AMMONIA INVESTIGATED

Research Development and Engmeenng

SYNTHESIS LOOP VARIABLES BY STEADY-STATE SIMULATION

LARRY
I)lvlslon,

GAINES
Inc. Pawluska Road, Bartlesvtlle, OK

Apphed Automation, 74004,USA

(Received 16 June 1977, received for pubhcatmn 11 May 1978) Abstract-A

steady-state model of an ammoma synthesis loop contauung two parallel quench-type converters IS developed The system modeled Includes converters, compressors, separator, purge and recycle and the model IS used to determme the effects of syntbesls loop vanables upon ammoma productIon Model slmulatlon mdxates that low purge rates lead to locreased production, however, rnefficlent converter operation may prohibit operation m this regon due to certam process constramts A low H2/N2 ratto also results m Increased production The optund ratio, however, 1s pnmanly dependent on synthesis compressor power costs

UWROXJUCTION

Ammoma IS produced by passmg a hydrogen-mtrogen mixture over a promoted uon catalyst at elevated temperatures and pressures High temperatures are employed to achieve a sticlent reaction rate Since the reaction IS exothermlc. the gas leavmg the catalyst and heat exchange sectlon IS at a high temperature between this stream and the feed stream IS employed to bring the feed gas to reactlon temperature Through this heat exchange the heat of reactlon supphes sufficient energy to mamtam the reactlon zone at desired reaction temperature Such processes are termed autothermlc processes and have been discussed m detd by van Heerden [ 11 The extent of reaction m the converter IS pnmardy a function of the synthesis reactlon eqtuhbrmm and ammonia content m the reacted gas 1s normally m the range of ll-13% for a process operating at 150 atmospheres Because the per pass converslon IS low, a recycle loop 1s required to make the process economically feasible Synttmsls gos mmpnnrsorr

Rgure 1 dlustrates how recycle IS accomphshed m the process modeled Part of the reactor effluent IS mlxed with feed gas, cooled, any condensed ammonia IS removed, and the remamder Is subsequently recycled back to the converter The feed to the synthesis loop contams a near stolchlometnc ratio of hydrogen and nitrogen Argon and methane are Inert gases and trace quantities are present m the feed gas As hydrogen and nitrogen react and ammonia IS removed, the merts level budds These merts ddute the gas stream and tend to quench the reaction[2.3] At high pressures, the merts level may stabthze at an acceptable value due to merts being dacharged from the synthesis loop m the hquld ammoma product stream When lower pressures are employed, part of the recycled gas must be purged to mamtam adequate reactlon Converter stabdlty and the effects of process variables upon converter efficiency have been dlscussed by Ammonia converters have numerous authors [4-6]

&-ramnla

aepamtor

Fig 1 Synthesis

loop flow dtagram 37

38

L D GAINES

frequently been modeled to obtam a better understanding of the effects of each variable upon converter operation [2,7-91 This work extends a previous converter model[lOl to include additional mayor synthesis loop processing (compressors and separators) and mcomponents, vestlgates the mdlvldual and collective effects of process vanables on the synthesis loop Process variables consldered are feed rate, merts level, merts level in the feed, converter temperature, separator efficiency, and HJN+ ratio Important constramts affecting synthesis loop behavior are compressor speed and compressor driver power, merts level, heat exchange, and synthesis loop pressure These constramts are discussed in hght of simulation results AMMONIA SWIYTHESIS LOOP DESCRIFIION The process modeled 1s a low pressure, 600 TPD plant as shown m Fig 1 Synthesis loop feed consists prunardy of a near stolchlometnc ratio (3 1) of hydrogen to mtrogen with trace quantities of argon and methane The feed IS compressed to the synthesis loop pressure by two centrtfugal compressors m series The compressors are on a common shaft and are dnven by steam turbines Recycle gas, containing approximately 1 l-13% ammoma, IS introduced mto the last stage of the second compressor The compressor discharge IS cooled m an array of heat exchangers m which several flow paths may exist sunultaneously to achieve the desired temperature The chdled gas enters a separator where hquld product ammoma IS removed The remammg gas passes through an exchanger where It IS heated by a process stream before being divided and fed to two identical parallel converters as shown in Fig 1 Each of these two streams must be further divided into five portions, the first of which enters the top of the converter to be heated, and the remammg four streams are used as quench as shown m Fig 2 The feed gas entering the top of the converter flows downward around the outside of the insulated catalyst section At the bottom of the converter, the gas IS heated by counter current heat exchange with the reacted gas and enters a central riser The riser empties into the top quench zone where cold feed gas 1s introduced The gas at the resulting temperature enters the first catalyst bed where reaction between hydrogen and nitrogen forms ammoma according to eqn (1)

Ouench#I

JJ

ouench

Quench 96 2

Quench # 3

Quench#4

----lr----

IL:

-*

FToduct

gos

Fig 2 Ammonia syntheslr converter separator The major portion of the converter effluent IS recycled to the last stage of the second compressor, thus completing the synthesis loop MODELDEWUWMENT

Compressors
Synthesis loop feed gas IS compressed m two nmestage centiugal compressors operatmg in series Recycle gas IS introduced on the runth stage of the second compressor m addltlon to the feed gas Such compressor configuratlons are commonly found m ammoma plants and are discussed by [1 1] The molecular weight, MW, of the stream IS computed from the component molecular weights, m, and stream composltlons, F, (lb mole/hr)

The temperature of the gas mcreases as it reacts in the bed and must be cooled in the next quench zone before entering the second bed Gas from the fourth bed has a near equlllbnum concentration of ammonia and supplies heat to the feed gas before leaving the converter The converter efluents are mixed, cooled, and a relatively small purge stream IS drawn off The purge gas IS further cooled and lighter gases enter a fuel system Liquid product ammoma IS drawn from the purge

and suction

volume,

V (acfm),

IS computed

from (3)

Ammoma

synthesis loop variables mvestlgated by steady-state sunulatlon

39

2 IS the compresslblllty factor, T IS suction temperature (OR), P, IS suction pressure (atm), and R IS the gas constant With these data and compressor speed, S, the compressor performance curves may be used to determme discharge pressure and the horsepower requued by the compressor The performance curves are computerized using equahons stmllar to those dlscussed by White1121 for centrifugal compressor surge control The surge flow, AS (acfm) may be computed as a lmear function of speed for the compressor operatmg range from AS = Cl,S+ C2, (4)

Where Cl, and C2, are constants The head at mmlmum flow, HM (ft) IS a function of speed squared and 1s computed from HM = C3,S2 f C4, and the head at operatmg condltlons H = HM+C5,(V-AS)2 This value of head 1s used to calculate discharge pressure, Pd (atm), from Pd = Ps(CQHMWI1545 IS obtamed from (6) compressor (5)

The separator operates at -10F and at a pressure several atmospheres below the discharge pressure At 140 atmospheres, only minor quantltles of reactants and merts are present m the liquid ammonia product The ammonia m the overhead gas, however, IS cntical since this stream IS fed to the converter Guerren [ 131 computed per cent ammonia as a function of temperature, pressure, and merts level HIS results show that the per cent ammoma leaving the separator m the gas phase will change by less than 0 2% over the pressure and merts range encountered m the separator Smce the separator operates at a specified temperature, constant values may be used for a hqmd-vapor eqmhbrmm constants, K, The liquid fraction, Lf, of the separator feed IS computed using the component molar flow rates, E (lb mole/hr) such that

(8)
The component vapor flows, F,, (lb mole/hr) from the top of the separator may then be computed from the inlet flows
F =

a
O/T + 1 0)c7, (7) Liquid-vapor Table 1 Constants Cl,-C7, m the above equations were determmed by regresslon with data from performance curves The first compressor discharge IS cooled and any condensate IS removed This stream becomes the feed for the second compressor which 1s computed in two parts The performance of the first section (compnsmg the first eight stages) of this compressor IS computed from eqns (2)-(7) using a new set of constants and P, set equal to the discharge pressure of the first compressor Before repeatmg this procedure for the mnth stage of the second compressor, the recycle gas and feed gas must be combined The suction temperatures and first stage suction pressure are taken from design data Heat exchange The compressor discharge IS split and cooled m an array of exchangers Heat IS removed by exchange with process water, a process stream and by refweratlon supphed from a refrlgeratlon umt not shown m Fig I A model of the refrlgeratlon unit and complex exchanger network IS beyond the scope of this study The only heat exchange equipment modeled IS that physically located m the converter It IS assumed that all other process streams may be mamtamed at design temperatures Factors affecting heat exchange requirements are, however, discussed since heat exchange limit&tons may be encountered Ammonca separator The compressor discharge, after bemg cooled, enters an ammonia separator where hqmd ammoma IS removed

Lf + K,(l - 4) constants, K,, are

KE(l-Lf)

(9) grven m

equthbrmm

Ammoma syntheses converters The gas leaving the ammonia separator 1s heated and the stream is split between the two converters Equal quantities of gas are assumed to enter two tdenttcal converters, thus, calculations for only one converter need be performed The converter catalyst section consists of an outer pressure shell and a catalyst basket with cold feed gas flowing m the annulus between the two (Fig 2) The catalyst basket IS coated with msulatlon to mlmmlze heat transfer from the hot catalyst to the cold feed gas An unmsulated riser tube transports gas from the heat exchanger section through the catalyst sectlon to the first bed Mmmtal heat transfer to the riser gas IS due to a small heat transfer area and because the riser gas has been heated to near reactlon temperature The catalyst section 1s nearly adtabatlc and an assumption of umform radml temperature IS made A umform velocity profile m the bed may also be assumed smce the bed dmmeter IS much larger than the catalyst dmmeter The assumptions of undorm radial temperature and velocity reduce the Table 1 Llquld-vapor eqtnhbnum constants at 140 atm and -10F
l69.oco 0.023
1oO.ooO 66,Qxl

Nitrogen

Anlnolua Argon
Methane

40

GAINES

equations to an easily usable desued accuracy of the model Marenal balance The hydrogen consumed catalyst bed IS aven by

form

while

retammg

the

m a dlfferentlal

element

of a

constant of the reverse reaction, y IS the catalyst actlvlty, 5 IS the effectiveness factor and al, UZ, and u3 are the actlvltles of hydrogen, nitrogen and ammonia respectively K, IS calculated from the equation of Glllesple and Beattle [ 151 log,,K, = -26911221ogjo T-S 519265x lo-- T
(13)

F,dx=rAdz

(10)

+1848863x10- T2+20016/T+26899 where

where A ISthe cross-sectional area of the bed in ft and x 1s the fraction Hz converted F, IS the flow rate of Hz mto the bed m lb mole/hr Units are temperature, R, pressure, atm and flow, lb mole/hr Figure 3 IS a sunphfied diagram of the synthesis converter which shows flows and temperatures used m the followmg equations The component flows at any point m the bed may be computed from mlet flows by F; = F,(l -x) F; = F2 - F,x/3 F; = F3 + 2F,x/3 FL= F4 F:=Fs where the order of components IS hydrogen, ammoma, argon and methane The rate of reaction r, for eqn (10) IS found Temkm [ 141 equatron r= 3+.~cl,(~)where K, F IS the equdlbnum mtrogen. from the (11)

T LSm K Activity coefficrents used to calculate the actlvltles for eqn (4) are computed from RTln Yr=[(B,-A,/RT-C,/T )+(A, -S,)*/RT] P (14)

where T IS m K and R has the value 0 08206 Constants A,, B, and C, are gven by Nlelsen[5] and appear in Table 2 S, IS computed as

($) -aJy

(12)

I In where rnI refers to the mole fraction of component the mixture and the summation includes all components m the mixture Nlelsen[S] discusses the possrble values of a and concludes that LI should have a value between 0 5 and 0 75 A value of 0 5 was used m this study to obtam the reverse reaction rate constant k, as outlmed by Dyson and Slmon[l6], but usmg actlvltles as dtscussed m this paper Data from Nlelsen[5] for an mdustrlal catalyst were fitted and the resultmg equation
k2 = 0 146578 x 10 ec-- nr) (16)

constant,

kz IS the rate

ru,

has units of lb molesh ft3 and T ISm R R ISthe umversal gas constant and has a value of 1987 Btu/lb mole R The effectiveness factor ,$ IS derived by Dyson and Sunon[l6] for Isothermal spherical catalyst particles They assumed the ddfuslon coefficients were mdependent of posltlon m the parucle and that Knudsen diffusion does not occur The resulting equation ~=bo+b,T+b2q+bjT2+b.+qf+b5T3+b6$ (17) gwes the effectiveness factor as a functton of T), temperature, K and pressure for a 3 to 1 H2/N2 ratio and 12 7% merts Constants for use wzth eqn (17) are gven by Dyson and Sunon[ 161 and appear m Table 3 for Table 2 Constants for calculation of actlvlty coefficrents 1
%J N2 9 A 1 2 3 4 5 A1 0.1975 1.3445 2.3930 1.2907 2.2769 BI 0.02096 0.05oLb 0.3w5 CplO-4 0.0504 0.420 476.87

Fig 3

Block diagram of synthesis converter

ml4

Ammoma synthesis loop variables Investigated by steady-state stmulatton Table 3 Constants for cakulatlon of effectweness factor Pressure, 150.0
225.0 300.0

41

ati

b. -17.5391
- 8.2126 - 4-6757

bl
0.07698 0.03774 0.02355

b2 6.90055 6.19On 4.68735

b3 x 104 -1.08279 -0.53547 0.346331

bq -26.4247 -20.8696 Il.2803

b5 x 10' 4.92765 2.37914 1.54088

b6 38.9373 27.8840 10.4663

pressures of 150, 225 and 300atm The fracttonal verston of nttrogen IS 7 and may be obtamed from v = molar flow of NH&molar flow of NH3 +2 molar flow of Nz) Catalyst actlvlty, Factors affecting Nielsen [5] Y deteriorates deterloratton with catalyst are discussed

con-

thermal

conductlvltles

are explained

elsewhere

m this

(18) use by

paper The remammg two heat terms refer to heat transferred from the bed to either the gas flowing in the annulus on the outside of the catalyst basket or the gas in the riser Heat transferred to the gas m the annulus IS computed by = k C (T - TAM dz = f&fL.(Ta. dQ annulus I+) dT, (23)

Energy balance The converter may be divided mto three major sections, catalyst beds, quench zones, and heat exchanger The energy balance for the converter may be obtamed from the energy balance equatrons for the three sections by combining them m the proper order The energy balance equations for each major section are developed The energy balance for a honzontal dlfferenteal element of catalyst bed mvolves four heat terms dQrcact,en + dQ,.s + dQr,scr+ dQannu,uo = 0 (19)

stnce the primary resistance to heat transfer IS the catalyst basket msulatlon Neglectmg all other heat transfer resistances reduces computational effort wlthout substantially affectmg the accuracy of the sunulation For converters without insulation, heat transfer to the feed gas would be conslderable and an overall heat transfer coefficient would be necessary Smce the riser 1s unmsulated, an overall heat transfer coefficient U IS considered m calculatrng thus heat term dQnscr= - lJC(T - TR) dz = f,M&(T,z, PF) dTR (24) The

of which the last two are small as already mdlcated but are included m the model The heat generated by the formation of ammonia IS dQractlon and IS expressed as dQ,,,,t,,, = - f AH,F, dx (20)

where C IS the outslde circumference of the riser overall heat transfer coefficient IS mven by l/U = l/ho+ l/h,,,+ A,/(;?& In (L&,/D))+ mslde packed E tubes

(25) as

A& IS the heat of reaction corrected for the heat of mlxmg m Btu/lb mole NH3 formed, and 1s computed from HR = - 23840 57 + (P - 300)(1 08 + (P - 300)[0 01305 + (P - 300)(0 83502 x lo- + (P - 300) x (0 65934 x lo- ))]} + 4 5(1391T) (21)

ho IS calculated for heat transfer descrtbed by J_eva[lB] ho=YAW where W IS the mass IS calculated from flow m lb/hr

(26) The geometllc factor

# = 3 5 etA4 6~ 01(Do/A) /D

(27)

This equation was derived from the heat of reaction data presented by Kazarnovskuf17] for the formation of a mixture contammg 17 6% NH3 in a 3 1 HJNz mixture Most of the heat liberated by reaction IS expended m ralsmg the temperature of the reaction mixture as expressed by dQea. = - MCJT, P)dT (22)

where D, 1s the catalyst diameter m feet and D IS the bed diameter The bed heat transfer factor A IS a function of reactton gas thermal conductlvtty K and gas viscosity and is given by A= ICI/LO7 The Colburn equation transfer coefficient mslde IS used to calculate the nser (28) the heat

where M 1s the moles of reaction gas C,(T, P) IS a functton of pressure, temperature, and composition and IS calculated from the BWR equation Calculation of mixture heat capacltles, enthalpies, viscosities, and

h,,, = 0 023 GC,, ( Tn. PF)N ;;213 N 2 DJDo G IS the mass velocity lb mole/hr

(29)

ftZ and the Prandtl

42 number 14 computed &r=

c,(TR.PF)dK

L D

GAINES

The energy tubes yields (30)

balance

for the gas m the heat exchanger

f,M&,(T=,

PF)~TT

= - UA (Ts - Tr) dz

(38)

D, and Da are the inside riser respectively m feet computed

and outslde diameters of the and the Reynolds number 1s

NRC = 0, Glcl

(31)

The thermal conductlvlty of the riser material IS k and l, the fouling factor, was assumed to have a value of 0 001 The energy balance for the quench zones above each bed IS developed assummg the zone to be adlabatlc and perfectly mlxed Equatmg the energy flow from the previous bed (Fig 3), (or the riser m the case of the first zone) and the energy m the quench stream to the energy flow mto the next bed yields for the ith quench zone

The mdlvlduat heat transfer coefficient for the tube side, !I,~, 1s computed according to eqn (29) Equation (33) and (37) may be solved by numerlcal integration or analytically as suggested by Shah[2] If C,( Tap) and C,(T,, P,) are assumed to be constant The solution may be obtamed by letting B =~,MFC~(TT.PF) and 4 = MFCJTS, P,) Equatmg eqns (33) and (38) and integrating Ts = Ts+PI+(TT TRB)

(39)

(40)

(411

M 1s the molar flow from the previous bed or riser and H IS the enthalpy, Btu/lb mole The enthalpy of the quench IS obtamed by multlplymg the fraction of feed used for quench m the ith zone by the total enthalpy of the feed Flow rate of a component out of the zone IS equal to the sum of the flows m smce no reactlon occurs The energy balance for the heat exchanger located at the bottom of the converter may be obtained from the heat transfer equations The cold gas flowing from the annulus passes upward through the exchanger tubes mto the riser and reacted gas flows countercurrent and IS cooled on the shell side The energy balance for the reacted gas m the shell IS M&,(T,, (T, Pp) dTs - UA - TT) dz (33)

where Ts and TRB result from evatuatmg the constant of integration Substitution of eqns (37), (40) and (41) into (38) and rearranging

(42) Integration rearrangmg over the length of the exchanger yields after

TRB =

TA( 1 - p/t@) - Ts( 1 - e( -P * UA ue) WB e( --8 9 uA - PI*

(43)

where A IS the heat transfer area m ft* per ft of heat exchanger height and Ts and TT are shell side and tube U, the overall heat side temperatures respectively transfer coefficient for the heat exchanger IS computed accordmg to eqn (25) ho for the heat exchanger 1s computed by the method of Donohue[l9] for dak-anddoughnut baffles

C,(TS, P,) and Cp(TT, P,) are evaluated at average conditions Tp may be obtamed from eqn (41) since at TA and Ts the bottom of the exchanger T,- and becomes becomes Tp

CAUXJIATIONAL

PROCRDURE

where

D, 1sthe equivalent

diameter

m inches perimeter) (35)

D, = 4(flow area/wetted and G, IS computed G, = W/S, S, IS the geometric baffle-hole areas, I e S, = (cross mean of the

(36) crossflow and the

flow area x baffle-hole

area)05

(37)

Component fresh feed rates and compressor speed, S, must be available to begm compressor calculations As each compressor computation (eqns 2-7) 1s performed, a check IS made to determine whether the compressor IS above surge flow rate, AS The computation of the last stage of the second compressor requires an estunate of the recycled component flows to be made The compressor discharge flow IS separated mto converter feed and product according to eqns (8) and (9) The separator gas IS split m half and each half enters separate converters at the same predetermined temperature The basic converter model eqns (lo), (111, (19), (331, (41) and (43) cannot be solved analytically for component flows and converter temperatures since they are nonhnear and coupled due to heat transfer between the feed and reacted gas The method of solution consrsts of assuming a value of TRT and T, IS then found such that

Ammonia syntheses loop variables mvestlgated by steady-state sunulahon eqn (32) IS sattsfied to within 0 1F on T, At th1.s pomt, values of TR, TN, TA and F exist and an integration through the first bed IS performed usmg a fourth order Runge-Kutte method The fraction HZ converted, x IS set to zero to start the integration Molar flows at any pomt in the bed may then be found by eqn (11) The pressure IS assumed to vary linearly with the fraction catalyst traversed P = P +AP(B-z)/B

43

component constants whch are used to compute mixture constants to be used m the BWR equahon Mxture computed according to Reid and constants are Sherwood[20] except for Bo, which IS computed
n n

Bc,, = 2 2 m,m,(B:,33 + ,-a j-L

B:,333)3

(46)

(44)

where P IS the pressure at the bottom of the bed, AP IS the pressure drop through the bed, B 1s bed depth and z IS posItIon measured from the top The pressure, temperature, and mole fractions are used to calculate a rate for eqn (10) and a value of dx/dz IS obtamed Values of dT/dz, dTJdz and dTA/dz for the element are found from eqns (19), (23) and (24) New values for TA, TR, T, and x result at the end of each mtegratlon step Ten steps are normally required to obtam desuable accuracy When the bed mtegratlon IS completed, composltlons are adjusted according to the value of x and the temperature and composltlon m the next quench zone IS computed, which leads to tnihd values for the next bed integration This procedure IS repeated for each bed unti the end of the catalyst section IS reached The temperatures of the reacted gas and the cold annulus gas are entered mto the exchanger equations along with estimates of Tn, and Tp Heat exchanger calculations are repeated ustng the new values of TR and Tp until convergence on the two temperatures ts obtamed Solution of the heat exchanger equahons completes one pass through the converter To check for convergence, the value of TRe from heat exchanger calculatlons 1s compared with the value obtamed after mtegratlon of the last catalyst bed If they differ by more than 0 25F, a new value of TN IS computed

Mxture vlscosltles and thermal conductrvltres are calculated by methods suggested by Reid and Sherwood[20] Pure component viscoslhes are obtamed usmg the theorehcal treatment of Chapman and Enskog Low pressure mixture vlscoslhes are then computed by the method of Wtike and corrected for pressure by the equatton proposed by Dean and She1 Pure component thermal conductlvltles are computed as suggested by Bromley and mixture thermal conduchvltles are computed accordmg to the method of Lmdsay and Bromley, the mixture value IS then corrected for pressure by the equations of Steel and Thodos The fraction of the converter effluent to be purged must be specified The remamder of the converter effluent IS recycled and the component flows are compared with the estunated values used to start the cycle Strrct convergence on these ilows 1s necessary and a convergence accelerator ts applied on odd loop Iteratlon cycles This IS done by computmg a new estnnate of each recycle component flow, F,, from the component flows of the previous two cycles, F: and F ;

F, = F:+E(F:-Fyn
The convergence cntenon 1s

(47)

Gw
and must be sunultaneously sahsfied for all component flows At the same tune, synthesis loop pressure drop must sum to zero with the pressure nse across the last stage of the second compressor Pressure drop, AP, is assumed to be proportlonal to the square of the flow mto the converter and mversely proportional to the density. p, of the stream AP = G 2 (FiMwi)*/p t-1

TRnkw = T~~~xcm.w + (TRW, - T=mwJ

(45)

and used to start another pass through the converter Four or five passes are usually reqmred to obtam convergence mxture heat capacihes and enthalples are computed usmg the BWR equahon of state Table 4 contams pure

Table 4 BWR constants

Nitroaen Ax-non Methane Amnda mmnen

A
A0

.03l2319 .8720e6 .0032351 .0281066 4 &X547364 .0078X375 .OUDO709232 .0045

.02sS3% .=3.U7 .002l5289 -0222852597 .0007982437 .Ol314J25 .oooo3558895 .00233827ll

.0494 1.855 .OQ338004 .0426 .a2545 -02257 .oool24359 ,006

.10354l29 3.784282 .ooo7195852 .05l646121 .ooO15753298 .17J35709 SWXCU652178 .019805156

.ooo8108534 .18267058 .01092708 .026%12097 .ooooo355307 .oooo99967II .oooo893277 .(X2576974

b % C X 10 0 Y co X 10-6

44

LD

GAINES

where G was determmed from operating data The converter pressure drop for the plant data was API3 with l/6 of the drop occurrmg between the converter outlet and the compressor suction The pressure drop computed by eqn (49) IS assumed to remam dtstrtbuted m this manner to provide mlet and outlet pressures for converter calculatlons Loop pressure drop ts determined by flow rate and must be matched by pressure rise across the compressor which 1s a function of flow and compressor speed The compressor speed 1s adlusted each loop in an effort to match pressures The new speed, S, 1s computed from the previously computed speed, S as follows S = S - ((Pd - Ps) - AP )Cm,

(50)

where Cl0 was determmed by trtai Equation (50) provldes an excellent esttmate of the speed for the next calculattonal cycle Convergence on pressure drop (atm) IS obtamed when eqn (51) 1s satisfied
ols

(51)

DISCU~EON

OF -Ts

model This paper 1s Intended to show the mteractlon of the converter with other components of the synthesis loop and variables investigated Include feed rate, merts level, methane leakage, separator efficiency, converter temperatures and hydrogen-nitrogen ratlo The combmed effects of several of these vanables are also included and constramts are dlscussed A typlcal sunulatlon result 1s shown m Table 5. where the feed rate, combmed converter flow rate, recycle flow and a complete temperature profile are shown Fortyeight such runs were made to Investigate variables effects upon ammoma production and synthesis loop efficiency The results of these runs are shown in Rgs 4-17 and are dlscussed m the followmg text Figure 4 mdlcates that ammonia productlon and synthesis compressor speed are almost hnear functions of feed rate at a constant merts level and H/N ratio tn the synthesis loop Figure 5 shows that recuculatlon rate also Increase with and compressor dtscharge pressure feed rate The synthesis compressors are major utility consumers m the process, compresston of the feed gas to synthesis loop pressure accounts for about 70% of the synthesis compressor s power requtrements whrle recurAs expected, mculation accounts for the remamder creased feed and product rates necessitate an increase m power input, as mdtcated by compressor speed
The synthesis the synthesis compressors and there are often the bottleneck are several related of loop con-

The synthesis loop model equations developed in the previous sectlons were solved on an Interdata 7132 to mvestlgate numerous modes of steady-state operation Convergence was dependent upon operatmg condttlons and mitml estimates of component recycle rates Thuty to sucty seconds of CPU tune was normally requtred for runs whtch converged to a steady-state solutton The prevtous study used the model presented m this work to determme effects of specific process vartables upon converter operatmg effictency and stabthty In that work, a sunple method of determrmng near optlmd converter temperature was presented Tlus new method has smce been unplemented on the converter modeled resultmg m an Increase m converslon and conformation of the Converter
Feed Riser

stramts which may become active as feed rate IS mcreased As already dacussed, compressor speed, horsepower requvements and dtscharge pressure all mcrease with feed rate and may become hmltmg Compressors are destgned to operate wtth a hmlted speed range, usually 70-105% of design speed Operation outside of thts range may result tn compressor damage and speed controls are deslgned so that the maximum rated speed cannot be exceeded Synthesis gas compressors are normally &ven by one or more steam turbmes and as horsepower reqmrements Increase, a restncted steam supply may hnnt compressor

Table 5 Typtcal model results

Temperat.uFe Profile (OF) Process Flow Rates (++=,

Bed 1 Inlet Bed 1 Outlet

Outlet

3co.cO 751.14 751.14 875.03 907.09 832.69

816.82

H2 N2 AR
wa

Feed

Eed2Inlet

Bed 2 outlet &d 3 Inlet Bed 3 Cutlet

BedLInlet Bed 4 Outlet Converter Outlet

6W.33 4793.80 1602.10 19.19 25.25 35791.o9

22383.22

Converter Feed
H2 N7 G3 a4 R.xxcle

897.36 832.00 883.29 566.28

7695.94

ccmpressor

Tim

10197.90

818.U 2161.96 2731.85 32431.80

Horsepower lO826.00 Discharge Pressure (atm) Recycle Pressure (atm) fk NH3 into cowetir 2:29 $ NH3 out of Converter Il.98 EQ/N2 Ratio 2.91 Fraction Feed Heated 0.70 Quench Fractxon Bed 1 0.00 Ciuench F'rectxon Bed 2 0.08 &ench Fracticn Bed 3 0.l.l Quench Fractum Bed 4 0.11
NH3

m?

2710.00 r&ed Purged k Inerts III Converter 4.06

Feed 13.47

63 AR

Produced

630.53

Tcm&'w

Ammoma

synthesis

loop variables mvestlgated

fO.400

by steady-state

stmulatlon 148

45

650

146

640

- 1OW

I44

630 2 t s' 620 E 3 Ii 610

I42 E 6 _ IWO r 3 t 5i. 360 1 362

-lO.200* ; 8 E 9 - 10.100

2 =600

590

34

60

32

l3g 4

Production

and compressor speed vs feed rate at constant mert level

l3g 5 Recirculauon

rate and &charge pressure constants merts level

vs feed rate at

operation If this occurs, compressor suction pressure will rise reqmrmg that part of the feed be vented The compressor discharge pressure may also become abnormally high as feed rate IS increased Since the synthesis loop IS designed with relief valves, this pressure must be mamtamed below some predetermmed level The maximum feed rate may also be determined by reclrculatlon rate Recuculation rate affects heat exchange and refrtgerabon requuements and converter stability At high feed rates, coolmg capacity may be

insufficient or the converter may lose reactlon as HrllI be discussed later The effects of feed rate upon each of the variables discussed above are shown m Table 6 This table shows the process vanables which were held at constant values and the dlrectlon of change of other pertment vmables Vmables which may reach constramts are also mdlcated The slmulatlon results shown in Fus 4 and 5 reflect feed rate vanatlons at one specific merts level Figure 6 indicates that pressure and recuculation rate also mvarrables

Table 6 Effect of variable Increase on other process

Vanable

mcreased

PI-Cduct1on

compressor

Fkc1rcu1ataon

Pressure

Horsepower

Temp.

9%
Ratio

,$

IIErtS Level

Speed

Ftate

Feed rate

-t

'T

'T

-7--

Inerts level

t-T-f-I--f---

-LCf--

Separator

efficxency

-11

il--------

Convertertemp.

I-I-T-I-T-

w-7-17cannot be held constant

%/N2

ratio

Nitrogen

feed rate

t7-t

+-l-T

_(_
t
I

I 1I t

a b
-c

Ccmverter
IZcreases

Decreases

Variable Vanable Variable

unstable and temperature of 2.2, then _ -. increases tiLl ratio Of about 2-q 18 reached held constant or did not change increased/decreased mcreasedandmay becomelznutang
tdl ratio

w-ill become

at high inerte

L D GAINEZS

144

143 E ij _

142 f t k

-I41

32poo -

$ 140 s

139

13

14 Percmt

I5 herts

16

17 feed

,e

1136
Fig 7 ProductIon and cowerston
rate vs merts level at constant feed

an converter

Fig 6 Reclrculatton rate and discharge pressure vs merts level at constant feed rate crease wtth tnerts concentratton at a constant feed rate Changes m recuculatlon rate are partially due to per-pass converston as shown tn Ftg 7 At tnerts concentrattons above 19%. the converston ts so low that the converter becomes unstable, t e heat produced IS not sufficient to mamtam the reaction zone at an elevated temperature The merts concentration IS controlled by ventmg part of the recycle gas as shown m Fig 1 Since reactants are also vented tn the purge stream, a loss of productron results from operation at low tnerts levels A high merts level affects the synthests loop tn much the same way as high feed rates and the same synthests loop constramts may be encountered as mdlcated in Table 6 Stnce the synthesis loop 1s normally operated agamst one of the mentloned constraints, a balance between feed and purge rates must be mamtamed For example, d the synthesis loop pressure constraint ts active and feed rate ts tncreased, there must also be a corresponding tncrease m purge rate Figure 8 shows that methane leakage has a detrunental effect on productton at a constant merts concentration A rise in methane concentration tn the feed of 0 06% resulted m a loss of production of 0 32% (ZTPD) Substantial losses tn production may result from meficlent reformer operation which leads to increased methane leakage Converter temperature profile affects converter efficiency and stability Figure 9 shows a reduction m reclrculatlon rate and compressor speed as the outlet temperature of the catalyst section 1s reduced Smce catalyst actlvtty also rapidly detertorates at Hugh temperatures, tt IS desuable to mamtam low converter temperatures Lower temperatures, however, decrease the reaction rate and tend to lead to stablltty problems Figure 10 tndlcates that synthests pressure also decreases with converter temperature Except for stabllrty related problems, lower temperatures wh tend to move synthesis loop operation away from compressor, pressure, and flow related constramts and increase synthesis loop capacity as shown m Table 6

62Y80-

6260

23 M*,ho:, &~5mo*26 27 2e

Fig 8 Production as a function of methane in feed

Figure 11 shows the effect of ammonia separator efficiency Runs were made with 2 0, 2 3 and 2 6% ammoma tn the converter feed Faure 12 shows that synthesis loop pressure and reclrculatlon rate increases with ammonia concentration tn the converter feed Higher ammonta concentrations also tend to reduce converter stab&y, as discussed by Shah[2] Converter efficiency and synthests loop operation are known to be affected by the hydrogen nitrogen ratio tn the synthests loop A value somewhat lower than the stotchometrlc ratio of 3 ts usually considered to be optunal Since the molecular wetght of the synthesis gas changes with H,/N, ratio, there are several factors which must be considered Fust, the pressure drop m the synthesis loop WIIIbe altered as shown by eqn (49) and at the same tune, the molecular wetght change will affect the compression ratio as predicted by eqn (7) Component activities wrll change with HZ/N2 ratio and

Ammoma
32.600

synthesis

loop variables mvestlgated

by steady state slmulatlon

bl-

47
I41

32.400 32.500 ,32,200 140 E f f wa

-0

32,300

Ei 0 I_ f 32.00

h f 0 36

3l@oO

-&yy!&J.lo,120
a 8-m
Temperature of gas leaving cotalyd section. *F

20 Percent NH,

23 I converter feed

26

37

Fig 9 Recmxlatlon
I4OF

rate and compressor speed vs temperature at constant feed rate

Fig

1I Reclrculatlon

rate and discharge efficiency

pressure
-

vs separator
12.ooo

4.m

I359 4;160 IE 6 f I g,3 s 5 B 7I3aY I!i P ll,5Qo

4.750

I_
4,740

$ f I

if \\

613 4 =0

I3585l Temperature of gas Ieavlng catalyst sectlm. F 4.720

I5

20

25 IN,

ratio

30

35

40

Fig 10 I)lscharge

pressure

and conversIon vs temperature at constant feed rate

Rg 12 Hydrogen feed and power Input at &fferent

and constant product rates

Hz/N2 ratios

except at composltlons very close to eqmhbnum. the reaction rate IS mcreased at ratios shghtly below stolchlometnc In order to determme the results of changmg the Hz/N2 ratlo, several sunulatlon runs were made at a constant total feed rate and constant merts level m the synthesis loop The merts composlhon m the feed was varied m relation to the concentration of reactants Figure 12 shows the effects of Hz/N2 ratlo on horsepower requirements and hydrogen consumption at three levels of merts and two temperature levels m the converter Each horsepower curve represents a constant ammoma production rate Horsepower requuement decreases W&I mcreasmg HJN2 ratio und a ratio of about 3 IS reached At this pomt, horsepower IS nearly constant with further Hz/N2 ratio changes Hydrogen

consumption goes up with Hz/N2 ratlo over the range investigated This result IS expected since the hydrogen concentration m the purge increases with Hz/N2 ratio Depending on the relative costs of power and hydrogen, an optional Hz/N2 ratio below 3 ~111 exist m each case As can be seen from Rg 12, operation above a ratio of 3 requues an elevated hydrogen feed rate with no reduction of power reqtured by the synthesis compressors Synthesis compressor discharge pressure curves (Fig I3), have the same general shape as the horsepower curves Higher molecular weights of the gas at low ratios result m a larger pressure rise across the synthesis compressors Since the feed rate Is constant and most of the power 1s required to compress the feed gas, horsepower IS greatly influenced by discharge pressure Reclrculatlon rate affects horsepower and the curves

GAINES

6295

I6 45%

TPD lnerts

6248 TPD 1360% lnerts

/
,6295TPD 1645%

harts 625.9 TPD 1395% Inerts

6248TPD 136D% lmrts

>
I I 1 4

20

25

30

35

49

H2/N2

Rat10

IS

20

25

30

35

40

H/N,

r-do

Rg 13 lhscharge

pressure at dlfferenl HJN, ratios and constant product rates

Ag

15 Compressor

speed at different HZ/N2 ratios and constant product rates

shown m Fig 14 have a somewhat different shape Recuculatlon rate IS a functron of per pass converslon m the converter and as already mentloned, component actlvltles result m higher con* erslons at low Hz/N2 although conversion WIII also mcrease with ratios, synthesis pressure Compressor speed IS another unportant variable which IS affected by Hz/N2 ratio, flow, and compression ratio and results are shown m Fig 15 Comparison of Figs 14

and 15 reveals that compressor speed and reclrculatlon rate curves are reIated and compressor speed exhibits a muumum at a Hz/N2 ratio of around 2 2 Thus indicates that d mexpenslve compressor driver power 1s avadable, a reduced Hz/N2 ratlo wdl not only reduce hydrogen consumption but will also decrease compressor speed Figures 12-15 also illustrate the importance of controJhng merts level and converter temperatures Approximately 5 tons/day increase m production results from operation at an merts level of 16 45% rather than

6295 TPD 16 45% Inats

I+ m,-35
30 6248 TPD 1360% lna?s

E
20 2.5 3D 35 40

Fig

14

Recuculauon rate at different Hz/N2 ratios and constant

product rates

Fig 16 Production

vs merts level at dtierent

Hz/N2 ratros

Ammoma synthests loop vanables mvestlgated by steady-state skmulauon

49

-1
E c mo e ii i 2 Z 8 @ 5 BIDB f b t 2 g -E I-

I, 2, 3. 4, 5.

36 H/N, 30 26 22 17

Ratlo

process constramt may be reached Methane leakage leads to increased purge rates and lost productron Decreased separator efficiency results m lugher operating costs and reduced converter stability Lower converter temperatures also result m reduced stability but increased synthesis loop efficiency There appears to be an optnnal HZ/N2 ratto at which the synthesis loop operates most efficiently Operation below this ratio results tn increased utdtty consumption while operation above requires more hydrogen feed The ophmal ratio IS prunarlly dictated by the cost of compressor drtver power
NOTATION

A, A' AS ; B,

Bo,
Born
Fig 17 Temperature vs merts level at different H2/Nzratios 13 6% Figure 12 also shows that an increase of 1 ton/day may be achteved at an merts level of 13 95% and tn this case, lower converter temperatures also resulted m a reduction m power requvements The synthesis loop vmables discussed are shown to be of sizable economtc consequence and illustrate the need for a basic understandmg of process vmable effects on the process Slmulatlon runs wtth a constant hydrogen feed rate give further Insight into synthesis loop operation If the process 1s feed limited These runs were made by changmg the mtrogen and argon feed rates and purge rate Figure 16 shows that production mcreases with nttrogen feed rate (reduced Hz/N2 ratlo) at a constant hydrogen feed rate and merts level In these runs, no attempt was made to hold converter temperatures constant and Fig 17 shows that the converter may become unstable d large changes are made m synthesis loop variables wlthout changmg quench flows Curve 1 shows that operation at high Hz/N2 ratios and merts levels ts not possible with the quench flows used Curve 5 shows that very low HJN2 ratios also tend to reduce converter stabrllty Frgure 17 also shows that higher tnerts levels tend to reduce converter temperatures and consequently reduce converter stab&y
CONCLUSIONS

b, C
Cl-C7 C C, (CP) D 9 0. DO DP E E, FL l-7 F, f. G G, w
A.HR

ho h 10 1, I K, K, k k kz L
Lf 1 M Ml

Sunulatlon results should provtde a better understandmg of process variable effects upon synthesis loop operation and a basis for synthesis loop optmuzatlon Large economrc benefits can be denved from good operatmg strategy Decreased purge rate (tncreased merts level) wdl rase the production rate since a smaller quantity of reactants 1s lost A hmltatlon to thus operatmg mode ts that It results m increased compressor reqmrements, synthesis loop pressure and recuculatron rate, and consequently a
CES Vol 34 No I-D

MF MP Mw m

cross-sectlonal area of catalyst bed constants in eqn (14) heat transfer area per foot of exchanger surge flow activity of component i catalyst bed depth constants in eqn (14) BWR constant for component 1 BWFZ mixture constant constants in eqn (17) circumference of riser constants used in compressor calculations circumference of catalyst section constants tn eqn (14) nuxture heat capacity bed diameter mslde tube diameter equivalent diameter outside tube diameter catalyst pticle diameter convergence accelerator for component 1 molar flow of component I molar flow of component I from separator fraction inlet flow mass velocity equivalent mass flow rate molar enthalpy of mixture heat of reaction outside heat transfer coefficient tube side heat transfer coefficient 1 refers to HZ, 2 refers to NZ, 3 refers to NHX, 4 refers to A, 5 refers to CH4 eqmhbnum constant m terms of acttvltles hquld-vapor eqmhbrmm constant thermal conductivtty of heat transfer surface thermal conducttvlty of catalyst basket msulatton rate constant for decomposltlon of ammonia length of heat exchanger fraction hqutd subscnpt refers to converter zone molar flow rate molar flow rate in zone 1 molar flow rate of feed molar flow rate out of converter molecular we&t of component 1 mole fraction of component I

50

GAINES

NR Prandtl number NRC Reynolds number

pressure pressure at bottom of bed AP pressure dlfferentml across bed Pd compressor discharge pressure PF pressure of feed PP pressure out of converter PS compressor suction pressure Q heat term R gas constant reaction rate s, B compressor speed Se geometric mean of the crossflow and the baffle-hole areas term computed from eqn (15) S, T temperature TI temperature m of Ith zone T* temperature in annulus TF temperature of feed TP temperature out of converter temperature in riser TR temperature at bottom of riser TRB temperature on shell side of exchanger TS temperature on 2 Je side of exchanger TT u overall heat transfer coefficient W moss flow rate fraction Hz converted x compresslbrllty factor Z distance from top of zone
P P Greek symbols a

thermal conductivity of gas mixture viscosity of gas mixture catalyst activity gas density effectiveness factor bed heat transfer factor defined by eqn (40) geometnc factor thickness of msulatlon
_CES van Heerden C , Ind Enana - - Chem 1953 45 1242 Shah M J , Ind Engng Chem 1%7 59( 1) 73 [31 Baddour R F, Bnan P L T , Loneats B A and Evmerv _ - J P , Chem Engng Sci 1965 20 281I41 Slack A V , Aiigood N Y and Maune H E , Chem Engng Prvg 1953 49 393 on Promoted Iron Catalysts for (51 Nielsen A, An hoestrgatron the Synrhesrs of Ammonra, 3rd Edn Jul G]eilerups, Copenhagen 1968 161 Annable D , Chem Engng SCI 1952 1 145 171 Kubec J . Burtanova J . Bunanec Z Int Chem EnPnn I I 1974 14(4) 629 I81 Hay J J and Pailar I M , Br Chem Engng 1%3 S(3) 171 [91 Kiaer J , Calculatron of Ammonra Converters on an Electromc Dtgual Computer Akademtsk Forlag, Copenhagen 1%3 ii01 Games L D . I&EC Proc Des Dev 1977 16 381 r iij Sultan R F , Br Chem Engng Equtp Sup I%8 81 ii21 Whrte M H , Chem Engng 1972 79(24) 54 Proc 1970 49(12) 74 n31 Guerreu Cl , Hydrocarbon [I41 Temkm M , J Phys Chem (USSR) 1950 24 1312 I151 Gtiiespre L J and BeattIe J A , Phys Rev 1930 36 743 ii63 Dyson D C and Stmon J M, Ind Engng Chem Fundis, 1968 7(4) 605 Ya S , Zhur Fiz Khrm 1945 19 392 [I71 Kazarnovakn [181 Leva M , Wemtratib M , Grummer M and Clark E L Ind Engng Chem 1948 40(4) 747 r191 Donohye D A Ind Engng Chem Fundls 1949 41(11) 2499 I201 Rerd R C and Sherwood T K , The Propertres of Gases and Llqmds, 2nd Edn McGraw-Htll, New York 1966

1:;

B Y E 7

kinetic parameters defined by eqn (39) activity coefficient fouling factor converslon based on mtrogen