,_-_-

ure'cr KnclwHcw.Eorn
Wttr"rr
hhp-' r-

pe lnclu:nt'^ rnp$t'

LJrE'dKnt:wHow-orn
w'r" f" f t:r
I'Ft

ur r E

.c' I d tJ,tt

t_ n-r c-nrr t

l. lnlroductlon
As described n

-[h

ar m o d y n i] nt

i r:

s': t t ir e l..f r r,r n t- r n ces

-- dlfferent countries and many contrlbutions to the process were made slnce then.

as or-lglnally suggested by Basaroff was flrst translated lnto lndustrlal manufacture by German chemlsts ln I. G. Farben ln about 1920. The development oF the process conflnues to go ahead ln

the February 2009 Procass Paper of UreaKnowHow.corn, the large scale manufacture of urea in rnodcrn tlrnes has bcen basnd on synthcsis from amrhonia and carbon dioxldc. Thls process

There are two main reactlons lnvolved ln the synthesis of urea lrom l_-arbon clioxlde ancl arnmonla; the formatlon of ammonlum carbarnate forn carbon dloxlde and ammonla, and the conversion of equatlons:
CO2

rnrnonlum carbarnotc lnto urca. Thc reactions involved cbn bc rcpresentcd by the following

lJreaKnowHow.corn Mark Brouwer General tvlanager

(G) + 2 NH! (G) c

(L)

NH2COONH4 (L)

Ireaction 1] Ireaction 2]

NH2CCIONHT

NHzCONH: (L)

+ HO (t.)

Su nr m ary As descrlbed ln rhe Febrlary 2009 Process Paper of UreaKnovJl-low.com, the large scale manufacture of urea in modern tlmes has been based on synthesls from ammonia and carbon?loxiOe. Thls process as originally suggested by Basaroff was first translated into lndustrial manufactur by errnan chenrlsts ln I. G. Farhen in about 1920. There are two maln reactlons lnvolved ln the synthesls of urea from carbon dloxlde and smrnonla; the formatlon of ammonlurn corbamatc from carbon dloxide and ammonla, and thc convcrslon of ammonium carbamate into urea, The reactlolls lnvolved cdn be represente<l by the followlng equatlons: Thls paper dlscusses the therrnodynamics of the urea process. The therrnodynamlc models of Frejacques and Lemkowitz, de Cooker and van de Berg will be presented and ln the lnfluence of varlouE process parameters llke N/C, H/C, temperature and pressure will be disctssed.

temperatute of 135 to 200 oC, tlre reaction as represented by l.eacUorr 1 is alrnost instantaneous and complete, provlded the pressure of the systern ls greater than the decomposlilon pressure of the ammonium carbamate at the system temperature. Wen the system ls dry, the only product ls arnmoniurn carbamate lf the proper relative proportlon of the two constituents are used, I the presence of water, carbonates of ammonia are also fclrmecl- Water anci ammonlum carbamate form a rneta-stable system wlrlch evolves slowly into a complex mlxture whose composltlon depends upon temperature and concentrailon. Tle formatlon of c'arbanrate is hlghly exotherntlc. The huge quanHty of heat evolverl ln the formailon of ammoniurn carbamate from clrbon dloxlde and arnmon neceisttates the conilnual removal of heatln.lts_ qreparation. At the polnt of temperature below the nreltlng point of amrnonlum carbamate, about 155 oC, the arnmonlurn carbarnate fornrs a cornpact coverlng-adhering fllm on the wall of th vessel whlch conducls heat por:rly and thus lncreases the dlfflculty of remov-ing the releasecl heat of ea{Uon. several means have been proposed to clrcumvent thls difflculty. Above the meltlng polnt of ammonlum carbamate, the problems resulHng from the formailon of a bad heat conduclng film no longer exlst, but they are replaced by serlous p.ol.m of c<lrroslon.
Slnce the reactlon represented by reactlon 1 is an equillbriunl reacon. a thorough knowledge for dlssoclation pressure of ammonlurn carbamate, equilibrium constants and free energles of arnrnonlum carbamate synthesis ls a "must" for the investlgation of the process. Heat removal s discssed ln the prevlous paragraph is very important ln the process of manufacture. It ls necessary to know about the quantlty of heat formatlon of ammonlurn carbarnate. Ammonium carbamate ltself ls not sultable for fertlllzer appllcatlon because of lts volaUllty and hygroscoplc nature and because lts appllcagon learts to crop "burnlng".

At tlre

Contents

1. lrrtroductiorr 2. Thermodynam lc models 2.1 Frejacques m odel 2.2 Lem kow itz m odel 2.3 Urea process lndlcators 3. lnfluence of various process parameters 3.1 lnlluence of Hl C ratio 3.2 lnfluence of N/ C ratio 3.3 I nf luence of tem pratu r 3.4 lnf luence of pressur6

As to the reactlon, re.presented by reactlon 2, the dehydratlon of carbarnate lnto urea is never complet-ed. The yield of urea lnvolves many factors, such as molar ratlo of amrnonla to carbon dioxde, effect of water, reactor pressure, tlrne of residence, etc. The reactlon ls assumed to proceed entirely ln the llquld phase. The resulting proclt"tct ls a complex mixture of water, urea, unconverted amrnonlum carbamate and arnmonlum carbonates resultlng frorn the actlon oi ammonlum carbamate on the water ibrmed. 'Ihe reaction 2 ls an endotherrnlc reaction; however, the quanflty of heat absorbed ls much smaller than the heat evolved ln the formation of antmonlum carbamate from carbon dloxlde
and arnrnonla. The rate of the urea fonnatlon reaction lncreases rapidly above

l60oc,

as can be seen ln Figure

l.

LJ
t'

recgKnclwHow. {:t:rn
l-r
G, r

LlrecaKnc:\4/How.cc:m
\/l'rarl $t f'lr'
.lr

f'f -;r 1- ;:r ,5

i*r

lJ

t.

: I t i.;

1'

ir

|;"

e' i,l-l]ji;'ir

r..l rTiE:,t'rt

Since

ammonlum carbamlte ls qulte

2. Thernl odyrtant tc models

temperatures necessary to carry

elevatc4 prcssurcs.

volatile at

these lt ls

2.1

F-rclaffueg xnadel

out the synthesis at

Flgure

that the

also shows
converslon

The flrst and still most widely used thermodynamlc modal for the ammonia-water-cqrbon dloxlde systern at urea synthesis conditlons Was presented ln 1948 by H. FreJacques in Chimie et lndustfe 60, 221 1. In thls model the llquid phase is described by one overall ractlon: co2

cartamate

of

ammonlum

does

complctely, lcadlng
to the necessity of dlssoclauon and
recycle process step.

to not

urea 90
a a

(L) + 2 NH3 (L) .;:,

N|{2CONHZ

(L) + t"t2o (L)

[reactiorr 3l

Kl

Xurea(L)
=

XH2O(L)

All
I
1

processes follow the same general

(xNH,(L))? + to

[reaction 4l
XCO(L)
Nl-13

---l - -.- ----.*.'L-!'iq:.rnaterialscarbon

Tni t nr
)

princlple: The

raw
ancl

XNI'i3(L) ancl XCOz(L) refer

ond CO2 ln the llqulct phase no[ exlstlng as urea,

.>--

clloxrde
carbemare

arnmonla enter the

Flgurg l: Converglon ot ammonlum dlllernl lem Peral urs

ro rrea wrrh rms ar

?l!o!Fue sornenmes as carbamate already,

or reactor'

Frejacques assumed, for his model, that the urea synthesls solution dld not contaln any ammonlum carbamate. Later Ivo Mavrovic clalmed to have improved the Kl values, derived by FreJaques, so that the conversions can be calculated accurately up to t9O-200 oC. Although Frcjacqucs modcl ls strong due to lts slmpliclty, it also cannot exploin somc observatlons such as for exatnple the fact that tlre conversion of carbornate into urea (Kl) increases with

ln

whlch

they

(further) react and forrn urea. The reacted nrlxture then flows rut from the reactor lnto a decomposer or strlpper, in which the non converted materals are decomposed and separated lrom the urea product ln the solution. The urea solution ls ln a condltlon to recover the final product urea. The unconverted ammonla and carbon dloxide recovered from the decomposer or stripper are Wplcally recycled back to the reactor to reach a complete conversion lnto urea; thls is the prlnclple of the so
called total-recycle Process.

tefnperature at least to (i90-20ooc), whlle rhe reacllon 3ls strong exothermlc (about -22 kcal/mol). However an equillbrium constant (Kl) which lncreases wlth temperature for an exothermlc reactlon ls in contradlctlon with the rule of Van't Hoff. The rule of Van 't Hoff in chemlcal thermodynarnics relates the change ln temperature (T) to the change ln the equllibrlum constant (K) glven the standard enthalpy change (AHo) for the process. The equation was flrst derlved by Jacobus Henrlcus van 't Hoff,

d hr

The corroslon worklng of carbamate ln the llquld phase, llke the klnetlc rate of the urea formatlon reaction and the vapour pressure ot the synthesis solution, are roughly an exponentlal lunctlon of the temperatlrre The conditions ln a urea reactor are therefore a conr,romlse of high reactlon rate and degree of conversion and low corrosion rate and reactor pressure.. Nornral operating corrdltions lle ln oC and 130-300 bars. the area of 170-200 All of the above mentioned factors such as removal (and optimurn use) of the large reoctlon heat of the carbarnate forrnatlon reoctlon, the hlgh pressures lnvolved, the necesslty of substantlal recrculation and the severe corroslveness of le liquid carbafnate have necessltated o rnuch more sophlsticated technology for the production of urea than for the protluction of other nitrogenous fertillzers.

/{ Al/tr ,lr -''' -ffi

So if the reactlon ls exothermic, Al'lo ls neqative and K should decrease with an increase ln temperature.

Later others developed a more sophlsticated model such as Effremova and Leonteva ln 1962 and Nilsen ln 1969, Here we like to discuss the rnodel of S.M. Lemkolitz, M.G.R.T de Cooker and P..1. van den Berg (for short called here the Lemkowitz modet) developed presented ln 1972 at The Feftillser Society ln London.

lJre'crKncwHow.ccrrn
W
l*l

f l-r

e' r.rr*'ei I n

L1

Lrg,t

f d.,

nr *'

er f

LJre"caKnowHclw.cclm
\i.h
lp r

{r ll-rt!

ur rF,,

dt lr'tcJ

Lra,

rr

t.,

rn

a:

ert*

2.2

Lem!gyrlt.unede! For calculatl<ln purposes

lt ls useful to comblne reacflon g and 9:

NHz-Co-NHz (L)

co2 (L) + 2 NH (L) NHt {e ) co2 [G

H2O (G)

c+ *

+ H2o (r)

[reaction 1O]

"------l -t-'--? tl

lt tt

K2=
Gar phese

Xurea(L)

XH2O(L)

(xNHs(L))2

XCO2(L)

Ireaction 11J

it

IL
coz (Ll

Llquid phase

NH, (rl

Please note

that ln thls model there ls made a dlfference between: Inltlal Co2 NH3 or H2O. The lllltlal mlxture ls the hypothetlrat rnixtur.e conslsting only of NH-,, co2.and H2o, lF all reactlons are shlfted cornptetely to the left, so the carbamate lormagon
reacon, the urea forrnatlon reactlon (and also the bluret formaton reacon). Free COr or NH3 ls the amount of CO2 or NH3 ln the llquld pf,are not exlsting aS ufea, carbgmate (or bluret). Bound CO2 or NH3 ls the amount of CO2 or NH, in the liqutd phase eristing as urea, carbamate (or bturet). Gaseous CO2 and NH3

NH4OCONH2{L)

il

HrO (L)

'
NH2OCONH(I}

l.'

Thi! model assumes the followlng:

2.3

Urea,prssgglodisolelg

a. b. c.

The llquld phase ls an ideal mixture of arnmonlurn carbamate, urea, water and free (unreacted) ammonla and carbon dloxlde. The presence of caronates, hlcarlronates, biuret etc ls neglected. Ideal rnlxture rneans that the activitles of the consfltuents are assurned to be equal to their mol fractions. The gas phase ls ideal and a rnixture of amrnonia, carbon rlloxlrle anrl water. The presence of urea and lsocyanlc acid ls neglected. Kl of Reaction 4 ere taken the values, measured by l,lt. Ivo Mavrovlc.

Before-we go turther lets flrst dlscuss sorne indicators often used tn urea industry. In tnls paragraph biuret formatlon ls assurned to be zero. In urea plant bluret ls howeveilvpinv anatyse. ' Bluret forrns vla the reacflon: 2 Nll?-CO-Nl.lz c+ NH2-CO-N}t-CO-Nil2 + Nltj [reactlon 12J

The model crnslsts of the followlng five reactions:

NH3 (G)

5o for one b'uret molecule two CO2 and three NHr molecutes are needed and with thls one is able to extend the formula here below. As an example thls is done for ttre fli ratio.
as:

c+ 4* c)
(L)

NH3 (t_) CO2

some process lndicators are related to denlng in composltlon of the mixhlre of the fiquld phase, such

Ireaction 5l Ireaction Ireacrlon

NH2-COO-NH (L) NH2-CO-NH: (L)
6J

co.(G)
r-r2o (G)

(L)

,y|C ratlo (or atso someilmes deftned as m or L) The N/C ratlo or NH/COz ratlo is the Arnrnonla
process.

l{?O (L)
,:)
/:i.

/]

/ Carbon dioxide molar rato of the liquid composition of the so-called inltial mixture. Thls parameter can be typicalty chosen fielV when deslgnlng'a urea
(2
N/C ratlo =

co2

(L) + 2 NH (L)

lreaction 8l [reaction
9J

NH2-COO-NHq

+ HzO (L)

'

wt4/o urea

/ 60) r (wt% NH3 / t7) 't3tvrto/oblurct/LO3

COz

(wt% urea / 60) + (wtVo

44)

+2*wtobluretlLo3

cot-(L) and NH3(L) refer to free co2 nd

exsting as urea or amrnoniurn carbamate.

NH3

ln the solution, not the Co2 and NH, ortginally added or

LJreKnctwHcrw.ccrrn
\Allri.r

Ure.KnowHcf w,trc:rn
Wl'gr" f l'ir rJrcFc r'i:1iJ5ilt t*l rrrl-'t! ectual co2 conversion
FAE = CO2 convet'slon

p ff*t" LJi'*:,r lrrclul"lrq

rnri.:ls"

H/C ratio (or also sonretn'res defined as W) The H/C rao or HzO/CO ratlo ls tne v,rater / carbon ctloxlde rnolar ratlo of the llquld composltlon of the so-called lnitlal mixture. Thls parameter glves an ndication of the amount of extra water
lntroduced in the synthesis, Wpically vla the recycle carbamate flow.

at equillbriurn

A similar equatlon can le rnade for the NH3 converslon.

H/c a*o

(wto/o urea

:11: 19{-i:._- __ / 60) + (wro/o co |

Atrd again otter process lndicattrs ar'e relattrl to cjefire tlre efficiency of a strlpper or decornposer aa)
such as: Atfa (o)

H/U ratio (or also sometirnes definecl as h) Somegmes one also uses the H/U ratlo or HzO/urea ratio is the Water / Urea ratlo of the liquid compositlon. As thc forrnation of one molc of urea lcads at thc sarnc tirnc to onc nrole of water the H/U ratlo shoukl be rnilnrunt l. The H/U ral.io glves a little nrote easy att intllcatiotl uf the anrount of extra water lntroduced to the synthesls typlcally vla the recycle carbarnate flow.
wto HO/ 18

Efficiency of a stripper or decomposer (heat exchanger) ls definecl as is the ammonia converted to urea (and bluret) dlvided by the total amount of ammrcnla, typlcally measured at the liquid ouHet of thc hcot exchonger. lr fact this is sarnc dcfinition as the NH3 convcrslon. 2 * wtVo urea Alfa =

60

H/U ratlo =

(2 *

wto/o

urea

6O)

(wto/o NH3

117)

wto/o ura

60

Other process lndicators are related to defining how far the urea formation eaction did or could
progress, such as:
COz converslon (or also sometlmes defined as etha 4 or Y) The CO2 conversion gives the amount of CO converted lnto urea divided by the total omount of CO2, both expressed ln moles. Thls parameter ls the rnosdy used pararneter to express how much urea has been formed, thus is an indicatlon of the chemical equllibriurr of the overall reactlon.

3.
3.

I nf

luence of various process param

eters
!

Intruensa-gl-Lle-raa

The lnfluence of the composltion of the lnltial rnixture on the cherrrical equllibriunr can be explained qualrtatlvely by the law o[ mass actron on the overall urea formatbn reaction.
For example a larger amount of water ln the lnlUal mxture (increaslng the H2O/CO ratlo) results ln a decrease in both CO2 and NH3 converslon. Obvlously because water "pushes" the chernical equilibrium of the overall reaction is pushed to the left slde. Figure 2 shows the influence of the H/C ratio on the CO2 convelon and the Nl13 converslon.

CO2 COnversi0n =

NHr converclon The NH3 convcrslon gives thc amount of NHr convetcd lnto urca dividcd by the total amount of NH3, both expressed hr moles. Also thts paratneter lndlcates how much urea has been formed and thus ls also an lncllcatlon of the chemical equilibrium of the overall teaction, but ls less widely used.

{ous El?
Efo.o F P

gon
EE

2 wtVo urea
NH3

conversion -

/ 60
17)

(2 + wto urea

/ 60) + (wt% NH3 I

Soro gF 5 0.65 II

I
L

cf. CL

When talking about CO2 and NH convrslon one shor.lld also define if one talks abclut the CO2 and NH3 converslon at equllibrlum conditions or at actual conditons. As the reactlon from carbam?te lnto ureE is a slow reactlon, in a real urea reactor one wlll never reach equilibrium conditions (please refer to Flgure 1). Tlre actual CO2 converslon divided by the CO2 convetslorr at equillbrluot ls typically deflnecl as Fractlon Approach

fi
6 L'

o60
F
E

o.ss

-0.

23 0
H0:

025 0.50 0,?5 1.0

rnixturq, noUmol

[Qratio h inifil

_--

l"5

to Equlllbrum or

FAE.

LlreaKnCIwHow.trcf rn
I'tr lr f"
r

f: t|r t

t J

tr ln d

U f:rt'r LJ ft't

t='

' ls.,

LlrecKnc:wHCIw.trCIm
\l,rf' pr Q. tl'l

q1r Gr:j

l'tdtJ5rt r U fri

e"e*

l"A

6 tts
CI

0.6 o.lt

{o*
$
oes
ao

ff

o,+z

$oco
P o:e .G 0.36 e ct ff
o.r,'

Ss

.E o.ts

p
J

0.?0

so,os
.E

E O.a F, ,, I rtr I ur. Ll-r-L-r

-,,, -0.5 0

0.25 050

0J5

re5

H20:C0 ratio in

hitial rnixtrrg mol/mol *-

g $

0.60 o,ss

Figure 2: The inl'uence ol

lhe H/ C ratio on the COz convrsion and the NH convarston.

However a ftlll quantltative derscrlptlnn cannot be deriverJ simply from the law of mass actinn. Other, not yet fully understood reactlon mechanlsms probably contribute to the chemlcal equilibrla to a'mlnor extent.

4 0 4.5 5.0 5,5 5,5 { :, zfi 2.5 3.0 3.5 4,0 B ilH,[0ratio in initiat mixture, mot/rnol -.-

oso 5 t,

3.2

Influeeel_N/e._rolls

A hlgher NHy'CO? ratlo (lnereaslng the NH1 concntration) inereases the CO2 converslon. The most sinrple explanation was made by Frelacques, who explalned lt by the laws of mass acflon (the
chemlcal equlllbrlum of the overall recction is pushed to the right slde by N[{3), Lter Otsuka explained lt by assumlng that an excess of NH lorvered the activlty of water present rn the reactlon mlxture. Here wlth actlvlty ls meant the measure of the "effectlve concentrauon" of water in the llguid solutlon. Activlty depends on temperature, pressure and composluon of the rnlxture, among other thlngs. The dlfference between actlvlty and rnole fractlon arlses because molecules in non-ldeal solutions interact wlth each other, elther to attract or to repel each other. The acHvlty of an ion ls particularly lnfluenced by lts sr.lrroundlngs.

oss
0.50

e
o'

E
E
CL

n 0.r5

E o.4o
.g
o 'E

temperatures below 190-200 oc the concentraton of free co ls very small relaHve ro the concentrations of the remainlng constltuents, 1.e., the dissoclatlon of carbarnate may be neglected. At these condltlons, the conversion to urca is controlled by reaction 9. In this reaction however, NH does not occur expllcltly, so how to explaln the influence of the hlgher N/c raHo? Lernkowltz states that the effect of the excess NH3 must be seen prlrnarily as that of an essengally dlluent and a general rule of thermodynamlc states that a diluent increases the converslon of a reactlon ln whlch the number of rnoles lncreases, so the urea formatlon reacilon ls shlfted to the rtght
slde.

E os
o.o
o.zs

fi
frt

Figure 3 shows the relatlon of CO and

NH3

converslon

at different N/C ratos.

= z,

7.0 2,5 3,0

].5 4.0 tl.s 5.0 5.5 0

NH:[(ratio in initiat mixlure, mol/mot

-*

ureKnwHow.trorn

urE"cKnswHow"trclrn
'\^/hfpfri t'h&x ufrFt3 i"fltj5tf U rnFipr

\futrerre lFlgl t.ri'trri lllUi,fl Ll flttrpt:r

Flgure 3 shows that although the COz conversion increases wlth a hlgher N/C ratlo, the NH3 cgnverslon de?reases. The fact that the NH3 convsrslon decreases can be Slmply explalned by the flct that there ls more lnitial NH3 at a hlgher N/C ratlo.

()
C.' f9 t-

Why we talk about CO2 convrsion and NH3 converslon 7 ln the tradlflonal urea literature, typiclly the urea coflversion ls expressed as CO2 converslon. Thls is based on the arbltrary cholce of co2 s the key cornponenr. Hlstorlcally, tnls rnay be Ju$lned by the fact that early in the urea processes, COz converslon was rnore lmportant than NHs convrsion. For example ln conventlonal urea plants NHr conversion ls not so lrnportant as these plants have a pure mmnta recycle so unconveed anrrnonla will be recycled back to the synthesls withttut addltlonal water. As lndicated in paragraph 3.1, water reduces the CO2 as well as the NH3 convqrsion, so the water content should bc minlnrized. Thls rneans in urea plants wlth a purc arnmonia recyclc, CO2 converslon ls more lnrportant than NH3 converslon. Typlcally these processes operate therefore at
hlgher N/C ratlo's. However fror example for a Stamicarbon CO stripplng process, gtvlnq a hlgher value to COr conversion ls not Justifled. Both NH3 as well as C0 wlll recycle together with addltional water in the forrn of carbamte to the synthesls, so both qonversions neert to be maximum. Certainly here the urea yleld (i.e. the concertratkn of urea ln the llquid phase) is a better tool to determlne the optlrnum process paranreters tlrarr CO or NH3 cortvelslon. Flgure 4 shows the ue yield at dlfferellt N/C nd H/C ratios.

lTo
IE
g
I a
J

0.,

to

:F

p0, ooF
tt
.E 0.
C

()

Eo c
c,
L' CJ

60.
r0 q|

IL 5
-0.2
HOr

c o
TJ

g-

C02ratio in initiat mixlurg motlrnol

025 0.50 a.75 t 0 *

1.?5

t
Flgure 4:The inlluencE ol

o 0.r2 F n J6 c o.s1
at' o.ro

lhs N/Cand H/Cratio on ths Urea yleld.

F
F

a 0.3e F p
a
.E

cr 5 0.3 F
.t-

Figure 4 illustrates that urea yield as function of NH/COz ratlo goes through a nraximqrn: The urea yield as functlon of NH/CO. ratlo reaches lts rnaxlmum around a value of 3/1. AnoEher lmpoftant parameter, vrhich determlnes the optimum process conditlons can be found from the physical plrase equlllbria (phase dlagrams) ln the NH-CO-HrO-urea system. Thls wlll be covered in a future paper. The flgure rlght shows again the delrimental effect of excess water on urea yield; thus it ls clear that one of the targets in deslgning a recycle system must be to minlmize water recycle.

c o
lp
a, L'

ou
036

& c

c o 5

onF
0J4
?,0

F
bt

3.3

tfluence_of.lempemture

As lndlcated earller the formation of urea from arnmonia and carbon dioxide can be descrlbed as a two step process. First amrnonla and carbon dloxide forrn arnmoniurn carbarnate, whldt reactlon is fast sn

U
ru ol 1-

50 55 6"0 ffir,[0, ratio in initialmixture, mol/rnot q

2

5 l0 3.5 {0

exothermlc.

}5

coz(G) + 2 NH3(C) ct NHzCOONH4(L) AH = -

117

kjlmol at 110 atm and 160

oc

The second reaction ls the conversion of ammonium carbamate into urea and water. This conversion is slow and slightly endothermlc.
Nll2COONll4

(L)

c+ Nl'l2CONl12

(L) + llO

(L) All = f

15.5 kJlrnol at 16O-180oC

ls

Slnce more heat is produced rn the

flrst reactlon than consumed ln the second. the overtll reactlon

exotherrnlc. The achlevable conversion per pss, dictated by the chernlcal equlllbrlum, 5 temperature goes through a maxlmum. Thls ls shown ln Figure 5.

function of

LJ

tr'y'lf e't

recKnc:wH clw.ccJrn
fr I Flf*
r,..,r'n'd! lfrr:Jt,.tg.t'f
1..

frr+let*

UrE caKncrwHrfw.com
\,Vl'rlF rg-, ll'lfr:,
t.Jf F5{5 |f?.fJI.-fSl-1,l_

ic:rrt5:r

(t 0.Tz E
olti 0 _?1

() 0.73

Tlte hlgher the temperature the faster the urea formation reactlon will proceed. Thls be accordlng the Anfienlus relatlon. The ArrhenluS equatlon gtves the depsOence oiif1" rate vrlll constant K of a chemlcal reaction on the ternperature T and acflvation energy u:

ft
Flgure

,{e

* E'

'/fir'

I shows

the relailon of convenslon versus the temperaturs.

g 0.69 :f tr
.E

tu 0.70 gL

3.4

lnflUnncc of pressurc

0.68

As Jndlcate!.ln paragraph 3.3, a hlgher temperature ln the reEctor and ls beneflclal for the approach toLquillbrlum and the positlon

.g
E,
(U

C 0.6?

wlil increase the reacflon speeds oitn" urea equffbrlum. However a hlgher temperature ls also related to a higher pressure (bolllng curve). And in case of a strlpping process a higher pressure results however in a reduced ;tilfi; fficleny. Thus the choice of reactor ternperature (or the correspondlng reactor pressure)-inl irippr"g process ls in general an optimlzatlon between hlgh reactor converslon on onc hand and hlgh strljjtng""m.lon"./ on te other.
lntroduced the urea synthesls section.. Partly these lnerts orlgln frofn the ammonla processare and parfly from passivatlon
ln

0.66

Further please reallze that wlth the feeds ammonla and carbon dtoxlcte also tnerts

o TJ

C) IJ AI

0.65 t0

fla

180 1e0 200

Temperaturg,tf

--...*

n0

220

430
3.5 and H/

G.

0.251

Thls effecf ls ttsually explalned by the fact that lhe arnmonlum carbamate concentration as a funcilon of temperature goes through a maximum. Thfs maxlrnum ln the ammonium carbamate concentration can be explalned, at least qualltatlvely, by the respective heot effects of the carbomate and ure

alr and air needed for the hydrogenationleactor (f preient). rnmonla and carbon dioxide convert vla carbamate lnto urea. At the outlet of the reactr rnnr part of the reactants are condensed and the percentage of lnerts increase. " The total pressure can be dlvlded up lnto an lnert pressure (determlnecl by the amount of lnerts, i.e. Itydlogen, oxygen, lrltrogen, Argon, nretlnne and methanolj arrd u rvit*l pressure (cjetern-rtned by the reactlve cornponents manly ammonla, carbon dloxtde'ano wai4, n nigner tnert pressure at constan-t overall pressure means a lower system pressure. Thls means te reactor temperature wlll be hlgher (better converslon) in case less lnerts are present.

formatlolr reactions'

At

controlling and a further increase ln temperature leads to a decrease in the converslon. Thls mechanlsm cannot however explain the observed conversion maximum fully and quangtagvely; other contrlbutlng mechansrns have been suggested. Lernkowltz beleved that aiso the'bct that one approaches crltleal eondltlons at higher temperatures ls a secondary factor. As the temperatures increase the concentratlon of frce ammonia and carbon dloxlde ln the llquid phase lncrease also due to the carbamate dlssociation reactlon. The llquld phase becomes rnore and more .gas llke". The crltical llne ln the NH-r-CO2 system occurs at lower temperatures and pressures a hllher N/C ratio. Tlris explains why the maxlrnum ln Flgure 5 occurs at lower temperatures when the N/ ragon ls htgher. Wlth the temperature here above ls meant the rnaxlmum reachable temperature in a reactor, There are some reasons that thls ternperature ls never reached in real conclltlons. One reason is because there are inerts present in the reactor, thls will be elaborated ln the next paragraph. Another reason ts that the urea formatlon reactlon ls very slow. The maxlmum temperaturJ ls the temperature at equlllbrlum, but equillbrlum ls never reached ln a real reactof. The temperatures measured ln a real reactor is the bolling temperature of the liquid. It increases from lnlet to the outlet due to the fact that ure.a (and water) are formed and the light bollng componenfs NH3 ancl Co ar converted into heavy billlng components urea anrl water. Tyilcally th temierature dlfference of the reactor is therefora a good lndlcation for the ura conversion. As the bolling llquld flows from lnlet to the outlet of the reacfe the urea formation reaction takes place. Thls reactlun ls endothermlc and needs some heat to be able to proceecl. Typfcally the condensation of gasses takes care of this heat requirement. A reactor ls thls tylcalfy a nuble column wlth a llquld at bolling point. Therefore temperature and pressure are obviously'relafbd to each other.

hlgher temperaturcs the dlssoclatlon reactiol

of

carbama[e becomes

As explalned in paragraph 3.3 a reactor ls a bubble column conslsflng of a bolllng lqud. The measured temperature ls ln foct the bolling temperature of the llquld at th system pressure and not
at the total pressure whlch one actually measures. When talking about bolllng poirrts of rnlxtures physical equllibria (phase dlagrams) are of trnportance and especlally ln the urea process phase equllibria are raiher cnifi.ateJ ut of rnaJor importance to understand better wlrat happens ln a urea plant. Thls wiil be thtto;i;;ilri,i,,." paFer.

Refer ences

l.

Wiklpedla

l3l, Some Fundamental Aspects of Urea s.M. Lemkovltz, M.G.R.T de cooker, p.J. van den Berg, L4 Dec 1972 of Uhlnann's Encyclopeclia of Inrlustrial Clrernlstry, VN vertagsgesellscafft nrbH, D69451, Wennhelm, 1996, Jozef l-1. Meesen, Harro petersen 4. IE Princlples of Chemical Equillbrlum, Kennth Denbigh, Carnbridge Universtty press, 4rh Edltion, _ Technology, 3' Fifth Edltion
1981

2. The Internatlonal Fertiliser Society, Proceedings No.

urecKncf wHow.Eclrn
fy'f1:r;:r l'litr r i, r,;ijl lr-lLll,j:rl i',_ I tJt f 5.

Mark Brouwr was born on July 6, 1966 n Groningen, The Netherlands. He graduated ln 1988 at the Technlcal Uni\s51y of Elndhoven at the faculty of Chemical Engineering. His thesis was atout the production of ethylene by partial oxidation of natural gas.

After university Mark joined Mllitary $crviccs, Dutch Royal Navy whcrc hc was working at the Prins Maurits Laboratory of TNo in Rijswiik. ln this perlod he was lnvolved ln Process slmulatlon studles on the absorptlon of
poisonous gasses on active carbon. DSM, working for the Ethylene plant No.4 as a process En8ineer. ln these seven years he was involved in the Basic Engineering of a debottlenecklng project at Stone & Webster in London ancl in the implernentation of the DSM Extraction Styrene project (from conceptual tngineerlng up to the successfulstart up) .

ln 1990 he joined

ln 1997 he joined Stamicarbon, the licensint subsidiary of DSM as Ucensing Manager Urea Revamps, Later he becarne Manager Starnicarbon Services responslble for all Stamicarbon's activitles in exlstlng urea plants, such s After Sales, Plant lnspedlons, Debottlenecklng ProJects, Reselllng proJects etc. ln these nearly twelve yeats he did visit nearly one hundred urea plants worldwide and was involved in numerous revamp, relocation, debottlenecking and grass root projects.
Sitrce January 1, 2009, lvlark Brouwer left Stanicarbon and startecl up UreaKnowHcw.ccn,

tlreaKnowHow.com ls an independent group of urea specialists with an irnpressive number of years experience in designing, matntalning and operating urea plants. UreaKnowHow,corn's mission rs to support, facllitate and promote the exchange of technical nformation in the urea industry with the target to improve the perforrnance ard safety of urea plants.

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