Yildirim (2012) RA in Chemical Process Industry

Chemical Engineering Journal 213 (2012) 371–391
Contents lists available at SciVerse ScienceDirect
Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej
Review
Reactive absorption in chemical process industry: A review on current activities

Ömer Yildirim a, Anton A. Kiss b, Nicole Hüser a, Katharina Leßmann a, Eugeny Y. Kenig a,⇑
a
University of Paderborn, Faculty of Mechanical Engineering, Fluid Process Engineering, Pohlweg 55, D-33098 Paderborn, Germany
b
AkzoNobel - Research, Development & Innovation, Process Technology ECG, Zutphenseweg 10, 7418 AJ Deventer, The Netherlands
h i g h l i g h t s
" A reactive absorption review covering industrial processes and research activities.
" Role of reactive absorption as a core environmental protection process and a key separation method is highlighted.
" A major application of reactive absorption is removal of CO2, H2S, SOx and NOx.
" Another major application is industrial production of basic chemicals such as nitric acid and sulphuric acid.
a r t i c l e i n f o a b s t r a c t
Article history: Reactive absorption (RA) is a unit operation comprising the absorption of gases in liquid solutions with
Received 13 June 2012 simultaneous chemical reactions within a single apparatus. The role of RA as a core environmental pro-
Received in revised form 24 September 2012 tection process has grown up significantly, and nowadays, this technology belongs to the most important
Accepted 25 September 2012
separation methods in the chemical process industry, among others, for gas treatment and purification,
Available online 23 October 2012
removal of harmful substances, as well as for the production of basic chemicals, e.g. sulphuric and nitric
acid.
Keywords:
This article provides a comprehensive review on current RA applications covering both industrial pro-
Reactive absorption
Gas treatment
cesses and research activities.
CO2/H2S/SOx/NOx removal Ó 2012 Elsevier B.V. All rights reserved.
Nitric acid
Sulphuric acid
Industrial applications
Research activities
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 372
2. Reactive absorption applications. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 373
2.1. Removal of CO2 and/or H2S . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 373
2.1.1. Industrial applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 375
2.1.1.1. CO2 removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 375
2.1.1.2. H2S removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 377
2.1.1.3. Removal of CO2–H2S mixtures and other impurities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 377
2.1.2. Research activities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 377
2.1.2.1. Improvement of solvents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 378
Abbreviations: ABB, Asea Brown Boveri; AEEA, N-(2-aminoethyl)ethanolamine; aMDEA, activated methyldiethanolamine; AMP, 2-amino-2-methyl-1-propanol; B&W,
Babcock and Wilcox; CCS, carbon capture and storage; DEA, diethanolamine; DEEA, N,N-diethyl ethanolamine; DETA, diethylenetriamine; DGA, diglycol amine; DIPA, di-
isopropanolamine; DMEA, N,N-dimethylethanolamine; DMP, N,N0 -dimethylpiperazine; DTI, Department of Trade and Industry; EDTA, ethylenediaminetetraacetic acid; EEA,
N-ethyl ethanolamine; EFMA, European Fertilizer Manufactures Association; EOP, electrical output penalty; EPA, US Environmental Protection Agency; FGD, flue gas
desulphurisation; HEA, high efficiency absorption; HETP, height equivalent to a theoretical plate; HTU, height of transfer units; LNG, liquefied natural gas; LPG, liquefied
petroleum gas; LLB, Lurgi Lentjes Bischoff; MDEA, methyldiethanolamine; MEA, monoethanolamine; MHI, Mitsubishi Heavy Industries; MMEA, N-methylmonoethanolamine;
NTU, number of transfer units; NGCC, natural gas combined cycle; OCFE, orthogonal collocation on finite elements; PZ, piperazine; RA, reactive absorption; SCOT, Shell Claus
Off-gas Treating Process; TEA, triethanolamine; TGT, tail gas treatment; TMEDA, N,N,N0 ,N0 -tetramethylethylendiamine.
⇑ Corresponding author. Tel.: +49 (0)5251 60 2408; fax: +49 (0)5251 60 2183.
E-mail addresses: eugeny.kenig@upb.de (E.Y. Kenig), tony.kiss@akzonobel.com (A.A. Kiss).
URL: http://mb.uni-paderborn.de/fvt
1385-8947/$ - see front matter Ó 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cej.2012.09.121
372 Ö. Yildirim et al. / Chemical Engineering Journal 213 (2012) 371–391
2.1.2.2. Improved integration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 379

2.1.2.3. Cement industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 379
2.2. NOx removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 379
2.2.1. Industrial applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 379
2.2.2. Research activities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 380
2.3. Nitric acid production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 381
2.4. Desulphurisation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 383
2.5. Sulphuric acid production. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 386
3. Concluding remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 389
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 389
1. Introduction Optimal design of RA processes requires adequate models cov-

ering mass and heat transfer, reaction kinetics and column hydro-
The current EU legislation imposes tighter restrictions aimed at dynamics. Different possibilities to model RA units are presented
reduction of the impact of process industries on the environment. by Fig. 1. Large-scale applications are modelled by sub-dividing
Consequently, substantial research work focuses on developing columns into smaller segments, so-called stages. Each stage corre-
sustainable processes allowing efficient handling of waste and pro- sponds to a single tray or to a segment of packed columns. The
duction of chemicals. Process industries intensively work with gas equilibrium stage model assumes that the gas and liquid streams
streams. Both natural and industrial gases are processed, for in- leaving a stage are in thermodynamic equilibrium. Due to its sim-
stance in gasification of different fuel sources (coal, oil and natural plicity, this model (first published in [5]) has been used in the past
gas) or in diverse manufacturing processes of chemical industry. decades for a variety of applications, especially for non-reactive
Before using gas streams as chemical feedstock or releasing systems. Yet, in real absorption processes, the thermodynamic
them into atmosphere, it is usually necessary to change their com- equilibrium is usually not attained within a stage. For this reason,
position by removing one or several components. Basically, there
exist five methods suitable for gaseous component capturing,
Table 1
namely, absorption, adsorption, permeation through a membrane, Industrial applications of absorption [2].
chemical conversion to another compound, and condensation [1].
The gas industry Gas dehydration
From these operations, absorption is undoubtedly the most impor-
Removal of CO2 and H2S
tant one. During absorption process, a gas to be treated is brought Selective absorption of H2S
in contact with a liquid stream and gas components are transferred
Refineries Hydrocarbon absorbers for lean oil etc.
into the liquid (solvent) phase in which they are soluble. Important H2S absorbers
gas purification applications are listed in Table 1 [2]. Various types of stripping columns
Depending on the mechanism binding the gas compounds in Sour water strippers
solvent, one can distinguish between physical and chemical (or The petrochemical industry Synthesis gas processing
reactive) absorption [3,4]. Physical absorption of gas or gas mixture Gas saturation
components in a liquid solvent comprises mass transfer at the gas– Ethylene oxide absorption
Acrylonitrile absorption
liquid interface and mass transport within the phases. It depends
The chemical industry Synthesis gas processing (CO2 removal)
on the gas solubility and the operating conditions (e.g. pressure
Chlorine drying
and temperature). A classic example of physical absorption of a HCl and ammonia absorption
gas into a liquid is the absorption of carbon dioxide (CO2) into Absorption of nitrous gases
water (H2O) – usual in the beverage industry. Chemical absorption, The cellulose industry Sulphur dioxide absorption
also known as reactive absorption (RA), is based on a chemical Chlorine dioxide absorption
reaction between the absorbed substances and the liquid phase. Flue gas scrubbing with sulphur recovery
It largely depends on the stoichiometry of the reaction, concentra- Food processing Stripping various components producing
tions of the reactants and mass transfer rates. odours
This paper focuses on RA operations. They may be carried out in Processing fatty acids
Hexane absorption and stripping
different units, with a wide spectrum of phase flow types and
interactions (see Table 2). In most cases, RA is carried out in plate The metal and packaging Absorption of triethylamine (in foundries)
industries Absorption of lube and cooling oils
or packed columns. In plate columns, the phases flow counter-cur-
Absorption and recovery of solvent
rently, whereas on each given plate, a cross-flow is usually estab- vapours
lished. In packed columns, a liquid flows along the packing
Exhaust air scrubbing Removal of acid components (wet- and
surface, whereas a gas stream occupies the rest of the free volume. dry-scrubbing of SOx and NOx)
There exist numerous plate and packing designs. In [1], guidelines Removal of base components
are given how to select the most appropriate internals for specific Removal and recovery of organic solvents
RA applications – depending on the Hatta number. RA may also Wastewater/sewage treatment Air stripping of chlorinated hydrocarbons
proceed in spray contactors, the simplest type of an absorption col- and pollution control Desorption and recovery of ammonia
Effluent neutralization
umn. The desired contact area is achieved by dispersing the fluid in
Deaeration of seawater
small droplets.
Ö. Yildirim et al. / Chemical Engineering Journal 213 (2012) 371–391 373
Table 2 transfer occurs by steady-state molecular diffusion, whereas the

Reactive absorption units [3]. bulk phases are ideally mixed. The multicomponent diffusion in the
Unit group criterion Unit type films can be described by the Maxwell–Stefan equations. Chemical
Both phases in a continuous form Packed columns reactions are considered by including reaction source terms in the
Thin film contactors balance equations for each bulk phase and in the mass transport
Wetted-wall columns equation for the film. The necessary model parameters, e.g. the film
Contactors with flat surface thicknesses, are determined using empirical correlations. For many
Laminar jet absorber
Disc (sphere) columns
applications, the two-film model parameters can be found in the
literature and, therefore, the method is often preferred [12].
A disperse gas phase and a continuous liquid Plate columns
phase Plate columns with packing
The present article gives a review on industrial applications of
Bubble columns RA for gas treatment/purification and for production of basic
Packed bubble columns chemicals. Among the considered systems are those containing
Mechanically agitated CO2, H2S, NOx and SOx, as well as nitric and sulphuric acid. In addi-
columns
tion, for each process, the latest research activities are discussed.
Jet absorbers
The fundamentals of RA are outside the scope of this article and
A disperse liquid phase and a continuous gas Spray columns
can be found elsewhere [3,13,14].
phase Venturi scrubber
2. Reactive absorption applications

tray efficiencies or HETP (height equivalent to a theoretical plate)
values [6] are introduced to build a link to real columns. 2.1. Removal of CO2 and/or H2S
Absorption is usually dominated by the mass transport kinetics.
Besides, in reactive processes, chemical reactions must be taken We consider the removal of the acid gases CO2 and/or H2S in a
into account. The equilibrium stage concept can hardly address single section, because these components are often met in the
these issues reasonably. A more theoretically justified approach is same gas stream and they are treated with similar solvents.
based on using HTU/NTU values [7]. The so-called HTU/NTU method The solvent must be chosen under consideration of the follow-
allows determining the column height as a product of two values, ing factors [15,16]:
HTU (Height of a Transfer Unit) and NTU (Number of Transfer
Units). The HTU value depends on column load, column internals Required purity of cleaned gas stream for further processing or
and empirical mass transfer correlations, whereas the NTU value end use.
is obtained by integrating the inverse of the driving force over the Composition of feed gas.
column height. In the HTU/NTU method, chemical reactions are Utility requirements, process costs.
usually considered with the aid of enhancement factors [8–10]. Corrosion and solvent degradation/solvent losses.
The enhancement factors depend on the type and order of the reac-
tion and the mass transport model. The complexity of the involved For the treatment of gases containing CO2 and/or H2S, aqueous
reaction scheme cannot be easily captured by a single parameter, solutions of ethanolamines, carbonates as well as ammonia can be
and, thus, this method often gives inaccurate results. used. The application of ammonia has decreased in the past years
The most adequate and reliable method for the description of [1,17]. However, absorption with aqueous ammonia offers many
staged absorption units is the rate-based approach, a method that advantages over conventional ethanolamine processes, e.g. higher
takes the rates of multicomponent mass and heat transfer and the CO2 absorption efficiency, lower decomposition temperatures and
chemical reaction into account directly [11]. The mass transfer be- lower costs [18,19]. In this review, we only consider amine and car-
tween the phases can be described by different theories, such as the bonate processes, as they are mainly used for acid gas removal [1].
two-film model or the penetration/surface renewal theory. The Amines: In general, alkanolamines have at least one hydroxyl
mostly used two-film model assumes that mass transfer resistance group and one amino group in their chemical structure. The hydro-
is concentrated in thin films at the interface. In these films, mass xyl groups increase the water solubility and reduce the vapour
Fig. 1. Modelling approaches for reactive absorption (adapted from [3]).

HO HO
H CC CC
HO C C N N H N CC OH
H CC CC
HO HO
Monoethanolamine Diethanolamine Triethanolamine
HO
CC OH
CC H
C
NH N CH3 HO C C O C C N
C
CC H
CC OH
HO
Diisopropanolamine Methyldiethanolamine 2 (2-aminoethony) ethanol
Fig. 2. Molecule structure of amines.
Table 3 Protonation of alkanolamine : RNH2 þ Hþ $ RNHþ3 ð4Þ

Qualitative characteristics of the amines for the removal of CO2 (adapted from [21]).
Amines
Primary Secondary Tertiary Carbamate formation : RNH2 þ CO2 $ RNHCOO þ Hþ ð5Þ
MEA DEA TEA, MDEA
Table 3 shows some characteristics of primary, secondary and
High Low tertiary amines used in the gas treatment. These properties are
High Low important for choosing the most appropriate solvent for the gas
High Low treatment process in consideration. The enthalpies of reaction
High Low and evaporation decrease from primary to tertiary amines. These
Low High enthalpies are directly related to the energy required for solvent
regeneration. Therefore the regeneration of tertiary amines re-
quires lower energy consumption than of primary amines. The
pressure of the alkanolamine. The amino group supplies the alka- reaction rate of primary amines is higher than of tertiary amines.
linity in aqueous solutions, which is necessary for the absorption Therefore high solvent circulation rates are necessary, when ter-
of acid gases. tiary amines are applied. Primary amines are more corrosive than
Alkanolamines can be subdivided into three groups according to secondary or tertiary amines. The corrosivity influences the choice
their chemical structure: (1) primary amines, (2) secondary amines, of equipment material and the efficiency of the absorption process
and (3) tertiary amines. Primary amines have a nitrogen atom with by limiting the working capacity [21]. The high corrosivity of pri-
two hydrogen atoms directly attached to it. Secondary amines have mary amines and their reaction products increase the investment
one hydrogen atom attached to the nitrogen atom and tertiary costs, since corrosion resistant materials are necessary. The loading
amines have no hydrogen atoms directly attached to the nitrogen describes the capability of one mole solvent to absorb one mole
atom. The chemical formulas of the most widespread amines, acid gas components. The loading increases from primary to ter-
MEA, DEA, TEA, DIPA, MDEA and DGA, are shown in Fig. 2. Other tiary amines. This implies higher amine concentrations of primary
amines and amine based solvents are discussed in [20]. In CO2/H2S amines for comparable removal results with tertiary amines. Some
absorption with primary amines, following reactions take place [1]: quantitative information for the most common amines can be
found in Table 4 [22].
Ionisation of water : H2 O $ Hþ þ OH ð1Þ
Carbonates: The processes are based on: (1) application of hot
potassium carbonate, (2) absorption by ambient temperature so-
Ionisation of dissolved H2 S : H2 S $ Hþ þ SH ð2Þ
dium or potassium carbonate solutions with vacuum regeneration,
Hydrolysis and ionisation of dissolved CO2 : and (3) absorption into solutions containing free caustics at ambi-
ent temperature. In this article, only high temperature absorption
CO2 þ H2 O $ HCO3 þ Hþ ð3Þ is considered, because this technology is applied for both, CO2
Table 4
Major properties for the most common amines (adapted from [22]) .
Property MEA MDEA AEEA DETA AMP PZ

Chemical formula C2H7NO C5H13NO2 C4H12N2O C4H13N3 C4H11NO C4H10N2
Molecular weight (g/mol) 61.08 119.16 104.15 103.17 89.14 86.14
Density (kg/m3) 1012 1038 1029 955 934 1100
Boiling point (K) 443 243 513 207 438 420
Vapour pressure, 293 K (kPa) 0.0085 0.0013 0.00015 0.02 0.1347 0.1066
Vapour pressure, 393 K (kPa) 15.9 n/a 0.969 n/a n/a 41.66
Solubility at 293 K Soluble Soluble Soluble Soluble Soluble 14%wt
Pseudo 1st order rate constant at 298 K (m3/kmol/s) 7000 3.5 12100 49740 681 53700
Activation energy (kJ/mol) 46.7 44.3 n/a n/a 41.7 35
Absorption capacity (mol CO2/mol amine) 0.5 1.0 1.0 1.0 1.0 1.0
and H2S removal, while processes at ambient temperatures are not Table 5
suitable for CO2 removal. The other processes are described in [1]. CO2 removal application in major industrial processes (adapted from [24]).
During acid gas removal, H2S reacts with the hydroxyl group: Process Common cleanup
targets
H2 S þ OH $ HS þ H2 O ð6Þ Hydrogen manufacture <0.1% CO2
Ammonia manufacture <16 ppm CO2
This reaction proceeds extremely rapidly. The reaction of CO2
Natural gas purification
with alkaline solutions usually occurs slower than the reaction of Pipeline gas <1% CO2
H2S. CO2 absorption is accompanied by the two following simulta- LNG feedstock <50 ppm CO2
neous chemical reactions [1]. Synthesis gas for chemical production (H2/CO) <500 ppm CO2
Mechanism 1. Formation of HCO Coal gasification 500 ppm CO2
3 via the reaction of CO2 with a
Ethylene manufacture (steam cracker gas 1 ppm CO2
hydroxyl group: treating)
Power plants
CO2 þ OH $ HCO3 ðfastÞ ð7Þ NGCC power plant <0.5% CO2
Coal fired power plant <1.5% CO2
HCO3 þ OH $ CO2

3 þ H2 O ðinstantaneousÞ ð8Þ
Mechanism 2. Reaction of CO2 with water and dissociation of
Table 6
HCO
3: Desired quality of treated syngas for various downstream applications (adapted from
[15]).
CO2 þ H2 O $ H2 CO3 ðslowÞ ð9Þ
Downstream use Power plants Hydroprocessing Chemical production
Sulphur (wppm) 10–15 <1 <0.01–1

H2 CO3 þ OH $ HCO3 þ H2 O ðinstantaneousÞ ð10Þ CO2 (vol.%) – <0.1 0.05–2.0
CO – <50 wppm H2/CO control
Which mechanism mainly takes place depends on the pH-value
as per requirement
of the solution. At pH-values higher than 8, the 1st mechanism pre-
dominates, otherwise the 2nd mechanism determines the process.
In industrial applications, the pH-value is mostly higher than 8
[23]. 2.1.1.1. CO2 removal. According to [25], CO2 is mainly produced by
gasification, reforming or in power plants. More than 97% belongs
to the fossil fuel combustion [26]. Possible sources are coal, oil, nat-
2.1.1. Industrial applications
ural gas and biomass. The applications of absorption processes are
The typical flow sheet of a RA process for gas cleaning includes
either post-combustion, as in power plants, or pre-combustion, as
an absorption column to perform the removal of the compounds
in the reforming or gasification of natural feed stocks. These appli-
from the feed gas. The outlet gas leaves the column nearly free of
cations are illustrated in Fig. 4 [27]. Depending on the type of the
unwanted compounds (clean gas). This step is followed by a strip-
power plant, the concentration of CO2 in the gas phase can vary
ping column, in which the solvent is recovered (Fig. 3).
from 3 to 16 mol%. In Table 7, typical compositions of exhaust
In our article, the industrial RA applications are subdivided
gases from coal-fired and gas-fired power plants are listed. Besides,
according to the captured components. In some cases, CO2 is the
CO2 removal occurs in ammonia and hydrogen production plants.
target component, as in the fossil fuel combustion. In other pro-
The choice of solvent depends on different given conditions, e.g.
cesses, it is necessary to capture H2S selectively (e.g. in the tail
feed gas composition and requirements concerning clean gas
gas treating). However, in the most applications, both CO2 and
specifications [1,15]. Table 8 lists the CO2 capturing processes
H2S are captured along with some other components, e.g. COS,
and their licensors. Additionally, this table gives information about
HCN, CS2.
the industrial applications, the used solvents and the numbers of
Table 5 shows examples of specifications for the CO2 removal
installations. The information is taken from the Gas Processes
for different gases depending on their further processing [24]. In
Handbook [28].
Ref. [15], the purity requirements for syngas in various down-
A typical flow sheet of a RA process consists of an absorption
stream applications are listed (Table 6).
column that captures CO2 from the feed gas (acid or sour gas) by
an amine solvent, thus leaving the outlet gas free of CO2 (clean
gas), followed by a stripping column that performs the CO2 desorp-
tion and the recovery of the amine used as recyclable solvent
(Fig. 3). Reactive absorption with MEA is an established technology
which is used since the seventies. The Econamine FG process (pur-
chased by Fluor Daniel) is one of the most widely used processes in
industry using MEA. There are more than 24 existing plants using
the Econamine FG process, each with a total capacity of 6–
1000 t absorbed CO2/day. It uses a 30 wt% MEA solution with cor-
rosion inhibitors. The process can recover 85–95% of the CO2 in flue
gases and produces CO2 with a purity of more than 99% – depend-
ing on parameters such as the CO2 content of the flue gas, the
height of the absorption column, the liquid-to-gas stream ratio
and the regeneration efficiency (CO2 loading of the lean solvent)
[25,29].
Alternatively, non-inhibited MEA solutions can be used for CO2
absorption. The so-called ‘‘ABB Lummus Crest-technology’’ applies
solutions with low MEA concentration of 15–20 wt%; thus,
Fig. 3. Process flow diagram of an absorption/desorption process. the addition of inhibitors against corrosion is not required. The
N 2 /O2
Post-combustion
Separation by
Power CO2 CO 2
absorption
Biomass
plant separation
Gasification
Natural Gas,
CO / H 2
H2 H2 N 2 /O 2
CO2 Power CO2
Shift plant
separation compression
CO 2
CO / H 2
Reforming Pre-combustion
Coal, Oil,
Power CO 2
plant Oxy-combustion
O2
N2
Air Air separation
Fig. 4. CO2 origin and process flow (adapted from [27]).
Table 7
Typical exhaust gas composition (adapted from [29]).
N2 (mol%) CO2 (mol%) O2 (mol%) Water vapour (mol%) NOx (mol%) SO2 (mol%) Ash (mol%)
Coal-fired powerplant 70–75 12–16 3–4 6–7 400 ppm 150 ppm Up to 30 ppm
Gas-fired powerplant 70–75 3–5 10–12 7–10 <50 ppm <10 ppm –
Table 8
Reactive absorption processes for the capturing of CO2 (adapted from [28]).
Process Licensor Solvent Installations

Amine Guard FS UOP LLC Ucarsol (MDEA-based) 500+ units worldwide
Mostly treating natural gas, ammonia syngas and hydro-
gen streams
Benfield UOP LLC Hot potassium 700+ units worldwide
carbonate 65+ treat natural gas
200+ treat ammonia syngas
110 in hydrogen plants
Other installations: in SNG, partial oxidation, coal gasifica-
tion and petrochemical applications
Kerr-McGee/ABB Lummus Global Randall Gas Technologies, ABB MEA 4 on coal-fired boiler flue gases
Absortion/stripping technology Lummus Global Inc. 2 produce gaseous chemical-grade CO2
2 produce food-grade liquid
Fluor Econamine FG Plus process Fluor Enterprises, Inc. MEA > 30% 24 units worldwide
Recover CO2 from low-pressure, O2 containing streams
LRS 10 – CO2 removal Advantica Ltd. DEA promoted 30 plants worldwide
potassium carbonate Mainly retrofits in the ammonia, hydrogen, natural gas
and chemicals industries
total capacity of all absorption plants operated world-wide varies Some companies use sterically hindered amines for the removal
in the range 180–720 t CO2/day. Depending on the inlet SOx con- of CO2. These amines are developed as alternatives for MEA (e.g.
centration, a preliminary desulphurisation step may be required. less corrosive or higher regeneration rate) [1]. By the reaction of
In the ‘‘ABB Lummus Crest-technology’’, the acceptable SOx con- hindered amines with CO2, higher loadings (1 mol/mol amine)
centration is maximum 50 ppm. However, the application of than by MEA (0.5 mol/mol amine) can be reached. Furthermore,
MEA-based processes is limited due to the corrosive salts formed the energy required for solvent regeneration with hindered amines
by MEA and SOx present in process streams. Other disadvantages is much lower than, e.g., with MEA. Therefore, hindered amines can
are relatively high enthalpies of reaction and evaporation. This re- reduce both capital and utility costs in the separation of carbon
sults in high energy requirements for the recovery of the solvent. dioxide. Kansai Electric Power Company and Mitsubishi Heavy
The Dow Chemical Company developed MDEA-based solvents Industries have developed and have been using a hindered amine
offered under the trade name UCARSOL. These solvents can be called KS1. It is now used at a fertiliser plant in Malaysia [25]. An-
applied for CO2 removal from ammonia syngas as well as for CO2 other hindered amine is 2-amino-1-methyl-1-propanol (AMP)
and H2S removal from natural gas. If required, selective H2S [20].
removal can be accomplished by a solvent from the UCARSOL CO2 removal is also carried out by hot potassium carbonate that
family [30]. This solvent is applied in the Amine Guard FS process is used in many plants (e.g. ammonia plants, natural gas treating).
for CO2 removal from ammonia syngas. There are more than 500 The most often applied technology is UOP’s Benfield process with
units worldwide using this technology in treating natural gas, more than 700 units worldwide [28]. In this process, diethanola-
ammonia syngas and hydrogen streams. mine (DEA) is used as an activator. The Catacarb process (Eickmey-
Table 9
Reactive absorption processes for the capturing of H2S (adapted from [28]).

Lurgi tail-gas treatment process (LTGT) Lurgi Oel-Gas-Chemie MDEA Six LTGT units for processing Claus tail gases in operation or under
GmbH design
Fluor hydrogenation/amine Claus tail gas treating Fluor Enterprises, Inc. – Three plants engineered or constructed
process
HCR (High Claus Ratio) SIIRTEC NIGI – First commercial plant started in November 1988
Since then 10 plants under construction
er and Associates) also uses hot potassium carbonate, which is

applied for the removing of CO2 from ethylene oxide recycle gas. CO2 content, ppm (mL/m³)
Exxon Flexsorb HP process uses a hindered amine activator, 10 100 1000 10000
whereas the Giammarco-Vetrocoke uses an organic activator for 30
the removal of CO2 [31]. In Ref. [32], it is reported that the ADIP Physical
Rectisol Sulfinol and
and ADIP-X process can be applied for the bulk and deep removal 10 ZnO Purisol MDEA
chemical
Partial pressure of H2S/COS and

of CO2 from gas streams. Spasolv DEA
solvents
Rectisol Selexol
2.1.1.2. H2S removal. Hydrogen sulphide is a colourless, toxic gas,

that can be found in biogas, petroleum and natural gas [33]. Gases
CO2 in gas feed , bar

containing H2S are called sour gases [1], while the removal of H2S 1
Chemical solvents
from the gas is called sweetening. Most often, hydrogen sulphide
must be removed because of its high corrosivity and due to envi- Sulfinol Hot pot
Amisol
Benfield- Benfield
ronmental reasons [31,32]. Hi-pure DGA
Coke oven gas from coke plants also contains H2S. For the 0,1
reduction of SO2 emissions and to fulfil technological and safety
requirements, the desulphurisation of coke oven gas is necessary.
ZnO
The H2S content of coke oven gas is limited to 500 mg=m3n [34].
Another example for H2S removal can be found in the Claus pro- Molecular sieves
cess that produces elemental sulphur from H2S containing gases. 0,01
The tail gas leaving this process consists of sulphur vapour and 0,1 1 5 10 100 1000
SO2, which is treated using the so-called tail gas treatment (TGT) Sulfur in product gas, ppm (mL/m³)
process. The product of this process is used as a feed stream in
Fig. 5. Selection of appropriate gas purification process for simultaneous H2S/COS
the Claus process. The TGT process consists of a reaction step form- and CO2 removal (adapted from [21]).
ing H2S from the mentioned tail gas components and an amine-
based absorption step to bring the H2S concentration to the value
that is required for the Claus process [33]. The Shell’s SCOT process In gas liquefaction processes, acid gas treatment includes the
is a TGT process that is often applied. removal of CO2 and sulphur compounds (H2S, COS and mercap-
H2S absorption can also be used in hydrodesulphurisation. In tans). This is applied in both LNG (liquefied natural gas) [33] and
this process, sulphur compounds are removed from mineral oil in LPG (liquefied petroleum gas) production [40].
products by hydrogenation. Table 9 shows suitable processes for As mentioned earlier, for choosing the appropriate absorption
selective H2S removal. The listed processes can recover sulphur processes for a given separation problem, the knowledge of the
from a gas stream up to 99%. The Lurgi Tail-Gas Treatment (LTGT) gas inlet as well as outlet concentrations is necessary. This is even
process is a wet-scrubbing process for the treatment of the tail gas more complex, when more than one component is to be removed.
from the Claus process. Nearly six LTGT units are in operation. The For the selection of the appropriate removal process for CO2 and
Fluor hydrogenation process and the High Claus Ratio process are sulphur containing gases, a schematic representation is given in
also applied for Claus tail gas treatment for nearly complete sul- [21] (see Fig. 5).
phur recovery [28]. Table 10 contains above mentioned processes for the removal of
CO2 and H2S containing gases. MEA, MDEA, DEA and DIPA are the
2.1.1.3. Removal of CO2–H2S mixtures and other impurities. Together most common amines for simultaneous CO2 and H2S removal,
with CO2 and H2S, raw gases often contain other impurities, e.g. due to their low cost, high reactivity and easy regeneration. The
mercury, COS, CS2 and organic sulphur compounds. For many disadvantages, e.g. corrosiveness, can be overcome by the addition
industrial applications, it is necessary to remove both CO2 and of corrosion inhibitors [1].
H2S and possibly other undesirable compounds for economic and The most widely used technologies for simultaneous CO2 and
ecological reasons [35]. Natural gases, refinery gases and synthesis H2S removal are the Benfield process based on hot potassium car-
gases contain high amounts of CO2 and H2S [32,36–38]. A high CO2 bonate (over 700 units worldwide), the Amine Guard FS process
content in natural gas reduces the heating value of the gas. There- applying the MDEA-based solvent UCARSOL (500 units) and the
fore, CO2 has to be removed from natural gas for increasing its ADIP process using DIPA or MDEA (over 400 units). The aMDEA
quality. H2S must be removed, because both this component and process, developed and licensed by BASF, is one of the few technol-
the products of its reaction are highly corrosive [15]. Levels of less ogies in which additional mercaptan removal is possible.
than 1% for CO2 and 4 ppm for H2S must be achieved for preventing
corrosion of the equipment and to fulfil fuel gas requirements
[36,39]. Syngas contains acidic compounds, such as H2S, COS and 2.1.2. Research activities
CO2. The aqueous solutions of these compounds are corrosive Current research activities concerning RA for the removal of CO2
and also must be removed for the avoidance of corrosion of process and/or H2S containing gases are mostly addressed to carbon cap-
equipment [15]. ture and storage (CCS). When integrating amine scrubbers into a
Table 10
Reactive absorption processes for the capturing of CO2/H2S and other components (adapted from [28]).

Resulf CB&I TPA MDEA or formulated MDEA 45 Resulf units
3 Resulf-10 units
2 Resulf-MM units
Purification of sulphur recovery unit (SRU) tail gas for incineration
ADIP Shell Global Solutions DIPA or MDEA 400+ ADIP units in operation or under construction
International B.V. Removal from natural gas, refinery gases and synthesis gases
Removal of H2S, CO2, COS from liquefied petroleum gas or natural gas
liquids
ADIP-X Shell Global Solutions MDEA + additive Applied in one natural gas application
International B.V. Removes products from natural gas, refinery gas and synthesis gas, H2S can
be reduced to low-sulphur levels
Advanced amines Prosernat-IFP Group High load DEA, selective MDEA, 120+ units
Technologies activated MDEA Amine based process to sweeten natural gases
Cover all types of acid gas removal applications
aMDEA process BASF AG MDEA 200+ plants operating
30+ under design or construction, mostly treating synthesis gas, natural
gas and hydrogen streams
Amine Guard FS UOP LLC Ucarsol (MDEA-based solvent) 500+ units worldwide
Mostly treating natural gas, ammonia syngas and hydrogen streams
Benfield UOP LLC Hot potassium carbonate 700+ units worldwide
65+ treat natural gas
200+ treat ammonia syngas
110 in hydrogen plants
Other applications: in SNG, partial oxidation, coal gasification and petro-
chemical applications
Fluor improved Fluor Enterprises, Inc. DGA 55+ Econamine plants
Econamine 7 improved Econamine plants
power plant, the energy requirements will increase enormously can be prepared from renewable resources. It was found, that the
[17]. However, Rochelle [41] claims that amine scrubbing will CO2 absorption rate was enhanced, when even a small amount of
probably be the dominant technology for CO2 capture from coal- EEA was added to an aqueous DEEA solution. Further, they studied
fired power plants in 2030. Hence, there is a huge potential for the kinetics of the reaction of CO2 with N-methylmonoethanol-
optimisation which will require significant research work. amine (MMEA) and N,N-dimethylethanolamine (DMEA) [49] and
acceleration of the CO2 reaction with DEEA in aqueous solutions
2.1.2.1. Improvement of solvents. The main room for improvement by PZ [50]. It was found that the CO2 absorption rate could be sub-
of the industrially used processes are related to the solvents. stantially enhanced by adding just a small amount of PZ.
According to Davidson [42] and Wang et al. [43], the ideal chemical Solvents containing diamines have a good potential for CO2 cap-
solvent possesses a high reactivity with respect to CO2, low regen- ture, because of the presence of one or more primary or secondary
eration cost requirements, high absorption capacity, high thermal amino groups. The kinetics of CO2 reaction with diamine N-(2-ami-
stability and reduced thermal degradation, a low environmental noethyl)ethanolamine (AEEA) was investigated by Bindwal et al.
impact and low costs. According to Veawab et al. [44], 70–80% of [51].
the operating costs arise due to the regeneration of the solvent. Parallel to its use as an amine blend activator, concentrated PZ
Additionally, the most commonly used, amine based, solvent is also applied as a solvent; besides, PZ-promoted potassium car-
MEA has several disadvantages like a low carbon dioxide loading bonate (K2CO3) solutions are also in use. These applications repre-
capacity, solvent degradation in case that SO2 and O2 are present sent separate research areas. For instance, Freeman et al. [52] made
in the flue gas, high equipment corrosion rate and high energy con- experiments to measure the oxidative and thermal degradation,
sumption [43]. the CO2 solubility, the CO2 mass transfer rates in PZ and the vola-
Lepaumier et al. [45,46] studied the degradation in the presence tility of aqueous PZ solutions. In addition, the energy requirement
of CO2 and oxidative degradation of several amines to find new was estimated using the simulation tool Aspen PlusÒ. The experi-
promising solvents. It can be seen that some amines are more sta- ments revealed that oxidative degradation of PZ is slower than that
ble than MEA. For example, MDEA (N-methyldiethanolamine), of MEA. Thermal degradation is insignificant for temperatures of
AMP (2-amino-2-methylpropan-1-ol), DMP (N,N0 -dimethylpipera- up to 150 °C. Therefore, high-pressure strippers are allowed to im-
zine) and TMEDA (N,N,N0 ,N0 -tetramethylethylendiamine) are more prove the energy performance. The mass transfer measurements
stable in the presence of CO2; furthermore, DMEA (N,N-dimethy- have shown that the rate of absorption into PZ is higher than that
lethanolamine) and AMP reveal less oxidative degradation. into MEA. The simulations of a simple stripper section indicated
Different types of amines and their mixtures were compared that the equivalent work required for the stripping of a PZ solution
experimentally and numerically by Dubois and Thomas [47]. The is 10–20% lower than for MEA. Furthermore, Bishnoi and Rochelle
CO2 absorption efficiencies increase when mixing different types [53] made experiments to measure reaction kinetics, mass transfer
of amines: tertiary or sterically hindered amines with an activator and solubility, Chen and Rochelle [54] studied derivatives of aque-
(e.g. piperazine (PZ)) or a primary amine (e.g. MEA). For example, ous piperazine solutions, and Plaza and Rochelle [55] demon-
the absorption efficiency of an aqueous mixture of MDEA (30%) strated the benefits of PZ in a 1-month pilot plant campaign.
and PZ (12.5%) is about 15 times higher than the absorption effi- Oexmann et al. [56] analysed the post-combustion CO2-capture
ciency of a 30% aqueous MDEA solution [47]. process using a solution of aqueous K2CO3 promoted by PZ with
Vaidya and Kenig [48] studied the reaction kinetics of aqueous the simulation tool ASPEN PlusÒ (equilibrium stage model). It
solutions containing N-ethylethanolamine (EEA) and N,N-diethy- was shown that the use of a mixture of 2.5 m K2CO3 and 2.5 m
lethanolamine (DEEA), which are potentially attractive, as they PZ may significantly reduce the required heat duty for solvent
regeneration in comparison to MEA. When attaining a CO2-capture Further studies on process integration of coal-fired power-
rate of 90%, the heat duty for this process is as low as 2.4 GJ/t CO2 plants were done by Stankewitz and Fahlenkamp [65] and Luc-
compared to 3.3 GJ/t CO2 (for MEA). By integrating this CO2-cap- quiaud and Gibbins [66]. In [65], heat sources and sinks were quan-
ture and a CO2-compression process into a coal-fired power plant, tified with the help of simulations (Aspen Custom ModelerÒ from
the overall energy requirement will reduce from 0.342 kW h el/ AspenTech and EBSILON ProfessionalÒ from STEAG Energy Ser-
kg CO2 to 0.288 kW h el/kg CO2. In contrast to this preliminary vices). Recovering of waste heat can significantly reduce the loss
evaluations Oexmann and Kather [57] found that the K2CO3 proof efficiency. Lucquiaud and Gibbins [66] proposed a method to
cess is better in terms of heat duty, but, considering higher opera- estimate electrical output penalty (EOP) values for CO2 capture
tional costs, due to the high price of PZ, the overall costs for CO2 and compression systems that are integrated within the power
removal are 18% higher than for MEA. More information on this plant. They designed a tool to assess solvent-based capture tech-
technology can be found in Cullinane and Rochelle [58]. nology integrated into the power cycle of new-build coal-fired
Further research is done on ammonia. The chilled ammonia pro- plants. The integration of supercritical coal-fired power plants with
cess was already patented in 2006 by Eli Gal and is still under re- high temperature (580 °C) and pressure (23 MPa) were studied by
search. Darde et al. [59] performed thermodynamic analysis of the Romeo et al. [67,68] and Aroonwilas and Veawab [69].
system. The study showed that the chilled ammonia process al-
lowed for a significant reduction of the energy consumption in 2.1.2.3. Cement industry. Carbon capture plays also an important
the desorber compared to the energy consumption of the process role in cement industry. Contrary to common flue gases, here,
based on amines. the gases contain relatively large amount of CO2. A recent theoret-
Amino acid salts are of great interest for CO2 capture. They are ical study in [70] considers a process flow diagram for the integra-
present in the environment in a natural way and, therefore, envi- tion of the carbon capture process in the cement production plant.
ronmentally friendly. In addition, they have the same functional In the absorption step, aqueous MEA is applied. It could be shown,
groups as alkanolamines, and their reactivity and CO2 absorption that each tonne CO2 that can be avoided in a 1 Mt/y European ce-
capacity are comparable to aqueous alkanolamines [60]. A study ment plant would cost 107€. The corresponding cost for a 3 Mt/y
on amino acid salt systems is published in [60]. Potassium sarco- Asian plant would be 59€. Furthermore, these costs can be reduced
sine showed a better absorption rate than MEA, but the energy if other solvents are applied and the process is integrated into the
requirement for regeneration was higher. Aronu et al. [61] studied adjacent power plants.
the performance of amino acid salts formed from the neutralisa-
tion by an organic base. It was shown that these amino acid salts 2.2. NOx removal
had a better CO2 absorption potential than amino acid salts formed
from neutralisation by an inorganic base. Vaidya et al. [62] investi- Nitrogen oxides are gases with high reactivity containing vary-
gated the kinetics of carbon dioxide removal by aqueous alkaline ing amounts of nitrogen and oxygen. Most of the NOx emissions are
amino acid salts and found that the CO2 absorption rate was en- in the form of NO that is then oxidised to NO2 in the atmosphere.
hanced, when even a small amount of potassium glycinate was All combustion processes are sources of NOx. During combustion,
added to an aqueous DEEA solution. some N2 is converted to NO at high temperatures and in the pres-
According to Wang et al. [43], another promising solvent is a ence of oxygen; the higher the combustion temperature is, the
mixture of alkanolamines and enzymes. The latter can catalyse more NOx is produced. Emissions of NOx remained more or less
very fast reactions at ambient conditions requiring only small sol- constant in the past decades, with the major sources being the
vent amounts. combustion in industrial facilities, electric power generation,
A new interesting possibility is the use of demixing solvents as non-road engines and on-road vehicles. Fig. 6 shows the primary
in the DMXTM process proposed by IFP Energies Nouvelles [63]. In sources of nitrogen oxides. Remarkable, the transportation sector
this process, a liquid solvent is used that splits onto two separate produces the highest amount of NOx (61%), while the total emis-
liquid phases after the heat exchanger between absorber and strip- sion of industrial activities is about 32%, according to Chung
per, thus building a water-rich phase, with a very high carbon diox- et al. [71].
ide loading, and an amine-rich phase. Consequently, the amine- The applied NOx removal processes can be classified as dry and
rich phase does not need to be sent to the stripper and the energy wet processes. Dry processes are catalytic or non-catalytic denitri-
requirements for solvent regeneration is lowered. Process simula- fication processes, while the scrubbing of nitrogen oxides by water
tions showed that the reboiler energy can be reduced from or aqueous nitric acid belongs to the wet methods [71,72]. The wet
3.7 GJ/ton CO2 typical for a standard MEA process down to 2.3 GJ/ methods belong to the class of RA processes [73].
ton CO2 for the DMXTM process.
2.1.2.2. Improved integration. Capturing CO2 from flue gas streams The industrial NOx treatment is carried out by capturing NOx in
requires cost-effective capture technology and energy-efficient water or aqueous nitric acid. In addition to gas cleaning, the same
integration of the capture unit into the power plant. According to RA process is also used for the manufacturing of nitric acid. The lat-
Pfaff et al. [64], currently such processes are characterised by large ter technology is addressed in Section 2.3. Absorption of nitrous
heat requirements for the regeneration of the solvent and auxiliary
power for pumps, blowers and the final compression of the sepa-
rated CO2. Due to these energy demands, the net efficiency of the
overall power plant process decreases to about 9–13%.
Pfaff et al. [64] analysed the integration of a CO2 capture process
into a greenfield hard-coal-fired power plant using the simulation
software EBSILON ProfessionalÒ from STEAG Energy Services. This
study shows that the integration of waste heat from the CO2 cap-
ture unit into the water-steam-cycle of the power plant will min-
imise the overall net efficiency loss. More specifically, the waste
heat from the desorber overhead condenser and from the CO2 com-
pressor can be used. Fig. 6. Primary sources of NOx emission in global scenario (adapted from [71]).
gases is a highly complex process, due to the interaction of several alternative aid to reduce the NOx level is to cool down the
components and chemical reactions in both the liquid and gas nitrous gas, so that more N2O4 is formed than NO2. The N2O4
phases. During the absorption of nitrogen oxides, the following is then scrubbed with nitric acid at 0 °C; in this way it can be
reactions may occur [73,74]: stripped out and converted to nitric acid (N2O4 + ½O2 + H2O ?
2HNO3) in an absorption reactor operated in the range of 60–
2NO þ O2 ! 2NO2 ðgas phaseÞ ð11Þ
80 °C. This technique is actually similar to that in concentrated
nitric acid production. However, the method is more suitable
2NO2 ! N2 O4 ðgas phaseÞ ð12Þ
for investment in a new plant than for the expansion/upgrading
of an existing plant [78].
NO þ NO2 ! N2 O3 ðgas phaseÞ ð13Þ
NO þ NO2 þ H2 O ! 2HNO2 ðgas phaseÞ ð14Þ Chemical scrubbing is a generic technology by which several
contaminants are removed from the gas stream by means of a
3NO2 þ H2 O ! 2HNO3 þ NO ðgas phaseÞ ð15Þ scrubbing liquid reacting with them. The chemical scrubbing of
NOx out of tail gas is covered in a number of patents and scientific
2NO2 þ H2 O ! HNO3 þ HNO2 ðliquid phaseÞ ð16Þ publications [78]. It is worth noting that all the scrubbing methods
have problems related to the scrub liquor: e.g. cost, regeneration,
N2 O3 þ H2 O ! 2HNO2 ðliquid phaseÞ ð17Þ quantity, and environmental impact. These problems are always
easier to manage, if the NOx removal is part of an integrated chem-
N2 O4 þ H2 O ! HNO3 þ HNO2 ðliquid phaseÞ ð18Þ ical plant, what is typically the case in practice. The following scrub
liquors have been proposed so far [78]: aqueous suspension of
3HNO2 ! HNO3 þ H2 O þ 2NO ðliquid phaseÞ ð19Þ magnesium carbonate and magnesium hydroxide [79], solution
of vanadium in nitric acid [78], ammonium sulphide and bisul-
Note that absorption of NOx can further be enhanced by the phide [80], milk of lime [81], ammonia [78], hydrogen peroxide
addition of hydrogen peroxide (H2O2), according to the following [82], and urea [78].
reaction mechanism: At industrial scale, ammonia scrubbing is used in the US by
2NOðlÞ þ 3H2 O2 ðlÞ ! 2HNO3 ðlÞ þ 2H2 OðlÞ ð20Þ Goodpasture (Texas) who has developed a safe process based on
scrubbing of the tail gas with ammonium nitrate solution. The ni-
HNO2 ðlÞ þ H2 O2 ðlÞ ! HNO3 ðlÞ þ H2 OðlÞ ð21Þ trite formation is suppressed by aeration and the presence of free
acid. The tail gas is then led through a scrub liquor containing
Hydrogen peroxide reacts with HNO2 and NO from the liquid ammonia (pH 7.5–8.5). The scrubbing product is a 30–50% ammo-
phase, and, as a consequence, it enhances the formation of nitric nium nitrate solution, while the tail gas has a residual level of
acid [75]. The NOx gas is charged with a certain amount of H2O2, 200 ppm NOx [78].
and the gas mixture reacts on a solid catalyst to hydrogen nitrate The hydrogen peroxide scrubbing method is based on the fol-
that is either withdrawn for further use or converted into nitric lowing overall reactions:
acid by condensation or by water scrubbing. This process, patented
by Degussa (now Evonik Industries), allows the removal of NOx NO þ NO2 þ 2H2 O2 ! 2HNO3 þ H2 O ð22Þ
(even at low concentrations, below 2000 ppm) with high efficien-
cies above 90% [76], depending on the NO2 concentration in total 2NO2 þ H2 O2 ! 2HNO3 ð23Þ
NOx – this aspect being discussed in [77]. Note that flue gases The reactions are carried out on sieve trays or in packed towers
and tail gases may have widely varying NO2/NOx-ratios and corre- with recirculation of the hydrogen peroxide solution. The benefit of
spondingly varying abatement efficiencies. this scrubbing process is that the reaction time is very fast. How-
Several basic approaches are typically used to reduce the tail- ever, the drawback is that the hydrogen peroxide scrub liquor is
gas NOx levels: improved RA, chemical scrubbing, adsorption and rather expensive.
catalytic tail-gas reduction [78]. Intense research and development Another process was developed by Norsk Hydro in Norway,
effort was invested in these methods during the past decades. In with the advantage that urea is readily available and quite inex-
what follows, we focus only on the methods related to RA. pensive [78]. The process is carried out at 50 °C using a solution
The efficiency of absorption depends mainly on the operating containing 20% urea and 10% free nitric acid for scrubbing tail
pressure, temperature and the number of stages. The temperature gas to remove NOx. By doing so, both nitrogen oxides are selec-
of the gas between stages is especially important, because it gov- tively reduced to N2 by urea that decomposes to yield nitrogen
erns the progress of oxidation, the limiting stage for the entire and carbon dioxide. The resulting stack gas trail is colourless and
absorption process [78]. In existing plants, the following improve- heavily loaded with water vapour.
ment options can be used:
2.2.2. Research activities
Expand the absorption volume: The advantage of this option is The latest research activities were dedicated to aqueous alka-
that it does not require any new technology. The absorption vol- line solutions, the main reason being the possibility to produce
ume is added in the form of a second tower – new absorption valuable substances, such as nitric acid and its salts – nitrates
tower designs with very few stages have been devised. How- and nitrites [83]. Pradhan and Joshi [84] used an aqueous NaOH
ever, large additional volumes only result in small reductions solution as a solvent in a tray column, in which sodium nitrite is
of tail-gas NOx levels, since the oxidation of NO to NO2 proceeds produced selectively. This process can also be improved by the
very slowly when the NOx concentration is low. The drawback is addition of H2O2 and the use of structured packing as column inter-
that added absorption volume in stainless steel is expensive nals [75]. Other alkaline solutions were analysed and a model was
[78]. developed by Patwardhan and Joshi [83], who incorporated the
Lower the absorption temperature: The use of cooling energy in HNO2 decomposition, as well as the neutralisation by alkali. This
the absorption process significantly accelerates the oxidation led to a unified model for NOx absorption, which can be used for
of NO to NO2. The disadvantage here is that the required refrig- predicting process rates and selectivity, for various gas composi-
eration equipment and piping means further investment. An tions and liquid-phase pH-values [83].
BioDeNOx is a novel process – developed and tested at Wagen- 1. Direct processes to produce NO by a reaction of atmospheric
ingen University and TU Delft [85,86] – for the removal of NOx from nitrogen with oxygen at temperatures over 2000 °C. The direct
industrial flue gas, in which the reactive absorption of NO in aque- combustion of air in an electric arc – developed by Birkeland
ous solutions of Fe-II(EDTA) plays a key role resulting in the forma- and Eyde (see [78]) – was abandoned due to its poor energy effi-
tion of a nitrosyl complex Fe-II(EDTA)(NO). Basically, the BioDeNOx ciency. Other direct processes developed later – such as thermal
process combines the principles of wet absorption of NO into an NO synthesis with fossil fuels or in nuclear reactors – did not
aqueous Fe-II(EDTA) solution with biological regeneration of the gain widespread acceptance.
scrubber liquor in a bioreactor. Note that the oxygen present in 2. Production of ammonia by hydrolysis of calcium cyanamide
the flue gas will also be absorbed and oxidise Fe-II(EDTA). This is under pressure – a process of only transient value, until the
in fact an undesired reaction, since the resulting Fe-III(EDTA) does Haber–Bosch process became available.
not react with NO. 3. Production of ammonia from nitrogen and hydrogen, by the
Winkelman et al. [87] developed a rate-based model for the Haber–Bosch process – a process used nowadays to produce
simultaneous RA of NO and O2 in aqueous Fe-II(EDTA) solutions ammonia feedstock for nitric acid production.
in a counter-current packed column, and evaluated the effect of
process conditions on the absorber performance (e.g. NO removal The crucial step in the nitric acid production is the catalytic
efficiency and selectivity). The absorber performance was particu- combustion of ammonia, a process developed by Ostwald and
larly dependent on the operating temperature, while lower tem- implemented at industrial scale in 1906 at Gerthe in Germany
peratures are in favour of both the NO removal efficiency and [78]. The Ostwald process involves three key chemical steps:
selectivity [87]. Notably, over-designing the absorber may result
in decreasing performance, because, at certain process conditions, Catalytic oxidation of ammonia with atmospheric oxygen to
desorption of NO may occur resulting in lower NO removal effi- yield nitrogen monoxide.
ciencies at increasing column lengths. Oxidation of NO product to nitrogen dioxide or dinitrogen
More recently, Kenig and Seferlis [88] also demonstrated the tetroxide.
ability of using rate-based models in a compact form – by using Absorption of the nitrogen oxides to yield nitric acid.
the orthogonal collocation on finite elements (OCFE) – to accu-
rately predict the steady-state and dynamic behaviour of industrial The following exothermic reactions occur in the above men-
and experimental columns for NOx absorption. OCFE formulation tioned process steps [91]:
reduces the overall size (total number of equations) of the RA pro-
cess model, while preserving its structure and accuracy. A compre-
4NH3 ðgÞ þ 5O2 ðgÞ ! 4NO þ 6H2 OðgÞ DHR ¼ 226 kJ=mol ð24Þ
hensive description of the OCFE method is given by Dalaouti and
Seferlis [89,90]. 2NOðgÞ þ O2 ðgÞ ! 2NO2 ðgÞ DHR ¼ 114 kJ=mol ð25Þ
3NO2 ðgÞ þ H2 OðlÞ ! 2HNO3 ðaqÞ þ NOðgÞ

2.3. Nitric acid production
DHR ¼ 117 kJ=mol ð26Þ
Nitric acid – also known as aqua fortis or azotic acid – is an inor- 4NO2 ðgÞ þ 2H2 OðlÞ þ O2 ðgÞ ! 4HNO3 ðaqÞ DHR ¼ 63 kJ=mol
ganic acid of major industrial importance. Due to its properties as a ðonly when air is presentÞ ð27Þ
very strong acid, a powerful nitration and oxidising agent, nitric
Note that the oxidation of nitrogen monoxide is a rare example
acid is crucial in the production of many chemicals, e.g., pharma-
of a homogeneous third-order gas-phase reaction, while the
ceuticals, dyes, synthetic fibres, insecticides, and fungicides [91].
absorption of NOx is a heterogeneous reaction [78]. The nitric acid
Remarkable, nitric acid is mostly used in the production of ammo-
production processes are characterised by the way in which the
nium nitrate for the fertiliser industry – about 70% of the global
three steps mentioned above are implemented. In single-pressure
production amounting 54.5 million tons in 2010 [92]. The world
processes, the ammonia combustion and NOx absorption take place
production of NH4NO3 is largely concentrated in two regions, the
at the same working pressure (in the range of 1–14 bar, cf. Ta-
former USSR (24.5%) and Western Europe (21.7%), although USA,
ble 11) – with very few plants currently employing only relatively
China and Central Europe are also large producers [93].
low pressure (1–2.2 bar) for both oxidation and absorption steps.
Nitrogen oxides (NOx) are formed not only as waste gases in
In dual-pressure (split-pressure) processes, the absorption
many industrial processes, but also during the oxidation of ammo-
pressure (6.5–13 bar) is higher than the oxidation pressure
nia in the nitric acid production process. From the eco-efficiency
(1–6.5 bar, Table 11). The modern plants feature oxidation at
viewpoint, it is beneficial to combine the removal of NOx from
4–6 bar and absorption at 9–14 bar, while older plants still
waste gases with the production of nitric acid by NOx absorption
employ atmospheric combustion and medium-pressure absorption
in water or diluted nitric acid. Overall, this is a very complex pro-
[95].
cess involving chemical reactions in both gas and liquid phase. A
Most new plants work with the dual pressure process – illus-
general approach to the description of such processes was gradu-
trated in Fig. 7 [95]. An air–NH3 mixture, with a composition ratio
ally developed in [73,74,88,94].
of 9:1 is catalytically converted mainly to NO that is afterwards
oxidised and reacts with residual O2 to form NO2 and NO2-dimer.
The mixture of NO2/dimer is introduced into the bottom of the
2.3.1. Industrial applications absorption tower, in counter-current with de-ionised process
Nitric acid is met in nature only in the form of nitrate salts, and water. Another air stream is introduced into the column to re-oxi-
sodium nitrate was used as feedstock when the large-scale produc- dise the NO that is formed in reaction. The nitric acid is withdrawn
tion of nitric acid started. Only in the beginning of the 20th cen- from the bottom of the column. Oxidation takes place in the free
tury, when the sodium nitrate reserves were considered to space between the trays, while absorption occurs on the trays –
approach exhaustion, other processes were developed to replace usually sieve or bubble cap trays [95].
nitrogen from nitrates with atmospheric nitrogen. The three tech- High-strength nitric acid (98–99%) is produced by dehydration
niques used industrially were [78]: followed by bleaching, condensation and absorption in a weak
Air Filtration Evaporation Ammonia
Air Filtration
Power compression
Heat Heating
Filtration
Mixing
Steam export
Catalytic
reactor
Superheated
steam
Boiled feed water Heat recovery Steam turbine
Cold tail gas Heat recovery

Hot tail gas Reducing
Cooler agent
Cooling water Condenser
NOx abatement
Power NOx compression Hot tail gas
Heat recovery
Cooling water Cooler
Condenser
Process water Absorption Expander

Cooling water
Atmosphere Power
Nitric acid
production
Fig. 7. Nitric acid production – dual pressure plant (adapted from [95]).
H2SO4
50-70% HNO3, NO2, O2 Cooling Water

HNO3
Condenser Air
Dehydrating Absorption
Bleacher O2, NO Column
Column
Strong
Nitric Acid
Weak
Nitric Acid
Fig. 8. Flow diagram of high-strength nitric acid production from weak nitric acid (adapted from [95]).
Table 11 production of nitric acid is dominated by five countries accounting

Pressures of single and dual pressure processes [95]. for 73.3% of total nitric acid production in 2010: Germany 17.7%,
Single pressure process (bar) Dual pressure process France 17.0%, Netherlands 16.4%, Belgium 12.0%, and United King-
Oxidation pressure 1–14 1–6.5 dom 10.2%.
Absorption pressure 1–14 6.5–13
2.3.2. Research activities
The current research activities are primarily driven by the main
nitric acid, while commercial grade nitric acid solutions (52% and pollution problem in the nitric acid manufacture, namely the abate-
68%) are produced via the Ostwald process [95]. Weak nitric acid ment of NOx in the tail gases. There are only few options to reduce
(30–70%) is produced by catalytic oxidation of ammonia, followed the emissions to acceptable levels: to capture the NOx and convert it
by condensation and absorption in water. In the high-strength ni- to additional nitric acid or nitrate–nitrite salts, or to render the NOx
tric acid process shown in Fig. 8, an acid concentration of 98–99% is harmless by converting it to non-polluting compounds. A large
obtained using extractive distillation. Weak nitric acid is intro- number of processes have been developed and patented to reduce
duced into a distillation column with a dehydrating agent (e.g. sul- the emissions, they can be classified into three main categories:
phuric acid 60%). Both acids are fed to the top of the column, at absorption, adsorption and catalytic reduction [93]. The absorption
atmospheric pressure, in counter-current to the ascending vapours. abatement deals with the optimisation of the existing absorption
The vapour leaving the column is concentrated nitric acid (99%) system, or modifications aimed at increasing the absorption capac-
that passes to a bleacher and then to a condenser. The concen- ity. Tail gases pass through an absorber containing either water or
trated nitric acid is obtained in the condenser, while the by-prod- an aqueous solution of ammonia, urea or NaOH. When water is
ucts (O2 and NO) are introduced into the absorption column that used, the resulting weak acid is recycled leading to slightly in-
produces weak nitric acid. creased nitric acid yields (1–3% higher). When other absorbents
The design of the nitric absorption columns requires the indi- are used, the recovered NOx is usually consumed in the production
vidual tailoring of each tray (typically bubble cap or sieve trays) of nitrogen solutions for fertiliser use. If NaOH is used, pure sodium
for its cooling requirements and the gas volume rates needed for nitrite and sodium nitrate may be recovered [93].
oxidation of the nitric oxide. A good summary of absorber design The need to make the nitric acid processes more efficient, while
aspects is available in the book of Keleti [96]. Capacities of around meeting the much stricter environmental regulations (e.g.
1800 t/d HNO3 were achieved in a single RA column of up to 6 m in 200 ppm in EU, or 1.5 kg NOx per metric ton of nitric acid in
diameter, 80 m high, and containing as many as 30–50 trays. For USA), led to new advances in understanding the absorption chem-
abatement reasons, single absorption columns reach tail gas NOx istry. One such development is the High Efficiency Absorption
compositions of about 200 ppm, although the economic optimum (HEA) technology developed by Rhône-Poulenc, which can reduce
for absorber efficiency would lead to higher tail gas NOx concentra- the size of an absorber column by up to 35%. HEA is applicable
tions (1500–2500 ppm). Various methods are used to reduce tail when the gas-phase NOx concentration is low (<8000 ppm), and
gas NOx concentrations to an acceptable level for discharge to the the rate-limiting step for nitric acid formation is typically the
atmosphere (200–230 ppm), the most commonly employed being gas-phase oxidation of NO. By directly oxidising nitrous acid in
the extended absorption and (non-)selective catalytic reduction the liquid phase to nitric acid, the decomposition of nitrous acid
(SCR and NSCR). Extended absorption uses an additional column is avoided and the large oxidation volumes for NO2 regeneration
for oxidation and reaction of nitrogen oxides with water to form from NO are greatly reduced [91].
acid. Relatively few trays are required, but large oxidation volumes Much effort has been put into the development of advanced
– often employing refrigeration to promote the oxidation and to rate-based models of NOx absorption. Here, bulk reactions and film
minimise the column size. This method is most effective for high reactions have to be considered in both phases. A comprehensive
pressure (HP) absorption in which abatement to less than analysis of such models including their implementation in Aspen
200 ppm NOx can be achieved in a single HP column [91]. Custom Modeller (AspenTech) and validation by comparison with
Table 12 provides an overview of the main producers of nitric experimental data for a pilot scale packed column and an industrial
acid in the US and Western Europe – the capacities being given sieve tray column is given in [73,88,97].
in thousands of metric tons per year on a 100% HNO3 basis, and More recently, catalysts were developed for the selective reduc-
the market share as percent of the regional market [93]. Remark- tion of NOx to N2 at relatively low temperatures, using NH3 as
able, on a country-by-country basis, the Western European reducing agent. Although additional NH3 is consumed, this process
may provide control of emissions in an efficient way, due to low
overall costs [93].
Table 12
Main producers of nitric acid in the US and Europe.
2.4. Desulphurisation
Company and location Capacity (thousands of Regional market share
metric tons) (% in 2010)
Sulphur compounds (e.g. SOx) are produced in several industrial
CF Industries (incl. Terra) 2635 30.7 (US) processes, such as combustion of organic fuels or reforming of oil.
PCS Nitrogen 1565 18.2 (US)
In the following sections, various ‘‘Flue Gas Desulphurisation’’
LSB Industries 1240 14.5 (US)
Dyno Nobel, Inc. 655 7.6 (US) (FGD) processes are presented, and the current industrial and aca-
Invista Inc. 470 5.5 (US) demic research activities are summarised.
Yara Internat. (incl. 50% 6760 45.8 (West EU)
GrowHow UK)
BASF (incl. 50% Prod. Eng. 2500 16.9 (West EU)
Chim. Rhin)
There is a wide range of industrial processes for removal of sul-
Grande Paroisse (+Prod. 1290 8.7 (West EU) phuric oxides from gases. The applications can be classified into
Eng. Chim. Rhin) wet processes (limeston gypsum, sea-water washing, ammonia
Fertiberia S.I. (incl. Adubos 925 6.3 (West EU) scrubbing, Wellman-Lord), semi-dry (circulating fluidised bed,
du Portugal)
spray dry, duct spray dry) and dry processes (furnace sorbent injec-
OCI Nitrogen (formerly 755 5.1 (West EU)
DSM Agro B.V.) tion, sodium bicarbonate injection) [98,99]. Out of these processes,
only the wet processes are performed by RA.
Precipitator
Flue gas Flue
By-pass damper
Fly ash
Waste-water
ID Fan Hydrocyclones treatment
Booster fan Water discharge
Reheater
Absorber
Limestone Sludge
Limestone
store mills
Slurry
Air
tank
Gypsum
Fig. 9. Schematic of a limestone gypsum FGD process (adapted from [98]).
Flue
By-pass
damper
Flue gas
Inlet damper Outlet

damper
Booster fan
Absorber
Reheater
Sea water from
condenser
Packing
Oxidation air
Return to sea
Fig. 10. The seawater washing process (adapted from [98]).
The limestone gypsum process (see Fig. 9) is the most common Flue gas can be desulphurised using seawater that has a natural
FGD process, which is applied in different variants for over alkalinity. This is a relatively new process (see Fig. 10) and it is pro-
30 years. This process is well understood and used by many com- vided by two suppliers only, ABB and LLB. However it is expanding
panies. Most commonly an open spray tower is applied in which very quickly, due to major advantages. ABB has already built 21
the flue gas is flowing upwards. Marsulex, ABB, Lurgi Lentjes Bisc- plants [98]. Contrary to other FGD processes, no solid components
hoff (LLB), Babcock Borsig, Kawasaki and IHI operate and sell this are produced. Moreover, the plant design is relatively simple. How-
technology. Babcock and Wilcox (B&W) and Babcock Hitachi have ever, the technology is limited to coasted sites, due to the sea-
a very similar design. In this variant, a tray is located in the bottom water requirements.
of the gas treatment zone. Mitsubishi Heavy Industries (MHI) uses The ammonia scrubbing technology (see Fig. 11) is similar to
a different design, without an open spray tower. In this case, a layer the limestone–gypsum process. Here, ammonia is used as the
of packing is used for an effective gas/liquid surface [98]. absorbent and reacts with SO2. As a result, ammonium sulphate
Precipitator
Flue
Flue gas
By-pass damper
Fly ash
ID Fan
Booster fan Ammonia

Reheater
storage tank
Absorber
Purge Water
Pre-scrubber
Hydrocyclone
Centrifuge
Compactor Air
Bleed
Dryer
Bleed
Fig. 11. The ammonia scrubbing process (adapted from [98]).
Precipitator
Flue gas Flue
By-pass damper Condenser

Fly ash
ID Fan
Booster fan
Reheater
Absorber
Sodium carbonate /
hydroxide
Blowdown
Water Sulphate
EDTA solids
Sodium carbonate or
hydroxide make-up Regenerated liquor
Tank Tank
Fig. 12. The Wellman-Lord process (adapted from [98]).
is produced that can be used, for instance, in the fertiliser industry logical explanation for such three-phase systems is given else-
[98]. This technology has been applied for over 50 years; currently where [100–104].
there are mainly two suppliers, LLB and Marsulex [98,99].
The Wellman-Lord process (see Fig. 12) uses an aqueous sodium
sulphite solution for the removal of SO2. In this process, valuable 2.4.2. Research activities
products can be obtained, for instance, elementary sulphur, sul- In the past decades, the research has focused on the wet pro-
phuric acid or liquid SO2. The Wellman-Lord process has more than cesses analysis. The limestone technology and the Wellman-Lord
40 implementations in Japan, USA and Germany. The main advan- process are well-known, and many applications are available.
tage of this process is that it does not need significant amounts of Newer technologies are the ammonia or seawater scrubbing, they
sorbent. Moreover, there is little waste produced during the pro- are still in the investigation stage.
cess [98]. A method presented by Ipek et al. [105] uses waste water
Note that some processes mentioned here use scrub liquors (e.g. ammonia for the absorption of SO2. In this study, the behaviour
milk of lime, limestone) with a suspension of solid particles, thus of SO2 is analysed experimentally. An investigation of the temper-
involving a quite complex gas–liquid–solid system. A phenomeno- ature impact on the SO2 removal can be found in [106].
Fig. 13. General diagram of sulphuric acid production (adapted from [112]).
Air Sulphur Feedwater
Main blower
Waste heat
Dryer Sulphur burner Stream
boiler
Inter- Oleum Converter bed 1

mediate absorber Heat
absorber exchanger
Converter bed 2
Heat
Heat
exchanger
exchanger
Converter bed 3
Heat Converter bed 4

exchanger
Water
Final
absorber Heat exchanger
H2SO4 96-98% Oleum 20-37%
Stack
Fig. 14. Sulphuric acid plant (double absorption) based on sulphur combustion (adapted from [112]).
Seawater absorption is analysed by several research groups. The of the total worldwide production. Sulphuric acid is mostly used as
solubility of SO2 in seawater was investigated in [107,108]. Mea- an ingredient, the fertiliser industry being its largest single con-
surements were carried out using a laboratory batch reactor at sumer, mostly for manufacturing phosphate fertilisers. Also the
1 bar and 298.15 K. In a later study, the impact of different pres- (petro-)chemical and the oil refining industries make use of sul-
sures and temperatures was investigated [109]. Rodriguez-Sevilla phuric acid, e.g., as an acidic dehydrating agent [111].
et al. [108,109] developed models for the determination of solubil-
ity and activity coefficients. Using Aspen PlusÒ, various influencing 2.5.1. Industrial applications
parameters, e.g., pH value or SO2 concentration in the feed stream, A general process diagram for the sulphuric acid production is
were analysed by Zhihua and Zhihong [110]. shown in Fig. 13, the main steps being the SO2 formation and con-
version to SO3, followed by the RA of SO3 to yield H2SO4. Note that,
2.5. Sulphuric acid production actually, there are various types of plants, but only two types pro-
duce sulphuric acid using RA methods [112]. The two major pro-
Sulphuric acid is the worldwide most produced chemical sub- cesses used for the sulphuric acid production are the lead
stance. The yearly production amounts up to 150 million tonnes. chamber process and the current contact process [113]. Remark-
North America, Japan and Western Europe produce nearly the half able, the contact process remained practically unchanged from
430°
Air
Steam
50° 610°
Furnace SO2 1 HX1

Boiler
450°
432°
2 539°
S (lq)
Air 420°
316°
3
50°
FEHE1 FEHE2
4
70°
434° 5 SO2
445°
242°
Reactor
H2SO4
65°
HX2
70° Abs1
HX3
H2SO4
65° 180° H2SO4
105°
Abs2
HX4
180°
H2SO4
88°
Fig. 15. Flowsheet of a modern sulphuric acid production plant [114].
Table 13
List of plants build after 1990 in Western Europe (adapted from [112]).
Location Process type Costs Company Capacity t H2SO4.d-1 Year Emission level
Hamburg, Germany Cu Smelter acid (5–8.4% SO2) 1M EUR Norddeutsche Affinerie 918t.d1 1991 < 800mg SO2.Nm3
Helsingborg, Sweden Sulphur burning (17.5% SO2) 36M EUR Kemira Kemi 1,000t.d1 1992 < 0.9kg SO2.t1 H2SO4
Harjavalta, Finland Copper and nickel based smelter acid (7–12% SO2) 33M EUR Outokumpu extension 2,430t.d1 1995 < 4,500t SO2.y1
Tessenderlo, Belgium Sulphur burner (11.5% SO2) n/a Tessenderlo Chemie 1,000t.d1 1992 300ppm SO2
Leuna, Germany Sulphur burner n/a Domo n/a 1996 99.9% conversion rate
Huelva, Spain Cu Smelter acid (5–10.2% SO2) 39M EUR Atlantic Copper 1,270t.d1 1996 >99.6%
Ludwigs-hafen, Germany Sulphur burner n/a BASF 900t.d1 n/a 0.65kg SO2.t1 H2SO4
Le Havre, France Sulphur burner (11.5% SO2) n/a Millennium 800t.d1 1992 2.6kg SO2.t1 H2SO4
Huelva, Spain n/a n/a Fertiberia 2,400t.d1 2000 n/a
Worms, Germany Spent acid regeneration; H2SO4 (NH4)2 SO4 53M EUR Rhöm GmbH 500t.d1 1994 n/a
its introduction in the late 1800s, until the seventies when the dou- main reaction in the absorber is highly exothermic, as shown by
ble absorption process was introduced in order to reduce the SOx Eq. 29:
emissions. The double absorption process is shown in Fig. 14, while
SO2 ðgÞ þ 1=2O2 ðgÞ ¢ SO3 ðgÞ DHR ¼ 96:2 kJ=mol ð28Þ
the process flowsheet is given in Fig. 15 [114]. However, the double
absorption part only reduced the SOx emissions – but it did not
change significantly the nature of the process or the equipment SO3 ðgÞ þ H2 OðlÞ ¢ H2 SO4 ðlÞ DHR ¼ 132 kJ=mol ð29Þ
used. Nowadays, all modern plants use the double absorption tech- The simplified flowsheet of such an industrial process consists
nique that can lead to SO3 conversion rates up to 99.85%, a signif- of a sulphur burner, a multi-pass converter (catalytic reactor),
icant improvement over single absorption processes (up to 98 % economisers, heat exchangers (HX), feed-effluent heat exchangers
only) [114]. Table 13 lists the new plants in Western Europe. (FEHE) and SO3 absorption towers (Abs) – as illustrated in Fig. 15
Rhone-Poulenc group has already built five plants producing [114]. SO2 conversion is further improved and tail gas emissions
3600 t sulphuric acid per day. are reduced by an intermediate SO3 absorption step (Abs1) in
Two fundamental steps are present in the production of SO3 which the production of sulphuric acid takes place. This absorption
and absorption of SO3. SO3 is produced by catalytical oxidation step is placed after the fourth bed of catalyst in order to change the
of sulphur dioxide (Eq. 28). Possible sources for producing sul- gas composition by removing most of the SO3 and thus shifting the
phur dioxide are sulphur burning, pyrites roasting, and smelting, conversion equilibrium to higher values. The absorption of SO3 is
sulphuric acid regeneration and some other processes [112]. The finalised in the second absorber (Abs2) which also purifies the
Bottom Top Bottom Top

455 455
Abs1_Temp_Gas Abs2_Temp_Gas
Abs1_Temp_Acid Abs2_Temp_Acid
435 435
Temperature / [K]
Temperature / [K]
415 415
395 395
375 375
355 355
335 335
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
Column length / [-] Column length / [-]
Bottom Top Bottom Top

0.1 0.1
Abs1_SO3 Abs2_SO3
Abs1_H2O Abs2_H2O
0.08 0.08
Molar fraction / [-]
Molar fraction / [-]
0.06 0.06
0.04 0.04
0.02 0.02
0 0
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
Column length / [-] Column length / [-]
Fig. 16. Temperature (above) and composition profiles (below) along the SO3 absorption columns.
outlet gas emissions. Fig. 16 shows typical temperature and com- ric acid has been produced for many decades at the highest world
position profiles along the two counter-currently operated absorb- production rate of any chemical.
ers [114]. SO3 concentration is reduced from 9.81% to 0.01% in the The main developments are in reducing (accidental) pollution.
intermediate absorber, and from 0.44% to only ppm levels in the fi- For example, there are improvements in the materials used in
nal step. Note that the dimensionless column length is in fact the the construction of the plants or their design, such as the use of
ratio between the real and the total absorber lengths. double shell vessels [112]. Currently, the need is to optimise sec-
The SO3 absorption towers are packed with ceramic saddles or tions in the different process stages depending on site require-
structured packing, for realising a maximum possible contact area, ments and local conditions [112,114]. Other developments are
and are typically carbon steel vessels lined with acid proof brick carried out with respect to energy recovery from primary energy
and mortar. As of early nineties, all metal towers – with no brick and demisters with very high efficiency.
lining – were built from high silicon stainless steel alloys, such as Some studies are related to the presence of NOx in acid plants
SX, Saramet, or ZeCor. Well-designed absorption columns operate that can appear through a number of mechanisms in the upstream
at very high absorption efficiencies (>99.5%), typically over 99.8% operations – mainly by oxidation of nitrogen from air (thermal
or even over 99.9%. Teflon or glass packed fibre bed mist elimina- NOx), as nitrogen containing impurities in the feed (feed NOx), or
tors are typically used in the interpass and final absorption towers, as the organic bound nitrogen present in some fuels during the
where high efficiency collection of the acid mist is critical [113]. combustion step (fuel NOx). Usually, nitrogen oxides have to be de-
stroyed and any remaining SO2 has to be stripped with air in order
to improve the product quality and avoid emission problems for
2.5.2. Research activities the customer [112]. Depending on the plant design, the concentra-
Sulphuric acid production is a mature industry and most of the tion of NOx in the feed gas is limited to 5–15 ppm in order to pro-
developments in production techniques were made in the last cen- duce an acid that would require no additional treatment.
tury. Hence, there seems to be little scope for improvement [112]. Wet sulphuric acid plants that directly convert hydrogen sul-
Not surprisingly, the research activities are very scarce, as sulphu- phide to sulphuric acid were also proposed as a way to reduce
the effort, energy and capital input [113]. More recently, Uhde [6] W.A. Peters, The efficiency and capacity of fractionating columns, Ind. Eng.
Chem. 14 (1922) 476–479.
GmbH presented the development of a new type of wet sulphuric
[7] T.H. Chilton, A.P. Colburn, Mass transfer (absorption) coefficients prediction
acid plant (Emission Free Sulphuric Acid Plant) covering the key from data on heat transfer and fluid friction, Ind. Eng. Chem. 26 (1934) 1183–
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emissions from coke oven plants in order to comply with legisla- Advances in Chemical Engineering, Academic Press, New York, 1981, pp. 1–
133.
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This article presents a comprehensive review on current appli-
[14] R. Zarzycki, A. Chacuk, Absorption: Fundamentals and Applications,
cations of reactive absorption (RA), covering both industrial pro- Pergamon Press, Oxford, 1993.
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Chemical Engineering Journal 213 (2012) 371–391

Contents lists available at SciVerse ScienceDirect

Chemical Engineering Journal

Reactive absorption in chemical process industry: A review on current activities

2.1.2.2. Improved integration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 379

1. Introduction Optimal design of RA processes requires adequate models cov-

Table 2 transfer occurs by steady-state molecular diffusion, whereas the

2. Reactive absorption applications

Fig. 1. Modelling approaches for reactive absorption (adapted from [3]).

Fig. 2. Molecule structure of amines.

Table 3 Protonation of alkanolamine : RNH2 þ Hþ $ RNHþ3 ð4Þ

Property MEA MDEA AEEA DETA AMP PZ

HCO3 þ OH $ CO2

Sulphur (wppm) 10–15 <1 <0.01–1

Fig. 4. CO2 origin and process ﬂow (adapted from [27]).

Process Licensor Solvent Installations

Process Licensor Solvent Installations

er and Associates) also uses hot potassium carbonate, which is

Partial pressure of H2S/COS and

2.1.1.2. H2S removal. Hydrogen sulphide is a colourless, toxic gas,

CO2 in gas feed , bar

Process Licensor Solvent Installations

3NO2 ðgÞ þ H2 OðlÞ ! 2HNO3 ðaqÞ þ NOðgÞ

Air Filtration Evaporation Ammonia

Cold tail gas Heat recovery

Power NOx compression Hot tail gas

Process water Absorption Expander

50-70% HNO3, NO2, O2 Cooling Water

Table 11 production of nitric acid is dominated by ﬁve countries accounting

Fig. 9. Schematic of a limestone gypsum FGD process (adapted from [98]).

Inlet damper Outlet

Fig. 10. The seawater washing process (adapted from [98]).

Booster fan Ammonia

Fig. 11. The ammonia scrubbing process (adapted from [98]).

By-pass damper Condenser

Fig. 12. The Wellman-Lord process (adapted from [98]).

Air Sulphur Feedwater

Inter- Oleum Converter bed 1

Heat Converter bed 4

H2SO4 96-98% Oleum 20-37%

Furnace SO2 1 HX1

Fig. 15. Flowsheet of a modern sulphuric acid production plant [114].

Bottom Top Bottom Top

Bottom Top Bottom Top

Molar fraction / [-]

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