Direct amination of benzene for aniline production

1
H. van den Berg,
2
A. J. Zeeuw, M. J. A. Dielwart, S. A. L. de Koster, S. A. G. Lawant, K.
Tang,
Delt !niversit" o Te#$nolog", De%. &$e'i#al (ngineering, Julianalaan 1)*, 2*2+ BL Delt,
T$e ,et$erlands-
1
!niversit" o Twente, .a#ult" o S#ien#e and Te#$nolog", /.0. Bo1 212,
2344 A( (ns#$ede, T$e ,et$erlands- e5'ail6 $.vanden7erg8utwente.nl-
2
Hunts'an Holland
B.9., Merse"weg 14, )1:2 KG Botle; <otterda'.
Aniline is %rodu#ed as a %re#ursor or t$e %rodu#tion o =,=5'et$"lenedianiline >MDA?.
T$is is a %re#ursor or t$e %rodu#tion o di5%$en"l di5iso#"anate >MD@?. Aniline is #urrentl"
%rodu#ed ro' 7enAene in an indire#t %ro#ess, wit$ eit$er %$enol or nitro7enAene as an
inter'ediate. However, t$is %ro#ess $as a low ato'i# ei#ien#". Moreover, t$e use o
nitro7enAene is environ'entall" $aAardous. T$ese disadvantages are t$e reason w$" a dire#t
a'ination %ro#ess is desired.
@n t$is %ro#ess design %roBe#t a dire#t a'ination %ro#ess $as 7een develo%ed. @t is
#olla7orative %roBe#t 7etween t$e Delt !niversit" o Te#$nolog", Hunts'an Holland B.9.
and t$e !niversit" o Twente. T$e 'ain goal is to design a dire#t a'ination %ro#ess t$at 'eets
t$e industrial reCuire'ents, e.g. or sele#tivit", %rodu#tion #a%a#it", saet". @n t$e s"ste'ati#
%ro#ess design a%%lied, irst t$e %ro#ess overall issues >eeds, %rodu#ts, 7oundar" #onditions
or alternative routes? $ave 7een e1a'ined. T$e e1%e#ted %ro#ess #$allenges were identiied
using a tree5diagra'. @n t$e ne1t ste% o t$e #on#e%tual design t$e reCuired %ro#ess un#tions
were deter'ined. SeCuentiall" 'ass and energ" 7alan#es, a detailed design and a te#$ni#al
and e#ono'i# evaluation were %re%ared.
Ater an in de%t$ literature stud", t$e dierent %ro#ess o%tions were evaluated. Two
o%tions inall" re'ained. T$e irst o%tion is to use $"dro1"l a'ine as an a'inating agent
>eCuation 1? at a'7ient te'%erature and %ressure.
>1?
T$e se#ond o%tion is to use a #atal"ti# 'e'7rane at $ig$ te'%erature and %ressure using
a''onia as an a'inating agent >eCuation 2?.
T$ese %ro#ess o%tions were urt$er develo%ed, 'ass and energ" 7alan#es $ave 7een
%re%ared. .ro' t$is, it 7e#a'e #lear t$at t$e irst o%tion was not e#ono'i#all" easi7le, due to
t$e $ig$ #osts o t$e use o $"dro1"la'ine. T$e design o t$e #atal"ti# 'e'7rane o%tion $as
7een #o'%leted, in#luding an esti'ation o t$e eCui%'ent siAe and t$e utilities reCuired.
A i1ed 7ed rea#tor wit$ a %alladiu' >/d? 'e'7rane $as 7een sele#ted, w$ere
/d&sD,aE5Zeolite >4.3 wtF /d, 4.3 wtF &s? is used as t$e #atal"st. T$e %ro#ess te'%erature
is 344G& and t$e %ressure is 34 7ar. T$e 7"5%rodu#t $"drogen is used to 'a;e a''onia on5
site, w$i#$ is ed to t$e 'e'7rane rea#tor. B" a%%l"ing t$is %ro#ess, a sele#tivit" towards
aniline o nearl" 144F #an 7e a#$ieved. Based on literature data, t$e single %ass #onversion o
7enAene is esti'ated to 7e 14F. At t$is #onversion, t$e %ro#ess is not e#ono'i#all" attra#tive,
due to t$e reCuired se%arations and t$e large re#"#le. To 'a;e %roit, t$e #onversion $as to 7e
in#reased to )2F. .urt$er resear#$ $as to o#us on t$e i'%rove'ent o t$e 'e'7rane rea#tor.
To 'a;e t$e irst %ro#ess o%tion easi7le we need less e1%ensive %rodu#tion o
$"dro1"la'ine.