The promoter effect of

piperazine on the removal of

carbon dioxide

by Rob Lensen
7th January 2004

Summary

Carbon dioxide, which falls into the category of acid gases (as does hydrogen sulfide,
for example) is commonly found in natural gas streams at levels as high as 80%.
In combination with water, it is highly corrosive and rapidly destroys pipelines
and equipment unless it is partially removed or exotic and expensive construction
materials are used.
Removal of CO2 from gases can be split up into two different methods. Firstly, the
removal with alkanolamines by which the CO2 is removed by absorption reactions.
The second method is the removal of CO2 with alkaline salts, for example sodiumor potassium carbonate. The major processes are based on aqueous solutions of
sodium and potassium compounds.
When alkanolamines are used for CO2 removal there are three main industry species.
Formerly monoethanolamine (MEA) was used. But MEA is rapidly displaced by
more efficient systems because of the corrosive properties and high heat of reaction
with CO2 . Diethanolamine (DEA) is used for the treatment of refinery gases with
COS and CS2 . DEA is less reactive with COS and CS2 than MEA and also a lower
vapour pressure is needed. The disadvantages of DEA treatment are that vacuum
distillary is necessary and therefore difficult. Methyldiethanolamine (MDEA) has
become an important alkanolamine because of the low energy requirement, high
capacity and high stability. The disadvantage the low rate of reaction with CO 2 .
The rate of the reaction can be increased by using promoters, without diminishing
the MDEA advantages.
In the major processes based on alkaline salts aqueous solutions of sodium and potassium compounds are used. The hot potassium carbonate process is effectively
used in many ammonia, hydrogen, ethylene oxide and natural gas plants. To improve CO2 absorption mass transfer and to inhibit corrosion, proprietary activators
and inhibitors are added. These systems are known as activated hot potassium
carbonate (AHPC) systems.
To improve the CO2 removal processes different promoters are used. In 1980 piperazine (PZ) was found as an effective promotor for alkanolamine processes. Several
research was done to the reaction mechanism and reaction kinetics of piperazine
with MDEA. It is proposed that the reaction of piperazine with MDEA can be
considered as rapid pseudo first order with respect to tertiary amine. The reaction
can be considered second order but the pH of MDEA-PZ systems is never low enough
for a second order reaction. A kinetics model that fits the expirimental data very
accurate is not found yet. The combined model off instantanous piperazine model
and pseudo-first-oder fits the experimental data most accurate. When the effect of
piperazine is compared to other known promoters it is shown that piperazine is a
more effective promotor for alkanolamines.

The most recent discovery is the use of piperazine as promotor for aqueous potassium carbonate systems. It is shown that the addition of an amine increases the
absorption rate dramaticly. When piperazine is added the rate behavior of aqueous
potassium carbonate systems approaches that of 5M MEA at both 40 C and 60 C .
At a rich loading, aqueous potassium carbonate systems are compareable with
MDEA-PZ systems.
The overall conclusion from the data presented in this thesis is that piperazine is an
effective promotor in combination with MDEA and aqueous potassium carbonate.
For usage on an industrial level further research is however needed.

Contents

Summary

1 Introduction

2 Overview of the current processes for CO2 removal

2.1 Procedures with alkanolamines . . . . . . . . . . . . . . . . . .
2.1.1 Reaction mechanism of alkanolamines . . . . . . . . . .
2.1.2 Advantages and disadvantages of several alkanolamines
2.2 CO2 removal with alkaline salts . . . . . . . . . . . . . . . . . .
2.3 Promoters and/or activators used in CO2 absorption . . . . . .

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3 Piperazine as activator for alkanolamines

3.1 Chemical data of piperazine . . . . . . . . . .
3.2 Reaction mechanism with MDEA and PZ . .
3.3 Reaction kinetics with PZ . . . . . . . . . . .
3.3.1 Kinetics with pseudo first-order model
3.3.2 Kinetics with other models . . . . . .
3.4 Comparison of PZ with other promoters . . .

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4 Piperazine as activator for hot carbonate solutions

4.1 Absorption and desorption of CO2 from hot carbonate solutions
4.1.1 Kinetics with un-promoted carbonate solutions . . . . .
4.2 Absorption with promoted carbonate solutions . . . . . . . . .
4.2.1 Kinetics with promoted carbonate solutions . . . . . . .
4.3 Results with piperazine as promotor . . . . . . . . . . . . . . .

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5 Conclusions

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Bibliography

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List of Figures

2.1

Structure of the alkanolamines . . . . . . . . . . . . . . . . . . . . .

3.1
3.2
3.3
3.4

Molecular structures of piperazine species . . . . . . . . . . . . . . .

Enhancement factors for 0.1M PZ / 4.2M MDEA at 40 C [9] . . . .
Enhancement factors for 0.6M PZ / 4.0M MDEA at 40 C [9] . . . .
Comparable absorption rates of different aqueous amine systems at
40 C , as function of CO2 concentration [18]. . . . . . . . . . . . . . .
Comparison of PZ/MDEA blends to conventional blends [9] . . . . .
Effect of piperazine on apparent reaction rate constants of the reaction of CO2 with aqueous solutions AMP at 40 C [32] . . . . . . . . .

13
15
17

3.5
3.6
4.1
4.2

Comparison of promoted K2 CO3 solutions . . . . . . . . . . . . . . .

CO2 heat of absorption in K2 CO3 /PZ . . . . . . . . . . . . . . . . .

17
18
18
24
24

Chapter 1
Introduction

Carbon dioxide, which falls into the category of acid gases (as does hydrogen sulfide,
for example) is commonly found in natural gas streams at levels as high as 80%.
In combination with water, it is highly corrosive and rapidly destroys pipelines
and equipment unless it is partially removed or exotic and expensive construction
materials are used. Carbon dioxide also reduces the heating value of a natural gas
stream and wastes pipeline capacity. In Liquified Natural Gas (LNG) plants, CO2
must be removed to prevent freezing in the low-temperature chillers.
Also to diminish the threat of a rapidly changing climate, emissions of CO2 should
be reduced. One way to reduce these emissions is CO2 removal.
Aqueous alkanolamine solutions are the most widely used solvents for the acid gas
absorption process. Isaacs et al. [20] reported that aqueous solutions of
monoethanolamine (MEA) have the properties of high reactivity, low solvent cost,
ease of reclamation, and low absorption of hydrocarbons. Aqueous solutions of
N-methyldiethanolamine (MDEA) were found to be the attractive solution for the
lower regeneration energy. MDEA is most used and described by Kohl et al.[22].
Chapter 2 gives an overview of the current processes for CO2 removal and the possibility of promoters. The next chapter contains information about the use of piperazine
as a promotor for alkanolamines. The recent discovery to use piperazine as a promotor for hot potasium carbamate systems will be discussed in chapter 4. In the
last chapter the use of piperazine is discussed and conclusions are drawn from the
gathered information.

Chapter 2
Overview of the current processes for CO2 removal

Removal of CO2 from gases can be split up into two different methods. Firstly, the
removal with alkanolamines by which the CO2 is removed by absorption reactions.
Depending on the process requirements, several options for alkanolamine based
treating solvents with varying compositions of solutions have been proposed [22].
These options can be classified into four groups. 1) Amine-Water, 2) Amine-WaterOrganic Solvent, 3) Amine promoted Carbonate Processes, and 4) Amine mixturesWater/Organic Solvent. The second method is the removal of CO2 with alkaline
salts, for example sodium- or potassium carbonate. The major processes are based
on aqueous solutions of sodium and potassium compounds.

2.1

Procedures with alkanolamines

Bottoms [11] firstly described the absorption of CO2 by tri-ethanolamine (TEA).

His patent was used for early gas-treating plants. Further research showed that
other alkanolamines could absorb CO2 as well. The most important and used alkanolamines, shown in figure 2.1, are:
a.
monoethanolamine (MEA)
b.
diethanolamine (DEA)
c.
methyldiethnolamine (MDEA)

HO C

C NH 2

(a) MEA

HO C Cpppppppppppppp
p
p p p p pNH
pp pp p pp
HO C C

HO
HO

(b) DEA

C C ppp pppp pppp

p H3
pC
ppppp ppp
C Cp
(c) MDEA

Figure 2.1: Structure of the alkanolamines

2.1.1 Reaction mechanism of alkanolamines

To understand and clarify the absorption mechanism of CO2 by alkanolamines there
has to be discriminated between the primary, secondary, and tertiary amines.

Chapter 2. Overview of the current processes for CO2 removal

The mechanism of the primary and secondary alkanolamines MEA and DEA can
be represented as the general equations (2.1) and (2.2).
The overall forward reaction between CO2 and primary and secondary alkanolamines usually has been represented as:
CO2 + R1 R2 N H  R1 R2 N COOH
R1 R2 N COOH + R1 R2 N H  R1 R2 N COO

(2.1)
+

R1 R2 N H2+

(2.2)

The first step is bimolecular, second-order, and rate determining, while the second
step was supposed to take place instantaneously. However, this scheme is a substantial simplification for the reaction mechanism that actually occurs. Since 1960
a large number of studies on the reaction between CO2 and alkanolamines in aqueous
solutions have been presented. These studies were reviewed by Blauwhoff et al. [10].
From the results that have been obtained it can be concluded that only for MEA
a general agreement exists on both the reaction order and the value of the kinetic
constant. Versteegh and Oyevaar [33] have shown for the alkanolamine DEA that
the reaction with CO2 occurs via the zwitterion type mechanism. For this amine no
generally valid, unique reaction order can be represented. For other primary and
secondary alkanolamines overall reaction orders varying between two and three were
obtained, both for aqueous and non-aqueous solutions. Therefore the mechanism of
the reaction between CO2 and alkanolamines is not as simple and straightforward
as suggested by the equations (2.1) + (2.2), even for MEA. Danckwerts [16] reintroduced a reaction mechanism proposed originally by Caplow [12] which described the
reaction between CO2 and alkanolamines via the formation of a zwitterion followed
by the removal of a proton by a base, B:

CO2 + R1 R2 N H  R1 R2 N + HCOO
R1 R2 N + HCOO

+ B  R1 R2 N COO

+ BH

(2.3)
+

(2.4)

Research by Donaldson and Nguyen [17] has shown that for a pH < 11 this reaction
can be described with the base catalysis of the CO2 hydration:
CO2 + R1 R2 R3 N + H2 O  R1 R2 R3 N H + + HCO3

(2.5)

Versteeg and Van Swaaij [34] and Benitez-Garcia et al. [5] demonstrated that the
absorption of CO2 in aqueous triethylamine solution is identical to alkanolamines.
Therefore the observed reactivity of tertiary alkanolamines towards CO2 at lower
pH-values of the aqueous solution could not be attributed to the formation of monoalkylcarbonate. Furthermore, according to the mechanism proposed by Donaldson
and Nguyen [17], no reaction should occur if CO2 is absorbed into a non-aqueous
tertiary amine solution. Versteeg and Van Swaaij have shown that the absorption
rate of CO2 into MDEA-ethanol could be described completely as a physical absorption. It was almost identical to the absorption of N2 O, corrected for the differences in physical constants, in the same solution. Moreover, the total amount of
CO2 absorbed was nearly the same as the amount which can be physically dissolved
in this solution. They were able to ascribe the differences completely to the presence
of primary and secondary amine impurities.

Chapter 2. Overview of the current processes for CO2 removal

From this result it is easy to conclude that in non-aqueous solutions no reaction,

even alkylcarbonate formation, occurs between CO2 and tertiary amines. This is in
good agreement with the proposed reaction mechanism. The reaction of tertiary
amines does not occur in non-aqueous solutions.

2.1.2 Advantages and disadvantages of several alkanolamines

In the industry many different alkanolamines are used. To understand why a amine
is used in a specific situation the differences need to be shown.
Formerly MEA was used in gastreating plants for CO2 removal. But MEA is rapidly displaced by more efficient systems. However, for low concentrations of H 2 S
and CO2 it is prefered. This is especially for low pressure and maximum removal
of H2 S and CO2 . The advantages are the high alkalinity and easy recovery from
contaminated solutions. On the other hand an irreversible product is formed with
COS and CS2 , it is more corrosive, high heat of reaction with CO2 and also a high
vapour pressure [22].
DEA is used for the treatment of refinery gases with COS and CS2 . DEA is less
reactive with COS and CS2 than MEA and also a lower vapour pressure is needed.
The disadvantages of DEA treatment are that vacuum distillary is necessary and
therefore difficult. And when a high content of CO2 is present, DEA isnt a good
choice because of the forming corrosive degradation products [22].
MDEA is another alkanolamine which can be used for the removal of CO2 . The
advantages given by Appl et al. 1980 [1] are low energy requirement, high capacity
and high stability, the disadvantage the low rate of reaction with CO2 . The rate of
the reaction can be increased by using promoters, without diminishing the MDEA
advantages. The different promoters will be discussed in section 2.3.

2.2

CO2 removal with alkaline salts

As mentioned in the introduction, CO2 can also be removed from the gases by the
use of alkaline salts. These salts are sodium and potassium carbonate, phosphate,
borate, arsenite and phenolate. The major processes are based on aqueous solutions of sodium and potassium compounds. The hot potassium carbonate process
is effectively used in many ammonia, hydrogen, ethylene oxide and natural gas
plants. To improve CO2 absorption mass transfer and to inhibit corrosion, proprietary activators and inhibitors are added. These systems are known as activated
hot potassium carbonate (AHPC) systems [22]. Which type of activators are used
will be discussed in section 2.3.
The accepted mechanism of CO2 absorption into water consists of two parallel mechanisms:
1.

Direct formation of HCO

3
CO2 + OH  HCO3
HCO3

+ OH

CO3

+ H2 O

(fast)

(2.6)

(instant)

(2.7)

Chapter 2. Overview of the current processes for CO2 removal

2.

10

Reaction of CO2 with water followed by dissociation of carbonic acid

CO2 + H2 O  H2 CO3
H2 CO3 + OH

HCO3

+ H2 O

(slow)

(2.8)

(instant)

(2.9)

According to Astarita [2] the predominant mechanism at pH > 10 is reaction (2.6)

The reaction rate at 105 C is not high enough to be considered instantaneous, Savage [30]

2.3

Promoters and/or activators used in CO2 absorption

Because of the low reaction rate of the CO2 removal by alkanolamines or alkaline
salts, promotors or activators are needed to improve the absorption process. The
following compounds can be used to increase the reaction rate:

Formaldehyde [22]
Methanol [22]
Phenol [22]
Ethanolamine [22]
Arsenious acid [21]
Glycine [28]
Hinderd amine [22]

The general mechanism for promoted solutions is proposed by Astarita [3]:

CO2 + promoter  intermediate
intermediate + OH

 promoter +

HCO3

(2.10)
(2.11)

The effect of the promotion can be quite well described in terms of a homogeneous
catalysis [3, 31]
In the Hot Potassium carbonate process, of Benfield [13], the alkanolamine DEA
is used as the activator of the process, but Bartoo [4] discovered a new organic
promotor. This new activator has a better absorption rate than DEA, at lower
vapour pressure. Another advantage is the excellent chemical stability. The activator
is called ACT-1.
The Giammarco Vetrocoke [19] process uses glycine as an activator. This leads to an
increase of 18% plantload compared to DEA. In dual-activated (amine + glycine)
systems a lower CO2 vapour pressure, a higher regenerator efficiency and a higher
O2 absorption rate is detected, then when a mono activated solution is used.
Addition of arsenic trioxide to aqueous sodium or potassium carbonate solutions
results in a marked increase in the rate of absorption and a desorption of carbon
dioxide, when it is compared with the conventional carbonate solutions. The reaction
rate increases because the rate of hydration of carbon dioxide to carbonic acid is
increased. There is also a shift of the pH toward the acid side in the regeneration
step, resulting in a more complete expulsion of the absorbed carbon dioxide.
The addition of a primary or secondary amine to a tertiary amine has found widespread application in the absorption and removal of CO2 from process gases.

Chapter 2. Overview of the current processes for CO2 removal

11

The success of these solvents is due to the high rate of reaction of the primary or
secondary amine with CO2 combined with the low heat of reaction of the tertiary
amine. By adding small amounts of the primary or secondary amine, a high rate of
absorption is seen in the absorber, while a low energy of regeneration is required in
the stripper. One such blend of amines is piperazine (PZ) activated methyldiethanolamine (MDEA). These solvents have been used successfully for high capacity
CO2 removal in ammonia plants and are patented by BASF [1]. In the next chapter
a more detailed description will be given of the use of piperazine.

Chapter 3
Piperazine as activator for alkanolamines

In this chapter the influence of piperazine (PZ) on the reaction of alkanolamines

with CO2 is described. PZ is most active as promotor when used in combination
with MDEA, therefore the most attention is payed to articles concerning this combination.

3.1

Chemical data of piperazine

In table 3.1 shows an overview of the chemical data of PZ.

Synonyms:
Molecular Formula:
Formula Weight:
Registry number:
Density:
Melting point
Boiling point
Flash point

Piperazine Anhydrous, Diethylenediamine

C4 H10 N2
86.13
110-85-0
146
108-112C
145-146C
82 C

N
Structure

N
Table 3.1: Chemical data of piperazine

PZ may be synthesised by, for example, reacting monoethanolamine with ammonia, or reacting ethylene oxide and NH3 and cyclising the ethanolamines thereby
obtained [1]. The ability of a solvent to remove carbon dioxide is dictated by its
equilibrium solubility as well as mass transfer and chemical kinetics characteristics.
In the next paragraph the kinetics are discussed.

3.2

Reaction mechanism with MDEA and PZ

As shown in paragraph 2.1.1 MDEA has a base catalytic effect on the CO2 hydrolytic
reaction.

Chapter 3. Piperazine as activator for alkanolamines

13

Xu et al.[37] was the first who studied the reaction kinetics of PZ with MDEA. In
this study it is proposed that the reaction can be considered as rapid pseudo first
order with respect to R3 N. Also the CO2 absorbed by free PZ can be transferred
to MDEA rapidly with itself resumed. As seen in table 3.1 piperazine contains
two basic nitrogens and can theoretically react with 2 mol of CO2 . However, the
second amine groups ability to bind a second CO2 can be neglected, which was first
reported by Liu et al. [24]. Bishnoi and Rochelle [8] proposed that the second amine
is reactive, but the pH of these systems is never low enough to observe di-protonated
PZ. It is proposed by Xu et al. [36] that the following reactions occur in a solution
of PZ mixed with MDEA:
M DEA + H +  M DEAH +
M DEA + CO2 M DEA CO2

(3.1)
(3.2)

M EA CO2 + H2 O  M DEAH + + HCO3

(3.3)

P Z + CO2 P Z CO2
P Z CO2 + H2 O  P ZH

(3.4)

+ HCO3

P Z CO2 + H2 O  P ZCOO H3 O
PZ + H

 P ZH

(3.5)

(3.6)

(3.7)

P Z CO2 + M DEA  M DEA CO2 + P Z

HCO3

 CO3

H2 O  H

+H

+ OH

(3.8)

(3.9)

(3.10)

The mentioned reactions are also shown by Bishnoi and Rochelle [9], but they
propose that also the following reactions take place:
P ZCOOO + H2 O + CO2  P Z(COO )2 + H3 O+
M DEA + P ZOO

+ CO2  P Z(COO )2 + M DEAH

(3.11)
+

(3.12)

In Figure 3.1 the piperazine species are shown that occur in the reactions.

Figure 3.1: Molecular structures of piperazine species

Now the reaction mechanism is known, the equilibrium constants can be calculated.
These equilibrium constants are shown by Bishnoi and Rochelle [9] and Xu et al.
[36].

Chapter 3. Piperazine as activator for alkanolamines

14

The difference between the two articles is that Bishnoi and Rochelle have equilibrium
constants for di-protonated piperazine. To calculate the total conversion of MDEA
to MDEAH+ , PZ to PZCOO and PZ to PZH+ the species balance has to be made.
The overall MDEA balance is proposed as [9, 36]:

CM
DEA+ = CM DEA + CM DEAH+

(3.13)

Bishnoi and Rochelle have a slightly different PZ balance, because they think diprotonated PZ also exists in the reaction. The difference is viewed in bold in equation (3.14):
CP Z = CP Z + CP ZH+ + CP ZCOO + CH + P ZCOO + CP Z(COO )2

(3.14)

Also the overall CO2 balance from Bishnoi and Rochelle differs from Xu et al.
CHCO

+ CCO

2
3

+ CCO2 + CP ZCOO + CH + P ZCOO + 2CP Z(COO )2

= y(CM
DEA + CP Z )
(3.15)

The influence of the extra parameters on the results is negligible at low loading,
but at high loading these parameters become more important. Without reactions
(3.11) and (3.12) the data was most of the time underpredicted for about 40%. [9].

3.3

Reaction kinetics with PZ

There are serveral articles describing the method to calculate the reaction kinetics of
PZ with MDEA [8, 9, 36, 37, 38]. Until the article of Bishnoi [9] the overall reaction
was proposed as pseudo first-order. Bishnoi proposed that pseudo first-order model
is a good assumption for MDEA solutions since the reaction of MDEA is slow
enough that no significant depletion of MDEA occurs at the interface. The pseudo
first-order curve for PZ/MDEA blends occurs only true at low loading, therefore the
kinetics model is changed to use a second-order rate. There is just one article that
proposes the use of a second-order model therefore the pseudo first-order model is
also shown.
3.3.1 Kinetics with pseudo first-order model
For low loading the pseudo first-oder model is used. This assumes the concentration
of the amine to be uniform across the cross section of the liquid boundary layer.
When this assumption is adopted the reaction represented in (2.1) is the dominant
reaction of absorption of CO2 into activated MDEA solution. Simultaneously, the
activator PZ may react with CO2 in liquid film to form an intermediate as:
R0 (N H)2 + 2CO2 R0 (N HCOO)2

(3.16)

This reaction is rapid and runs parallel with reaction (2.1). The hydrolytic reaction
of R0 (NHCOO)2 also takes place in equilibrium in the liquid phase as:
R0 (N HCOO)2 + 2H2 O
R0 (N H2+ ) + 2HCO3

(3.17)

Chapter 3. Piperazine as activator for alkanolamines

15

If these reactions are taken into consideration the reaction rate has been proposed
as [37, 38]:
r = (k2 Cam + kp Cp )(pCO2 pCO2 )

(3.18)

This expression assumes that the conversion of MDEA and PZ is constant in the
liquid film.
It is shown by Savage et al. [30] that chemical absorption theory can be applied to
chemical desorption in a fast reaction regime. Therefore Xu et al. [37, 38] proposed
that the chemical absorption and desorption rate for activated MDEA solutions can
be expessed as:
NCO2 = HCO2

q
DCO2 (k2 Cam + kp Cp )(pCO2 pCO2 )

(3.19)

NCO2 = HCO2

(3.20)

DCO2 (k2 Cam + kp Cp )(pCO2 pCO2 )

This is only true when the partial pressure of CO2 is not very high and the free
concentration of MDEA is not very low. It is claimed by Bishnoi et al. [8] that
the results of Xu et al. [37] are not valid, because of the high partial pressure
of CO2 . Therefore the pseudo-first-order assumption breaks down, the reaction
occurs in a region where the piperazine concentration is depleted at the interface.
In Figure 3.2 the results of Xu et al. are displayed. Bishnoi [9] proposes that the
measured enhancement was not significantly different from the enhancement in
MDEA solutions, making it impossible to gain any information about the effect
of PZ. The results are therefore best described as pseudo-first-order absorption into
unpromoted MDEA.

Figure 3.2: Enhancement factors for 0.1M PZ / 4.2M MDEA at 40 C [9]

Figure 3.2 also demonstrates the experimental error of the Xu et al. data [37]. Its
unreasonable to expect that PZ has a negative effect on the enhancement factor.
This negative effect is seen when the loading is above 0.3 mol.

Chapter 3. Piperazine as activator for alkanolamines

16

3.3.2 Kinetics with other models

The kinetics model need to be changed, since the model data does not fit the
experimental data at higher loading. Bishnoi [9] reviewed the different models to fit
the data.
The following models are discussed by Bishnoi:

Pseudo first-order (EP F O )

Pseudo first-order model, discussed in section 3.3.1. Bishnoi used the expression:
s P
( kAm [Am])DCO2
(3.21)
EP F O =
kl 2

Model with instantanous reactions and small driving force

(EGLBL,IN ST )
The enhancement factor predicted by the simple model of instantaneous reactions and small driving force isnt a good approximation of the data.
E GLBL,IN ST =

k l, P ROD [Am]T HCO2

PCO
/
kl,CO
2

(3.22)

Model with only instantaneous reactions for PZ (EP Z,IN ST )

Good approximation is obtained at high loading if only the PZ reactions are
considered instantaneous. This is done by increasing all carbamate and dicarbamate formation rate constants to very large numbers.

Combined model off instantanous PZ model and pseudo-first-order

(EP Z,IN ST + EP F O )
The pseudo first-order model and the instantaneous PZ model can also be
combined. As seen in Figure 3.3 the results of this model are quite accurate.
This model can be expressed as follows:

E=

E P Z,IN ST

EP F O

(3.23)

The results of this review are displayed in Figure 3.3.

With a model that fits the experimental data the real effect of piperazine can be
found. In next section piperazine willl be compared to other promoters.

3.4

Comparison of PZ with other promoters

To conclude if piperazine is an effective promoter for carbon dioxide removal the

effect of piperazine needs to be compared to other promoters.

Chapter 3. Piperazine as activator for alkanolamines

17

Figure 3.3: Enhancement factors for 0.6M PZ / 4.0M MDEA at 40 C [9]

A first rough comparison is done by Erga et al.[18]. Figure 3.4 gives rate data as
function of the CO2 concentration for the primary amines MEA(25%), DGA(25%),
KGl(4.0M), the secondary amine DEA(50%), the tertiary amine MDEA(50%), as
well as for the mixture of MDEA(50%)-piperazine(5%), and piperazine(5%) alone
(% = weight-%). Since the mass transfer surface area are not strictly controlled,
these rate data are just a guideline. Erga et al. [18] concluded that the MDEApiperazine system can be a promising solvent for recovering CO2 .

Figure 3.4: Comparable absorption rates of different aqueous amine systems at

40 C , as function of CO2 concentration [18].
Later on Bishnoi [9] compared the MDEA-piperazine blend with DEA/MDEA and
MEA/MDEA blends. It was seen that the piperazine blends enhances the performance of MDEA by a factor of 50 at low loading. Even at high loading (0.5 mol
CO2 /mol amine), the piperazine blend can be up to a factor of 5 more effective
then 50% MDEA. Piperazine is found to be a more effective promoter than MEA or
DEA, especially at low loading. The high driving force is not seen to have a major
effect on the predicted enhancement factor except at high loading.

Chapter 3. Piperazine as activator for alkanolamines

18

The decrease in enhancement is due to the depletion of piperazine and piperazine

carbamate at the interface. An overview of the results is displayed in Figure 3.5 [9].

Figure 3.5: Comparison of PZ/MDEA blends to conventional blends [9]

Piperazine is not only an effective promoter in combination with MDEA. It is
proposed by Seo [32] that the addition of piperazine to an aqueous mixture of
2-Amino-2-methyl-1-propanol (AMP) increases the reaction rate constant remarkably. The apparent rate coefficient increased with increasing piperazine concentration. In Figure 3.6 the apparent reaction rate constants for the reaction of CO2 into
aqueous solutions of AMP and mixtures of AMP and piperazine at 40 C is displayed.
As shown in Figure 3.6 the promotion effect of piperazine decreased at high AMP
concentration. It is proposed that the decrease of promoter effect is the result of the
decrease of the molar concentration of piperazine in the mixture of amine solution.

Figure 3.6: Effect of piperazine on apparent reaction rate constants of the reaction
of CO2 with aqueous solutions AMP at 40 C [32]
Not mentioned before is the use of piperazine as promoter in combination with
MEA.
A recent study of Rochelle et al. [27] showed that piperazine can also used as

Chapter 3. Piperazine as activator for alkanolamines

19

promoter for MEA systems. An addition of 0.6M PZ in 1.0M MEA increases the
rate by a factor 2 to 2.5 at 60 C .
The relative effect of piperazine is practically independent of CO2 loading, except
at very high loading. This is because PZCOO is also a reactive species with CO2 .
Only at very high loading (0.8-0.9), are both PZ and PZCOO depleted. From
this data it may be concluded that piperazine is also promising promoter for MEA
systems.

Chapter 4
Piperazine as activator for hot carbonate solutions

The hot carbonate process for CO2 removal from gas streams is of interest because of
the high efficiency it exhibts. This process usually operates at temperatures around
100C . At this temperature chemical absorption and desorption takes place, and
it is believed that the liquid side mass transfer rates are significantly enhanced by
chemical reactions.
The most recent discovery is the use of piperazine as promotor for aqueous potassium carbonate systems. Because of this recent discovery there is only one unpublished article [14] that describes that effects of piperazine on the absorption of
carbon dioxide. In this chapter some data of this article of Cullinane [14] is used.
The reaction mechanism without piperazine is decribed in reaction (2.6). It is shown
by serveral investigators [6, 7] that potassium carbonate has a low heat of regeneration, but its rate of reaction is slow compared to amines.

4.1

Absorption and desorption of CO2 from hot carbonate

solutions

To understand the influence of piperazine the reaction kinetics without piperazine

is described first.
The overall reaction can be described as:
CO2 + CO32 2HCO3

(4.1)

In absorption the reaction (4.1) proceeds from left to right, and takes place essentially through the following sequence of elementary steps:
CO2 + OH  HCO3
H2 O  H
CO32

+H

+ OH

HCO3

(4.2)

(4.3)
(4.4)

Reaction (4.2) is rate controlling, and the reactions (4.3) and (4.4) are occuring
everywhere at equilibrium. Another mechanism proposed by Wall [35] known as the
direct reaction of CO2 with water is not be accounted. Because the contribution to
the overall reaction is negligible unless the pH of the liquid solution is very low.

Chapter 4. Piperazine as activator for hot carbonate solutions

21

It is proposed by Savage [30] that the kinetic constant can be calculated with the
film theory equations. The results of this kinetic constant indicates that, at temperatures as high as 105 C , the rate of the chemical reaction is not large enough for
the reaction itself to be regarded as instantaneous. Therefore, even at the highest
tempratures of industrial practice the possibility of rate promotion by additives is
of significant interest.
4.1.1 Kinetics with un-promoted carbonate solutions
Since reaction (4.2) is the rate controlling step, the rate equation can be described
as [30]:
rOH = kOH [OH ][CO2 ] kOH [HCO3 ]
(4.5)
Where kOH and kOH are forward an backward rate constants of reaction (4.2). At
equilibrium conditions equation (4.5) leads to:
kOH [HCO3 ] = kOH [OH ][CO2 ]e

(4.6)

The equilibrium concentration of CO2 is defined as [CO2 ]e .

The expression for the reverse reaction (4.2) in equation (4.6) has been evaluated
by considering conditions at equilibrium, but it is generally true, even when the
system is not at equilibrium [15, 23]. Substituting equation (4.6) into (4.5) gives:
rOH = (kOH [OH ])([CO2 ] [CO2 ]e )

(4.7)

Carbonate bicarbonate system is a buffer solution, so the concentration of OH ion

in the solution near the surface of liquid is not significantly depleted by the absorbed
CO2 . In this case, the carbon dioxide undergoes a pseudo-first order reaction and
equation (4.7) may be rewritten as [3, 15]:
rOH = (k1 ([CO2 ] [CO2 ]e )

(4.8)

where k1 denotes apparent first-order rate constant.

4.2

Absorption with promoted carbonate solutions

Since there is just one article where piperazine is used as promoter for carbon dioxide
absorption, most of the kinetics are based on the theory of other amines. When the
results are compared there are not many differences so it is believed that piperazine
has a comparable reaction mechanism and the same kinetics.
4.2.1 Kinetics with promoted carbonate solutions
When a small amount of amine is added into a carbonate solution, the absorption
rate is enhanced greatly according the following reactions: [3]

CO2 + RR0 N H
RR0 N COOH
0

RR N COOH + OH

HCO3

(4.9)
0

+ RR N H

(4.10)

Chapter 4. Piperazine as activator for hot carbonate solutions

22

At higher temperatures, in the range of industrial operating conditions, the rate

of reaction (4.10) increases significantly. Therefore the system is better represented
by the homogeneous catalysis mechanism [3, 15] and reaction (4.9) is the ratecontrolling step. It is proposed by Rahimpour et al. [25] that the rate equation
of carbon dioxide with promoted hot potassium carbonate in liquid phase can be
described as pseudo first order:
r = (kOH [OH ] + kAm [Am])([CO2 ] [CO2 ]e ) = k([CO2 ] [CO2 ]e )

(4.11)

where k is the overall apparent first-order rate constant and is defined as:
k = (kOH [OH ] + kAm [Am])

(4.12)

When reaction (4.9) is not rate-controlling, but reaction (4.10) is rate-controlling

the rate equation can be described as follows [14]:
r=

kf [CO2 ][Am]
kr
1+ P
kb [B]

(4.13)

Equation (4.13) is the same as equation

P (4.11) when reaction (4.9) is rate-controlling,
since the contribution of the bases,
kb [B] , is large and the denominator reduces
to a value of P
one. When deprotonation of the intermediate (reaction (4.12)) is ratecontrolling ,
kb [B], is small so that the denominator is taken into consideration.
In addition to chemical reaction, mass transfer becomes an important consideration
in absorption processes. The mass transfer can be described by several theorys.
As proposed by Rahimpour et al.[25] the mass transfer can be described with the
penetration surface renewal theory developed by Danckwerts [15]. The theory that
Cullinane [14] uses is known as the eddy diffusivity theory. This theory has the
advantage that it is time-independent.

When the penetration surface renewal theory is used the mass transfer can be
described as:
(4.14)
NCO2 = Ekl (CCO2i CCO2e )
Where CCO2i is the concentration of carbon dioxide at the interface and CCO2e
is the equilibrium concentration of unreacted carbon dioxide in the bulk of liquid
when the reverse reaction of carbon dioxide is appreciable. kl is liquid phase mass
transfer coefficient and E is the enhancement factor and describes the mass transfer
coupled by chemical reactions as[15]:
s
DCO2 k
(4.15)
E = 1+
2
kL
Where k is defined by equation (4.12). The rate of absorption which is defined by
equation (4.14), can be rewritten in terms of physical solubility of carbon dioxide
in solution, H, in the reactive K2 CO3 solution as:
NCO2 = kL HE(PCO2i PCO2e )

(4.16)

In the gas phase the mass transfer as:

NCO2 = kgCO2 (PCO2 PCO2i )

(4.17)

Chapter 4. Piperazine as activator for hot carbonate solutions

23

Where kgCO2 is the gas phase mass transfer coefficient of carbon dioxide.
The total mass transfer is found by combining equations 4.16 and 4.17 and eliminating the interface partial pressure of carbon dioxide, PCO2i . This gives the following
equation:
!
kgCO2 kL EH
NCO2 =
(PCO2 PCO2e )
kgCO2 + kL EH
= KgCO2 (PCO2 PCO2e )

(4.18)

Where KgCO2 is overall gas phase mass transfer coefficient of carbon dioxide.
The eddy diffusivity theory for carbon dioxide can be described by Cullinane [14]:



[CO2 ]
(DCO2 + x2 )
+ RCO2
a
x

(4.19)

In this equation, the diffusion of CO2 is important near the gas-liquid interface. The
value of D/ as it occurs in the solution is approximated by the diffusion coefficient
of CO2 [14].

4.3

Results with piperazine as promotor

Rahimpour et al. [25] and Cullinane [14] proposes that the addition of an amine increases the absorption rate dramaticly. When piperazine is added the rate behavior
of this solvent approaches that of 5M MEA at both 40 C and 60 C . At a rich loading, both promoted K2 CO3 solutions compare favourably with a MDEA/piperazine
blend, as mentioned in section 3.4.
When the amine amount is increased beyond a specific amount, the promoter effect
decreases. Rahimpour et al. [25] proposes that this can be explained due a higher
enhancement factor in the liquid phase, which is directly proportional to the overall
mass transfer coefficient in the case of liquid-phase controlled mass transfer.
By increasing the amine concentration, the gas phase mass transfer is considered
the major factor controlling the absorption process so the CO2 removal is unaffected
by increasing the promoter concentration.
Cullinane [14] compared the PZ-promoted K2 CO3 with other promoters used in
K2 CO3 solutions diethanolamine (DEA) and an unspecified amine investigated by
Satari and Savage [29]. The results are seen in Figure 4.1.
For this promoter comparison, CO2 loading was represented as the conversion of

CO2
3 to HCO3 and Henrys constant was estimated accounting only for the K 2 CO3
in solution. While each promoter improves the rates over un-promoted K2 CO3 to
some degree, piperazine at 60 C gives the best improvement. It is proposed that at
the temprature of 90 C piperazine is much more favourably then the promoter DEA
and the hindered amine. This behaviour can be partially attributed to improved rate
behaviour and partially to salting out CO2 at high temperatures and high ionic
strengths [14].

Chapter 4. Piperazine as activator for hot carbonate solutions

24

Figure 4.1: Comparison of promoted K2 CO3 solutions

It is concluded by Cullinane [14] that the heat of absorption of CO2 increases with
the addition of PZ to aqueous potassium carbonate. With a comparable loading and
piperazine concentration, more potassium carbonate serves to decrease the heat of
absorption only slightly, indicating that the amine is largely responsible for the
reaction with CO2 . A decrease in loading results in a marked increase in the heat
of absorption, most likely due to a difference in heats of absorption of piperazine
and of piperazine dicarbamate. The results also suggest that promoted potassium
carbamate solutions would possess a lower heat of absorption then comparable
amine systems. An overview of the results is displayed in figure 4.2 [14].

Figure 4.2: CO2 heat of absorption in K2 CO3 /PZ

Chapter 4. Piperazine as activator for hot carbonate solutions

25

Proton NMR done by Cullinane suggests that piperazine carbamate is the dominant
species at high loading. Consequently, it is responsible for most of the reaction rate.
Given that piperazine reacts much faster than the carbamate, it can be concluded
that loading has a significant effect on absorption rates.

Chapter 5
Conclusions

The current processes for CO2 removal are used on a large scale. Most processes
are based on well known data and therefore optimising the processes is not really
an option anymore. Therefore the process need to be enhanced with promotors.
One of the promotors that can be used is piperazine. Appl et al. [1] was the first
who researched the influence of piperazine on the CO2 removal. It was shown that
piperazine accelrates the absorption considerably.
The effect of piperazine on CO2 removal is researched in depth since 1992. The first
published results where from Xu et al. [37]. Later on also Bisnoi and Rochelle [8]
researched the influence of piperazine. From the results that both research groups
have published it can be concluded that the MDEA-piperazine system is a promosing solvent for CO2 removal. It is concluded that a solvent of piperazine/MDEA
(5 wt. %/45 wt. %) provides almost two orders of magnitude and more enhancement then 50 wt. % MDEA at low loading and one order of magnitude enhancement
at moderate loading.
The use of piperazine as promotor for the CO2 absorption in aqueous potassium
carbonate is recently found to be effective [14, 25]. Piperazine increases the absorption rate of CO2 substantially. Current studies reveal that, coupled with the low
heat of absorption associated with aqueous K2 CO3 , the piperazine/K2CO3 system
could potentially reduce energy costs associated with CO2 removal. More studies are
needed for this solvent over a broader range of industrially significant conditions.
Since most articles are from just two research groups (University of Texas and East
China University) it is necessary that more research is done by different research
groups. Also because the research group from the East China University is not
always that accurate with their results [26].
The overall conclusion from the data presented in this thesis is that piperazine is an
effective promotor in combination with MDEA and aqueous potassium carbonate.
For usage on an industrial level further research is however needed.

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