Synthesis of ethylenediamine

experimental and theoretical kinetics

Xinzhi Chen, Shaodong Zhou, Haijiang Zhang and Chao Qian*
Department of Chemical Engineering, Zhejiang University, Hangzhou 310027, P.R. China
*E-mail: supmoney@163.com

ABSTRACT
The basic process for producing ethylenediamine involves contacting
monoethanolamine with ammonia at elevated temperature in the presence of a
catalyst. The mechanism and kinetics of the ammonolysis of monoethanolamine
in the gas phase have been investigated using a combination of experimental
and theoretical methods. The experiments was carried out in tubular reactors
type fixed bed single tube. A catalytic route to ethylenediamine (EDA)
via monoethanolamine (MEA) using nickle catalysts has been studied in detail.
The reaction as carried out at 33 atm and 235-335OC, with ratio of
n (ammonia) : n (monoethanolamine) are 5.6 : 1 gave the optimum result.

KEYWORDS: ammonolysis, monoethanolamine, tubular reactor

INTRODUCTION
Ethylenediamine plays an important role in the chemical industry. Among all the
methods used to synthesize ethylenediamine, the ammonolysis of
monoethanolamine is most economical. Thus it is important to perform
investigations on this reaction both experimentally and theoretically. Ethanol
and buthanol are known to give their corresponding aldehyde and primar,
secondary, and tertiary amines when reacted with ammonia (Pasek et al.1972).
In testing hydrogenating catalysts in the ammonolysis of dodecanol, Baiker and
Richarz (1997) isolated the intermediate aldehyde. Langden et al. (1962)
presumed the intermediate aminoacetone to explain the synthesis of 2,5-
dimethyl piperazine from isopropylamine. Aston et al. (1934) theorized that
aminoacetaldehyde is the first step in the synthesis of pyrazine from MEA and
deduced that non isolation was due to further reaction of aldehyde to resinous
products. The most direct evidence is from work done by Bashkirov et al.
(1971), who investigated the amination of ethanol with isotopic labelling. Using
iron catalysts shown to be active for dehydrogenation of alcohols and aldehydes,
they compared conversions of unlabeled ethanol with deuterated ethanol, and
their data support the dehydrogenation step as opposed to a direct dehydration of
the alcohol with ammonia.
Details on the role of the components of the catalyst are sparse. Baiker
and Richarz (1997), using several long-chain alcohols over copper catalysts,
showed that dehydrogenation and hydrogenation take place on Cu center.
Catalysts of Cu or Ni were found to be more active than other metals.
Karpeiskaya and Gorshkov (1970) concluded that the carrier plays an important
role in the dehydration step and proposed a mechanism for Co-catalyzed
ammonolysis of MEA. Based on thermodynamic data in the literature or
estimates using group contributions, an array of possible over all reaction can be
deduced. Most of the reprted work on MEA ammonolysis is recorded in the
patent literature. While the results are not strictly comparable because of
difference in reactor type, hydrogen partial pressure, and other facrors, some
general observations can be made about reactions. In this experimental the
temperature is 235-335OC and the pressure is generally 33 atm. The main
reaction is reaction of MEA with ammonia produced ethylenediamine (EDA)
and water. The conversion of MEA in this reaction is 84%. The side reaction is
reaction of MEA with EDA produced diethylenetriamine (DETA) as a by-
product. The conversion of MEA in this reaction is 16%. Over all, The total
conversion of MEA is 75%.

CALCULATION
All calculation were performed using GAUSSIAN 03 software [7].
The hybrid DFT theory was applied to this problem with the B3LYP method,
which uses Backes three-parameter hybrid functional [8], together with the non-
local correlation provided by the LYP expression [9,10], and VWN functional
III [11] for local correlation. The polarised continuum (overlapping spheres)
model [12-14] (PCM).
The geometries of the reactants and products were fully optimised
until a stationary point on the potential surface was found. The geometries of the
transition states were searched and reoptimised. Subsequent calculation, such as
frequency calculation and the intrinsic reaction coordinates [15,16] (IRC)
calculation were performed to confirm the transition states as the saddle points
of the reactions. The frequency calculations on the optimised geometries were
also used for the zero point energi (ZPE) corrections to calculate the
thermodynamic properties.
The thermodynamic properties were calculated for a pressure 33 atm
and 235-335OC. The rate constants of the reaction were also calculated. As there
are continuous interaction between each molecule and neighbours, even the
simplest physical transport processes cannot be treated accurately. There is thus
no satisfactory general theory of solution kinetics. However, the rates can be
predicted using gas-phase theories in mostcases when the influences of
neighbours on the reactants are relatively small, making it reasonable to cnsider
for reactions two-molecule collisions only.
 REACTION AND KINETIC
The monoethanolamine (MEA) route to ethylenediamines seems to be
the preferred route when ethylenediamine is the preferred product. The process
produce ethylenediamine (EDA) as main product and diethylenetriamine
(DETA) as by-product. The reaction as carried out at 33 atm and 235-335OC and
use raney nickle as catalyst.
The main reaction

H2NCH2CH2OH (g) + NH3 (g) H2NCH2CH2NH2 (g) + H2O (g)

MEA (g) + NH3 (g) EDA (g) + H2O (g)

for main reaction :

kmol
r1 = k1 PMEA PNH3 , kg katalis. hour

The side reaction

H2NCH2CH2OH (g) + H2NCH2CH2NH2(g) H2NCH2CH2NHCH2CH2NH2(g) + H2O (g)

MEA (g) + EDA (g) DETA (g) + H2O (g)

for side reaction :

kmol
r2 = k2 PMEA PEDA , kg katalis. hour

From this experiment, the equation for the rate reaction are :

1.4201 104
1 = 4.2726 102 exp [ ]

1.1284104
2 = 2.8601 102 exp [ ]

In order to obtain the obseved kinetic parametes, several approximations

have been included, but the relative error of the calculated rate constant is still within
one order. Also the calculated results also give an explanation for the low
concentration of monoethanolamine throught the reaction. Therefore, the kinetic
model used in this study is suitable for this similar systems. Also, the theories
employed can be also suitable for the study of similar reactions. If more accurate
prediction of apparent kinetic parameters is required, a more sophisticated mass
transfer model needs to be established.
CONCLUSIONS
The reaction between monoeyhanolamine and ammonia has been investigated both
theoretically and experimentally. The reaction pathways have been probed using DFT
theory, with the transition state located for each elementary reaction, and the
dominant pathway has been determined. The kinetic model is compiled to estimate
the observed rate constant. Also, the theoretical result is consistent with the
experimental data, with a relative difference of one order. More investigation is
needed both theoretically and experimentally to gain a deeper

ACKNOWLEDGEMENT
We acknowledge the funding support by a grant from the National Natural
Science Foundation of China (No. 20776127), the National Key Technology
R&D Program (No. 2007BAI34B07).
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