is rodu$ed b8 the re'$tion o7 meth'ne "ith "'ter# ;o"ever, be7ore this $'n be$'rried out, 'll sul7urous $om ounds must be removed 7rom the n'tur'l %'s to revent$'t'l8st A4B oisonin%# .hese 're removed b8 he'tin% the %'s to 400 o) 'nd re'$tin% it "ith :in$o=ide# @ollo"in% this, the %'s is sent to the rim'r8 re7ormer 7or ste'm re7ormin%, "here su er-he'ted ste'm is 7ed into the re7ormer "ith the meth'ne# .he %'s mi=ture he'ted "ith n'tur'l%'s 'nd ur%e %'s to >>0o) in the resen$e o7 ni$/el $'t'l8st# 3t this, meth'ne $onverts to h8dro%en,$'rbon dio=ide 'nd sm'll 5u'ntities o7 $'rbon mono=ide# 2.1.2. Nitrogen Addition .he s8nthesis %'s is $ooled sli%htl8 to >350)# 6t then 7lo"s to the se$ond'r8 re7ormer "hereit is mi=ed "ith ' $'l$ul'ted 'mount o7 'ir# .he hi%hl8 e=othermi$ re'$tion bet"een o=8%en'nd meth'ne rodu$es more h8dro%en# 6n 'ddition, the ne$ess'r8 nitro%en A6B is 'dded in the se$ond'r8 re7ormer#3s the $'t'l8st th't is used to 7orm the 'mmoni' is ure iron, "'ter, $'rbon dio=ide 'nd$'rbon mono=ide must be removed 7rom the %'s stre'm to revent o=id'tion o7 the iron# .hisis $'rried out in the ne=t three ste s# 2.1.3 Removal o !ar"on #ono$ide ;ere the $'rbon mono=ide is $onverted to $'rbon dio=ide ("hi$h is used l'ter in the s8nthesiso7 ure') in ' re'$tion /no"n 's the "'ter %'s shi7t re'$tion#.his is '$hieved in t"o ste s# @irstl8, the %'s stre'm is 'ssed over ' )r!@e3<4$'t'l8st A9B 't3600) 'nd then over ' )u!Ln<!)r $'t'l8st 't 2100)# .he s'me re'$tion o$$urs in both ste s,but usin% the t"o ste s m'=imi:es $onversion# 2.1.%. &ater Removal .he %'s mi=ture is 7urther $ooled to 400), 't "hi$h tem er'ture the "'ter $ondenses out 'ndis removed# 2.1.'. Removal o !ar"on ($ides .he %'ses 're then um ed u throu%h ' $ounter-$urrent o7 -)324<O solution ('1+*3 solution)# )'rbon dio=ide

is hi%hl8 soluble in -)324<O, 'nd more th'n 99#9C o7 the )<2in the mi=ture dissolves in it# .he rem'inin% )<2 ('s "ell 's 'n8 )< th't"'s not $onverted to )<2 in 4te 3) is $onverted to meth'ne (meth'n'tion) usin% ' Ni!3l2<3$'t'l8st 't 3250)# .he "'ter "hi$h is rodu$ed in these re'$tions is removed b8 $ondens'tion 't 400) 's 'bove#.he $'rbon dio=ide is stri ed 7rom the -)324<O 'nd used in ure' m'nu7'$ture# .he-)324<O is $ooled 'nd reused 7or $'rbon dio=ide remov'l# 2.1.). *ynt+esis o Ammonia .he %'s mi=ture is no" $ooled, $om ressed 'nd 7ed into the 'mmoni' s8nthesis loo # 3 mi=ture o7 'mmoni' 'nd unre'$ted %'ses "hi$h h've 'lre'd8 been 'round theloo 're mi=ed "ith the in$omin% %'s stre'm 'nd $ooled to 50)# .he 'mmoni' resent isremoved 'nd the unre'$ted %'ses he'ted to 4000) 't ' ressure o7 330b'r% 'nd 'ssed over'n iron $'t'l8st# -nder these $onditions 26C o7 the h8dro%en 'nd nitro%en 're $onverted to'mmoni'# .he outlet %'s 7rom the 'mmoni' $onverter is $ooled 7rom 2200) to 300)# .his$oolin% ro$ess $ondenses more the h'l7 o7 the 'mmoni', "hi$h is then se 'r'ted out#.he rem'inin% %'s is mi=ed "ith more $ooled, $om ressed in$omin% %'s# .he re'$tiono$$urs in the 'mmoni' $onverter#.he 'mmoni' is r' idl8 de$om ressed to 24b'r%# 3t this ressure, im urities su$h 'smeth'ne 'nd h8dro%en be$ome %'ses# .he %'s mi=ture 'bove the li5uid 'mmoni' ("hi$h'lso $ont'ins si%ni7i$'nt levels o7 'mmoni') is removed 'nd sent to the 'mmoni' re$over8unit# .his is 'n 'bsorber-stri er s8stem usin% "'ter 's solvent# .he rem'inin% %'s ( ur%e%'s) is used 's 7uel 7or the he'tin% o7 the rim'r8 re7ormer# .he ure 'mmoni' rem'inin% ismi=ed "ith the ure 'mmoni' 7rom the initi'l $ondens'tion 'bove 'nd is re'd8 7or use in ure' rodu$tion, 7or stor'%e or 7or dire$t s'le#

#. Results and $iscussions

,8 usin% 1#0>e?005/mole!hr meth'ne, 2#(e?005/mole!hr h8dro%en, 1#02e?005/mole!hr nitro%en "e h've rodu$ed4#6e?004/mole!hr 'mmoni'# @rom %r' h "e $'n see th't 'mmoni' rodu$tion in$re'ses "ith the rise o7 ressure o7 7resh 7eed# @rom 7i%ure-03, it h's been seen th't "ith in$re'se o7 ressure o7 resh 7eed tube side delt' . de$re'ses %r'du'll8 to -46#450) 't 1#200e?004 /P'# 37ter re'$hin% this v'lue delt' . in$re'ses 't hi%h r'te# @rom 7i%ure -04, in the $'se o7 tube side delt' .(0)),delt' . in$re'ses to -242#5 0) in ' line'r 7'shion "ith ositive slo e "ith res e$t to 7resh 7eed tem er'ture# <n the other h'nd, in the $'se o7 shell side delt' .(0)),delt' . de$re'ses in ' line'r 7'shion "ith ne%'tive slo e# @rom 7i%ure-05, rodu$t 7lo" r'te in$re'sses 5ui$/l8 "ith the in$re'se o7 7resh 7eed ressure to 4#000e-004 't 1#>50e?004 /P'# 37ter re'$hin% this oint rodu$t 7lo" r'te slo"s do"n 'nd tends to be$ome $onst'nt# 6n 7i%ure-06, rodu$t mol'r 7lo" in$re'ses "ith the

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1# 2# 3min et al.: 4imul'tion o7 3mmoni' 48nthesis

in$re'se o7 7resh 7eed mol'r 7lo" in line'r 'ttern#

Figure 0). Case &tudy* effect of fresh feed molar flow "kgmole)hr# on !roduct molar flow "kgmole)hr#. Figure 03. Case Dtrdy1 effect of fresh feed !ressure "kPa# on heat e$changer 1 %ube &ide Delta % "'C#.

.here 're sever'l boilin% oint $urve 'sso$i'ted "ith the simul'tion "hi$h 're in$luded belo"-

Figure 0,. Case %em!erature "'C# +s +olume !ercent",# !lot.

Figure 0%. Case &tudy( effect of fresh feed tem!erature "'C# on heat e$changer 1 %ube &ide Delta % "'C# and &hell &ide Delta % "'C#.

Figure 0-. Critical %em!erature "'C# +s +olume !ercent",# !lot.

Figure 0'. Case &tudy1 effect of fresh feed !ressure "kPa# on !roduct molar flow "kgmole)hr#.

@rom 7i%ure-0>, "e $'n see th't 't 0C volume er$ent boilin% oint is -3250) 'nd 't 100C it be$omes -(00) "ith %r'du'l in$re'se 7rom 0-100C# @rom 7i%ure-0(, $riti$'l tem er'ture st'rts 7rom -2900) 'nd in$re'ses in line'r 7'shion u to -1000) 't >0C volume er$ent# .h'n it be$omes $onst'nt u to >5C 't the s'me tem er'rure# 6t '%'in in$re'ses in line'r 7'shion "ith

3meri$'n Nourn'l o7 )hemi$'l *n%ineerin% 2013; 1(3): 59-64

63

%re'ter slo e th'n revious one#

Figure 12. 0i1uid Density "kg)m2# +s +olume !ercent",# !lot. Figure 0.. Critical Pressure "kPa# +s +olume !ercent",# !lot.

@rom 7i%ure-11, '$entri$ 7'$tor in$re'ses 5uite r' idl8 7rom -0#5000 to -0#2(00 't 1C volume er$ent# 6t th'n in$re'ses slo"l8 "ith slo e sm'ller th'n revious in$re'se u to 0#0300 't 50C# 6t then de$re'ses 'nd rem'in $onst'nt u to (0C 'nd then st'rts to in$re'se# @rom 7i%ure-12, li5uid densit8 in$re'ses line'rl8 7rom 4>5#0 /%!m3 to 1390 /%!m3 't 60C 6t is then de$re'ses line'rl8 u to 300#0/%!m3 't (0C 'nd in$re'ses 7or the rem'inin% volume er$ent u to 600 /%!m3#

%. &onclusions
3mmoni' is ' ver8 im ort'nt rodu$t# 6t is used in v'rious ur oses# 3mmoni' rodu$tion de ends on lenti7ul su lies o7 n'tur'l %'s, ' 7inite resour$e, to rovide the h8dro%en# +ue to 'mmoni'Ps $riti$'l role in intensive '%ri$ulture 'nd other ro$esses, sust'in'ble rodu$tion is desir'ble# ;8s8s hel ed us ' lot to underst'nd 'nd to desi%n'mmoni' rodu$tion# .he "or/ dis$ussed in this ro&e$t "'s 7o$used on the develo ment usin% di77erent /ind o7re'$tors "hi$h $'n be ro$essed to rodu$e 'mmoni'# +i77erent units h've been s e$i7ied '$$ordin% to the desired re5uirement o7 the rodu$t# Produ$t 7lo" r'te "'s in$re'sed b8 in$re'sin% 7resh 7eed 7lo" r'te# <ther th'n 7resh 7eed 7lo" r'te, rodu$t 7lo" r'te $'n 'lso be in$re'sed b8 in$re'sin% 7resh 7eed ressure# 6t "'s 5uite simil'r to the re'l l'nt o er'tion# 4o "e $'n redi$t 5uite '$$ur'tel8 'bout the ro$ess b8 simul'tin% it in ;8s8s#

Figure 10. -olecular .eight +s +olume !ercent ",# !lot.

@rom 7i%ure-09, $riti$'l ressure in$re'ses 't slo"er r'te st'rtin% 7rom 1500 /P' u to 5000 /P' 't 60 volume er$ent# 6t then rem'ins 'lmost $onst'nt 't the s'me ressure to (0C 'nd then in$re'ses it r' idl8# @rom 7i%ure-10, mole$ul'r "ei%ht in$re'ses 7rom -5#00 to 40 't 60C in 'lmost str'i%ht line 'ttern#6t then de$re'ses in line'r 7'shion to 16 't (0C 'nd rem'ins $onst'nt 7or rem'in% volume er$ent#

Re'erences
A1B Host, +on 1# (200>)# F3mmoni' 'nd Oi5uid 3mmoni' 4olutionsF#&ystematic 3norganic Chemistry#64,N 1-406>>302-6# P'r/es, Q# +#; 1ellor, N# K# (1939)# -ellor4s -odern 3norganic Chemistry (Ne" *dition, 2evised 'nd 2e"ritten ed#)# Oondon: Oon%m'ns, Qreen 'nd )o# # 255R256 S 362# .orrelles, N# 1#, ;o, P# .# P#, 2odri%ue:, O# @#, )'nto, N# (19(5)# F9O3 observ'tions o7 'mmoni' 'nd $ontinuum in re%ions "ith hi%h-velo$it8 %'seous out7lo"sF#APJ2((: 595#

A2B

Figure 11. Acentric /actor +s +olume !ercent ",# !lot.

A3B

64

1# 2# 3min et al.: 4imul'tion o7 3mmoni' 48nthesis

A4B A5B

."8%%, 1'rt8n 9# (19(9)# Catalyst Handbook (2nd *dition ed#)# <=7ord -niversit8 Press#64,N 1-(>4545-36-># /ertili5er 3ndustry6 Processes7 Pollution Control and Energy Conser+ation b8 1'rsh'll 4itti% (19>9) No8es +'t' )or #, N#N# 64,N 0-(155-0>34-( @# ,o:so, Q# *rtl, 1# Qrun:e 'nd 1# Keiss (19>>)# F6nter'$tion o7 nitro%en "ith iron sur7'$es: 6# @e(100) 'nd @e(111)F# Q 3ustin, &hre+e8s Chemical Process 3ndustries, 5th ed#, 1$Qr'"-;ill6ntern'tion'l *ditions, Ne" Hor/, 19(4#

A(B

; ,'/emeier 'nd others, 3mmoni', 9llmann8sEncyclo!edia of 3ndustrialChemistry, 9ol# 32, 9); 9erl'%se%esells$h'7tmb;, Keinhein,199># LTo"'l$:8/, 4 Nodi: 'nd N 4ente/, A!!lied Catalysis A6 :eneral, 13(, (3, 1996#

A9B

A6B

A10B L 1 Qor'n, %he &tory of /rit5 Haber, -niversit8 o7 </l'hom' Press, 196># A11B ;H4H4# 3s en ;H4H4 user %uide# 3s en .e$hnolo%8 6n$# """#'s ente$h#$om

A>B