Review Reactive Absorber

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Reactive absorption in chemical process industry: A review on current

activities
Article in Chemical Engineering Journal · December 2012

DOI: 10.1016/j.cej.2012.09.121
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Reactive absorption in chemical process industry: A review on current activities Ö. Yildirim et al.
1 Reactive absorption in chemical process industry:

2 A review on current activities
3
4 Ömer Yildirim1, Anton A. Kiss2, Nicole Hüser1, Katharina Leßmann1, Eugeny Y. Kenig1,*
1
5 University of Paderborn, Faculty of Mechanical Engineering, Chair of Fluid Process
6 Engineering, Pohlweg 55, D-33098 Paderborn
2
7 AkzoNobel Research, Development & Innovation, Process Technology ECG,
8 Zutphenseweg 10, 7418 AJ Deventer, The Netherlands. E-mail: Tony.Kiss@akzonobel.com
*
9 Corresponding author:
10 E-mail: eugeny.kenig@upb.de, Tel: +49 (0)5251 60-2408, Fax: +49 (0)5251 60-3522
11
12
13 KEYWORDS
14 Reactive absorption, gas treatment, CO2 / H2S / SOx / NOx removal, nitric acid, sulphuric
15 acid, industrial applications, research activities
16
17 ABSTRACT
18 Reactive absorption (RA) is a unit operation comprising the absorption of gases in liquid
19 solutions with simultaneous chemical reactions within a single apparatus. The role of RA as a
20 core environmental protection process has grown up significantly, and nowadays, this
21 technology belongs to the most important separation methods in the chemical process
22 industry, among others, for gas treatment and purification, removal of harmful substances, as
23 well as for the production of basic industrial chemicals, e.g. sulphuric acid and nitric acid.
24 This article provides a comprehensive review on current applications of reactive absorption,
25 covering both industrial processes and research activities.
26
1
1 1. Introduction
2 The current EU legislation imposes tighter restrictions aimed at reduction of the impact of
3 process industries on the environment. Consequently, substantial research work focuses on
4 developing sustainable processes allowing efficient handling of waste and production of
5 chemicals. Process industries intensively work with gas streams. Both natural and industrial
6 gases are processed, for instance in gasification of different fuel sources (coal, oil and natural
7 gas) or in diverse manufacturing processes of chemical industry.
8 Before using gas streams as chemical feedstock or releasing them into atmosphere, it is
9 usually necessary to change their composition by removing one or several components.
10 Basically, there are only five methods suitable for gaseous component capturing, namely,
11 absorption, adsorption, permeation through a membrane, chemical conversion to another
12 compound, and condensation [1]. From these operations, absorption is undoubtedly the most
13 important one. During absorption process, a gas to be treated is brought in contact with a
14 liquid stream and gas components are transferred into the liquid (solvent) phase in which they
15 are soluble. Important gas purification applications are listed in Table 1 [2].
16 Depending on the mechanism binding the gas compounds in solvent, one can distinguish
17 between physical and chemical (or reactive) absorption [3, 4]. Physical absorption of gas or
18 gas mixture components in a liquid solvent comprises the mass transfer at the gas-liquid
19 interface and mass transport within the phases. It depends on the gas solubility and the
20 operating conditions (e.g. pressure and temperature). A classic example of physical absorption
21 of a gas into a liquid is the absorption of carbon dioxide (CO2) into water (H2O) – usual in the
22 beverage industry. Chemical absorption, also known as reactive absorption (RA), is based on
23 a chemical reaction between the absorbed substances and the liquid phase. It largely depends
24 on the stoichiometry of the reaction, concentrations of the reactants and mass transfer rates.
25 This paper focuses on RA operations. They may be carried out in different units, with a wide
26 spectrum of phase flow types and interactions (see Table 2). In most cases, RA is carried out
27 in plate or packed columns. In plate columns, the phases flow counter-currently, whereas on
28 each given plate, a cross-flow is usually established. In packed columns, a liquid flows along
29 the packing surface, whereas a gas stream occupies the rest of the free volume. There exist
30 numerous plate and packing designs. In [1], guidelines are given how to select the most
31 appropriate internals for specific RA applications – depending on the Hatta number. RA may
32 also proceed in spray contactors, the simplest type of an absorption column. The desired
33 contact area is achieved by dispersing the fluid in small droplets.
2
1 Optimal design of RA processes requires adequate models covering mass and heat transfer,
2 reaction kinetics and column hydrodynamics. Different possibilities to model RA units are
3 presented by Figure 1. Large-scale applications are modelled by sub-dividing columns into
4 smaller segments, so-called stages. Each stage corresponds to a single tray or to a segment of
5 packed columns. The equilibrium stage model assumes that the gas and liquid streams leaving
6 a stage are in thermodynamic equilibrium. Due to its simplicity, this model (first published in
7 [5]) has been used in the past decades for a variety of applications, especially for non-reactive
8 systems. Yet, in real absorption processes, the thermodynamic equilibrium is usually not
9 attained within a stage. For this reason, tray efficiencies or HETP (Height Equivalent to a
10 Theoretical Plate) values [6] are introduced to build a link to real columns.
11 Absorption is usually dominated by the mass transport kinetics. Besides, in reactive
12 processes, chemical reactions must be taken into account. The equilibrium stage concept can
13 hardly address these issues reasonably. A more theoretically justified approach is based on
14 using HTU/NTU values [7]. The so-called HTU/NTU method allows determining the column
15 height as a product of two values, HTU (Height of a Transfer Unit) and NTU (Number of
16 Transfer Units). The HTU value depends on column load, column internals and empirical
17 mass transfer correlations, whereas the NTU value is obtained by integrating the inverse of
18 the driving force over the column height. In the HTU/NTU method, chemical reactions are
19 usually considered with the aid of enhancement factors [8-10]. The enhancement factors
20 depend on the type and order of the reaction and the mass transport model. The complexity of
21 the involved reaction scheme cannot be easily captured by a single parameter, and, thus, this
22 method often gives inaccurate results.
23 The most adequate and reliable method for the description of staged absorption units is the
24 rate-based approach, a method that takes the rates of multicomponent mass and heat transfer
25 and the chemical reaction into account directly [11]. The mass transfer between the phases
26 can be described by different theories, such as the two-film model or the penetration/ surface
27 renewal theory. The mostly used two-film model assumes that mass transfer resistance is
28 concentrated in thin films at the interface. In these films, mass transfer occurs by steady-state
29 molecular diffusion, whereas the bulk phases are ideally mixed. The multicomponent
30 diffusion in the films can be described by the Maxwell-Stefan equations. Chemical reactions
31 are considered by including reaction source terms in the balance equations for each bulk
32 phase and in the mass transport equation for the film. The necessary model parameters, e.g.
33 the film thicknesses, are determined using empirical correlations. For many applications, the
3
1 two-film model parameters can be found in the literature and, therefore, the method is often
2 preferred [12].
3 The present article gives a review on industrial applications of RA for gas treatment /
4 purification and for production of basic chemicals. Among the considered systems are those
5 containing CO2, H2S, NOx and SOx, as well as nitric and sulphuric acid. In addition, for each
6 process, the latest research activities are discussed. The fundamentals of RA are outside the
7 scope of this article and can be found elsewhere [3, 13, 14].
8
9 2. Reactive absorption applications
10
11 2.1 Removal of CO2 and/or H2S
12 We consider the removal of the acid gases CO2 and/or H2S in a single section, because these
13 components are often met in the same gas stream and they are treated with similar solvents.
14 The solvent must be chosen under consideration of the following factors [15, 16]:
15 • Required purity of cleaned gas stream for further processing or end use
16 • Composition of feed gas
17 • Utility requirements, process costs
18 • Corrosion and solvent degradation/solvent losses
19 For the treatment of gases containing CO2 and/or H2S, aqueous solutions of ethanolamines,
20 carbonates as well as ammonia can be used. The application of ammonia has decreased in the
21 past years [1, 17]. However, absorption with aqueous ammonia offers many advantages over
22 conventional ethanolamine processes, e.g. higher CO2 absorption efficiency, lower
23 decomposition temperatures and lower costs [18, 19]. In this review, we only consider amine
24 and carbonate processes, as they are mainly used for acid gas removal [1].
25
26 Amines: In general, alkanolamines have at least one hydroxyl group and one amino group in
27 their chemical structure. The hydroxyl groups increase the water solubility and reduce the
28 vapour pressure of the alkanolamine. The amino group supplies the alkalinity in aqueous
29 solutions, which is necessary for the absorption of acid gases.
30 Alkanolamines can be subdivided into three groups according to their chemical structure: 1.
31 primary amines, 2. secondary amines, and 3. tertiary amines. Primary amines have a nitrogen
32 atom with two hydrogen atoms directly attached to it. Secondary amines have one hydrogen
33 atom attached to the nitrogen atom and tertiary amines have no hydrogen atoms directly
4
1 attached to the nitrogen atom. The chemical formulas of the most widespread amines, MEA,
2 DEA, TEA, DIPA, MDEA and DGA, are shown in Figure 2. Other amines and amine based
3 solvents are discussed in [20]. In CO2 / H2S absorption with primary amines, following
4 reactions take place [1]:
5
6 Ionization of water: H 2O ↔ H + + OH − (1)
7 Ionization of dissolved H2S H 2 S ↔ H + + SH − (2)
8 Hydrolysis and ionization of dissolved CO2: CO2 + H 2O ↔ HCO3− + H + (3)
9 Protonation of alkanolamine: RNH 2 + H + ↔ RNH 3+ (4)
10 Carbamate formation: RNH 2 + CO2 ↔ RNHCOO − + H + (5)

11
12 Table 3 shows some characteristics of primary, secondary and tertiary amines used in the gas
13 treatment. These properties are important for choosing the most appropriate solvent for the
14 gas treatment process in consideration. The enthalpies of reaction and evaporation decrease
15 from primary to tertiary amines. These enthalpies are directly related to the energy required
16 for solvent regeneration. Therefore the regeneration of tertiary amines requires lower energy
17 consumption than primary amines. The reaction rate of primary amines is higher than of
18 tertiary amines. Therefore high solvent circulation rates are necessary, when tertiary amines
19 are applied. Primary amines are more corrosive than secondary or tertiary amines. The
20 corrosivity influences the choice of equipment material and the efficiency of the absorption
21 process by limiting the working capacity [21]. The high corrosivity of primary amines and
22 their reaction products increase the investment costs since corrosion resistant materials are
23 necessary. The loading describes the capability of one mole solvent to absorb one mole acid
24 gas components. The loading increases form primary to tertiary amines. This implies higher
25 amine concentrations of primary amines for comparable removal results with tertiary amines.
26 Some quantitative information for the most common amines can be found in Table 4 [22].
27
28 Carbonates: The processes are based on: 1. application of hot potassium carbonate, 2.
29 absorption by ambient temperature sodium or potassium carbonate solutions with vacuum
30 regeneration, and 3. absorption into solutions containing free caustics at ambient temperature.
31 In this article, only high temperature absorption is considered, because this technology is
5
1 applied for both, CO2 and H2S removal, while processes at ambient temperatures are not
2 suitable for CO2 removal. The other processes are described in [1].
3 During acid gas removal, H2S reacts with the hydroxyl group:
4 H 2 S + OH − ↔ HS − + H 2O (6)
5 This reaction proceeds extremely rapidly. The reaction of CO2 with alkaline solutions usually
6 occurs slower than the reaction with of H2S. CO2 absorption is accompanied by the two
7 following simultaneous chemical reactions [1].
8 Mechanism 1. Formation of HCO3 via the reaction of CO2 with a hydroxyl group:
9 CO2 + OH − ↔ HCO3 − (fast) (7)
10 HCO3− + OH − ↔ CO32 − + H 2O (instantaneous) (8)
11 Mechanism 2. Reaction of CO2 with water and dissociation of HCO3:
12 CO2 + H 2O ↔ H 2CO3 (slow) (9)
13 H 2CO3 + OH − ↔ HCO3− + H 2O (instantaneous) (10)
14 Which mechanism mainly takes place depends on the pH-value of the solution. At pH-values
15 higher than 8, the 1st mechanism predominates, otherwise the 2nd mechanism determines the
16 process. In industrial applications, the pH-value is mostly higher than 8. [23].
17
18 2.1.1 Industrial applications
19 A typical flowsheet of a reactive absorption process for gas cleaning includes an absorption
20 column to perform the removal of the compounds from the feed gas. The outlet gas leaves the
21 column nearly free of unwanted compounds (clean gas). This step is followed by a stripping
22 column, in which the solvent is recovered (Figure 3).
23 In our article, the industrial RA applications are subdivided according to the captured
24 components. In some cases, CO2 is the target component, as in the fossil fuel combustion. In
25 other processes, it is necessary to capture H2S selectively (e.g. in the tail gas treating).
26 However, in the most applications, both CO2 and H2S are captured along with some other
27 components, e.g. COS, HCN, CS2.
28 Table 5 shows examples of specifications for the CO2 removal for different gases depending
29 on their further processing [24]. In reference [15], the purity requirements for syngas in
30 various downstream applications are listed (Table 6).
31
6
1
2 CO2 Removal
3 According to [25], CO2 is mainly produced by gasification, reforming or in power plants.
4 More than 97% belongs to the fossil fuel combustion [26]. Possible sources are coal, oil,
5 natural gas and biomass. The applications of absorption processes are either post-combustion,
6 as in power plants, or pre-combustion, as in the reforming or gasification of natural feed
7 stocks. These applications are illustrated in Figure 4. Depending on the type of the power
8 plant, the concentration of CO2 in the gas phase can vary from 3 to 16 mol%. In Table 7,
9 typical compositions of exhaust gases from coal-fired and gas-fired power plants are listed.
10 Besides, CO2 removal occurs in ammonia and hydrogen production plants.
11 The choice of solvent depends on different given conditions, e.g. feed gas composition and
12 requirements concerning clean gas specifications [1, 15]. Table 8 lists the CO2 capturing
13 processes and their licensors. Additionally, this table gives information about the industrial
14 applications, the used solvents and the numbers of installations. The information is taken from
15 the Gas Processes Handbook [27].
16 The typical flowsheet of a RA process consists of an absorption column that captures CO2
17 from the feed gas (acid or sour gas) by an amine solvent, thus leaving the outlet gas free of
18 CO2 (clean gas), followed by a stripping column that performs the CO2 desorption and the
19 recovery of the amine used as recyclable solvent (Figure 3). Reactive absorption with MEA is
20 an established technology which is used since the seventies [28]. The Econamine FG process
21 (purchased by Fluor Daniel) is one of the most widely used processes in industry using MEA.
22 There are more than 24 existing plants using the Econamine FG process, each with a total
23 capacity of 6-1000 t absorbed CO2/day. It uses a 30wt% MEA solution with corrosion
24 inhibitors. The process can recover 85-95% of the CO2 in flue gases and produces CO2 with a
25 purity of more than 99% – depending on parameters such as the CO2 content of the flue gas,
26 the height of the absorption column, the liquid-to-gas stream ratio and the regeneration
27 efficiency (CO2 loading of the lean solvent) [25, 29].
28 Alternatively, non-inhibited MEA solutions can be used for CO2 absorption. The so-called
29 “ABB Lummus Crest-technology” applies solutions with low MEA concentration of 15-
30 20wt% MEA, thus the addition of inhibitors against corrosion is not required. The total
31 capacity of all absorption plants operated world-wide varies in the range 180-720t CO2/day.
32 Depending on the inlet SOx concentration, a preliminary desulfurisation step may be required.
33 In the “ABB Lummus Crest-technology”, the acceptable SOx concentration is maximum
7
1 50ppm [29]. However, the application of MEA-based processes is limited due to the corrosive
2 salts formed by MEA and SOx present in process streams. Other disadvantages are relatively
3 high enthalpies of reaction and evaporation. This results in high energy requirements for the
4 recovery of the solvent.
5 The Dow Chemical Company developed MDEA-based solvents offered under the trade name
6 UCARSOL. These solvents can be applied for CO2 removal from ammonia syngas, CO2 and
7 H2S removal from natural gas. If required, selective H2S removal can be accomplished by a
8 solvent from the UCARSOL family [30]. This solvent is applied in the Amine Guard FS
9 process for CO2 removal from ammonia syngas. There are more than 500 units worldwide
10 using this technology in treating units for natural gas, ammonia syngas and hydrogen streams.
11 Some companies use sterically hindered amines for the removal of CO2. These amines are
12 developed as alternatives for MEA (e.g. less corrosive or higher regeneration rate) [1]. By the
13 reaction of hindered amines with CO2, higher loadings (1mol/mol amine) than by MEA (0.5
14 mol/mol amine) can be reached. Furthermore, the energy required for solvent regeneration
15 with hindered amines is much lower than, e.g., with MEA. Therefore, hindered amines can
16 reduce both capital and utility costs in the separation of carbon dioxide. Kansai Electric Power
17 Company and Mitsubishi Heavy Industries have developed and have been using a hindered
18 amine called KS1. It is now used at a fertiliser plant in Malaysia [25]. Another hindered
19 amine is 2-amino-1-methyl-1-propanol (AMP) [20].
20 CO2 removal is also carried out by hot potassium carbonate that is used in many plants (e.g.
21 ammonia plants, natural gas treating). The most often applied technology is UOP’s Benfield
22 process with more than 700 units worldwide. In this process, diethanolamine (DEA) is used as
23 an activator. The Catacarb process (Eickmeyer & Associates) also uses hot potassium
24 carbonate, which is applied for the removing of CO2 from ethylene oxide recycle gas. Exxon
25 Flexsorb HP process uses hindered amine activator, whereas the Giammarco-Vetrocoke uses
26 an organic activator for the removal of CO2 [31]. In reference [32], it is reported that ADIP
27 and ADIP-X process can be applied for the bulk and deep removal of CO2 from gas streams.
28
29 H2S Removal
30 Hydrogen sulphide is a colourless, toxic gas, that can be found in biogas, petroleum and
31 natural gas [33]. Gases containing H2S are called sour gases [1], while the removal of H2S
32 from the gas is called sweetening. Most often, hydrogen sulphide must be removed because of
33 its high corrosivity and due to environmental reasons [31, 32].
8
1 Coke oven gas from coke plants also contains H2S. For the reduction of SO2 emissions and to
2 fulfil technological and safety requirements, the desulphurisation of coke oven gas is
3 necessary. The H2S content of coke oven gas is limited to 500 mg/mn3 [34].
4 Another example for H2S removal can be found in the Claus process that produces elemental
5 sulphur from H2S containing gases. The tail gas leaving this process consists of sulphur
6 vapour and SO2, which is treated using the so-called tail gas treatment (TGT) process. The
7 product of this process is used as a feed stream in the Claus process. The TGT process
8 consists of a reaction step forming H2S from the mentioned tail gas components and an
9 amine-based absorption step to bring the H2S concentration to the value that is required for
10 the Claus process [33]. The Shell’s SCOT process is a TGT process that is often applied.
11 H2S absorption can also be used in hydrodesulphurisation. In this process, sulphur compounds
12 are removed from mineral oil products by hydrogenation. Table 9 shows suitable processes
13 for selective H2S removal. The listed processes can recover sulphur from a gas stream up to
14 99 %. The Lurgi Tail-Gas Treatment (LTGT) process is a wet-scrubbing process for the
15 treatment of the tail gas from the Claus process. Nearly six LTGT units are in operation. The
16 Fluor hydrogenation process and the High Claus Ratio process are also applied for Claus tail
17 gas treatment for nearly complete sulphur recovery [27].
18
19 Removal of CO2-H2S mixtures and other impurities
20 Together with CO2 and H2S, raw gases often contain, other impurities, e.g. mercury, COS,
21 CS2 and organic sulphur compounds. For many industrial applications, it is necessary to
22 remove both CO2 and H2S and possibly other undesirable compounds for economic and
23 ecological reasons [35]. Natural gases, refinery gases and synthesis gases contain high
24 amounts of CO2 and H2S [32, 36-38]. A high CO2 content in natural gas reduces the heating
25 value of the gas. Therefore, CO2 has to be removed from natural gas for increasing its quality.
26 H2S must be removed, because both this component and the products of its reaction are highly
27 corrosive [15]. Levels of less than 1 % for CO2 and 4 ppm for H2S must be achieved for
28 preventing corrosion of the equipment and to fulfil fuel gas requirements [36, 39]. Syngas
29 contains acidic compounds such as H2S, COS and CO2. The aqueous solutions of these
30 compounds are corrosive and also must be removed for the avoidance of corrosion of process
31 equipment [15].
32 In gas liquefaction processes, acid gas treatment includes the removal of CO2 and sulphur
33 compounds (H2S, COS and mercaptans). This is applied in both LNG (liquefied natural gas)
9
1 [33] as well as in LPG (liquefied petroleum gas) production [40].

2 As mentioned earlier, for choosing the appropriate absorption processes for a given separation
3 problem, the knowledge of the gas inlet as well as outlet concentrations is necessary. This is
4 even more complex, when more than one component is to be removed. For the selection of
5 the appropriate removal process for CO2 and sulphur containing gases, [21] gave a schematic
6 representation (see Figure 5).
7 Table 10 contains above mentioned processes for the removal of CO2 and H2S containing
8 gases. MEA, MDEA, DEA and DIPA are the most common amines for simultaneous CO2 and
9 H2S removal, due to their low cost, high reactivity and easy regeneration. The disadvantages,
10 e.g. corrosiveness, can be overcome by the addition of corrosion inhibitors [1].
11 The most widely used technologies for simultaneous CO2 and H2S removal are the Benfield
12 process based on hot potassium carbonate (over 700 units worldwide), the Amine Guard FS
13 process applying the MDEA-based sol-vent UCARSOL (~500 units) and the ADIP process
14 using DIPA or MDEA (over 400 units). The aMDEA process, developed and licensed by
15 BASF, is one of the few technologies in which additional mercaptan removal is possible.
16
17
18 2.1.2 Research activities

19 Current research activities concerning RA for the removal of CO2 and/or H2S containing
20 gases are mostly addressed to Carbon Capture and Storage (CCS). When integrating amine
21 scrubbers into a power plant, the energy requirements will increase by 25-40% [28]. However
22 Rochelle [41] claims that amine scrubbing will probably be the dominant technology for CO2
23 capture from coal-fired power plants in 2030. Hence there is a huge potential for optimization
24 which will require significant research work.
25
26 Improvement of solvents
27 The main room for improvement of the industrially used processes are related to the solvents.
28 According to Davidson [42] and Wang et al. [43], the ideal chemical solvent possesses a high
29 reactivity with respect to CO2, low regeneration cost requirements, high absorption capacity,
30 high thermal stability and reduced thermal degradation, a low environmental impact and low
31 costs. According to Veawab et al. [44], 70-80% of the operating costs arise due to the
32 regeneration of the solvent. Additionally, the most commonly used solvent MEA has several
33 disadvantages like a low carbon dioxide loading capacity, solvent degradation in case that
10
1 SO2 and O2 are present in the flue gas, high equipment corrosion rate and high energy
2 consumption [43].
3 Lepaumier et al. [45, 46] studied the degradation in the presence of CO2 and oxidative
4 degradation of several amines to find new promising solvents. It can be seen that some amines
5 are more stable than MEA. For example, MDEA (N-methyldiethanolamine), AMP (2-amino-
6 2-methylpropan-1-ol), DMP (N,N’-dimethylpiperazine) and TMEDA (N,N,N’,N’-tetra-
7 methylethylendiamine) are more stable in the presence of CO2; furthermore, DMEA (N,N-
8 dimethylethanolamine) and AMP reveal less oxidative degradation.
9 Different types of amines and their mixtures were compared experimentally and numerically
10 by Dubois & Thomas [47]. The CO2 absorption efficiencies increase when mixing different
11 types of amines: tertiary or sterically hindered amines with an activator (e.g. piperazine (PZ))
12 or a primary amine (e.g. MEA). For example the absorption efficiency of an aqueous mixture
13 of MDEA (30%) and PZ (12,5%) is about 15 times higher than the absorption efficiency of a
14 30% aqueous MDEA solution [47].
15 Vaidya and Kenig [48] studied the reaction kinetics of aqueous solutions containing N-
16 ethylethanolamine (EEA) and N,N-diethylethanolamine (DEEA), which are potentially
17 attractive, as they can be prepared from renewable resources. It was found, that the CO2
18 absorption rate was enhanced, when even a small amount of EEA was added to an aqueous
19 DEEA solution. Further, they studied the kinetics of the reaction of CO2 with N-methylmono-
20 ethanolamine (MMEA) and N,N-dimethylethanolamine (DMEA) [49] and acceleration of the
21 CO2 reaction with DEEA in aqueous solutions by PZ [50]. It was found that the CO2
22 absorption rate could be substantially enhanced by adding just a small amount of PZ.
23 Solvents containing diamines have a good potential for CO2 capture, because of the presence
24 of one or more primary or secondary amino groups. The kinetics of CO2 reaction with
25 diamine N-(2-aminoethyl)ethanolamine (AEEA) was investigated by Bindwal et al. [51].
26 Parallel to its use as an amine blend activator, concentrated PZ is also applied as a solvent,
27 besides, PZ-promoted potassium carbonate (K2CO3) solutions are also in use. These
28 applications represent separate research areas. For instance, Freeman et al. [52] carried out
29 experiments to measure the oxidative and thermal degradation, the CO2 solubility, the CO2
30 mass transfer rates in PZ and the volatility of aqueous PZ solutions. In addition, the energy
31 requirement was estimated using the simulation tool Aspen Plus®. The experiments revealed
32 that oxidative degradation of PZ is slower than that of MEA. Thermal degradation is
33 insignificant for temperatures of up to 150°C. Therefore, high-pressure strippers are allowed
11
1 to improve the energy performance. The mass transfer measurements have shown that the rate
2 of absorption into PZ is higher than that into MEA. The simulations of a simple stripper
3 section indicated that the equivalent work required for the stripping of a PZ solution is 10 to
4 20% lower than for MEA. Furthermore, Bishnoi & Rochelle [53] made experiments to
5 measure reaction kinetics, mass transfer and solubility, Chen & Rochelle [54] studied
6 derivatives of aqueous piperazine solutions and Plaza & Rochelle [55] demonstrated the
7 benefits of PZ in a one-month pilot plant campaign.
8 Oexmann et al. [56] analysed the post-combustion CO2-capture process using a solution of
9 aqueous K2CO3 promoted by PZ with the simulation tool ASPEN Plus® (equilibrium stage
10 model). It was shown that the use of a mixture of 2,5m K2CO3 and 2,5m PZ may significantly
11 reduce the required heat duty for solvent regeneration in comparison to MEA. When attaining
12 a CO2-capture rate of 90%, the heat duty for this process is as low as 2,4 GJ/tCO2 compared
13 to 3,3 GJ/tCO2 (for MEA). By integrating this CO2-capture and a CO2-compression process
14 into a coal-fired power plant, the overall energy requirement will reduce from 0,342 kWhel/kg
15 CO2 to 0,288 kWhel/kg CO2. In contrast to this preliminary evaluations Oexmann & Kather
16 [57] found that the K2CO3 process is better in terms of heat duty, but, considering higher
17 operational costs, due to the high price of PZ, the overall costs for CO2 removal are 18%
18 higher than for MEA. More information on this technology can be found in Cullinane &
19 Rochelle [58].
20 Further research is done on ammonia. The chilled ammonia process was already patented in
21 2006 by Eli Gal and is still under research. Darde et al. [59] performed thermodynamic
22 analysis of the system. The study showed that the chilled ammonia process allowed for a
23 significant reduction of the energy consumption in the desorber compared to the energy
24 consumption of the process based on amines.
25 Amino acid salts are of great interest for CO2 capture. They are present in the environment in
26 a natural way and therefore environmentally friendly. In addition, they have the same
27 functional groups as alkanolamines, and their reactivity and CO2 absorption capacity are
28 comparable to aqueous alkanolamines [60]. A study on amino acid salt systems is published
29 in [60]. Potassium sarcosine showed a better absorption rate than MEA, but the energy
30 requirement for regeneration was higher. Aronu et al. [61]studied the performance of amino
31 acid salts formed from the neutralisation by an organic base. It was shown that these amino
32 acid salts had a better CO2 absorption potential than amino acid salts formed from
33 neutralisation by an inorganic base. Vaidya & Kenig [62] investigated the kinetics of carbon
12
1 dioxide removal by aqueous alkaline amino acid salts and found that the CO2 absorption rate
2 was enhanced, when even a small amount of potassium glycinate was added to an aqueous
3 DEEA solution.
4 According to Wang et al. [43], another promising solvent is a mixture of alkanolamines and
5 enzymes. The latter can catalyse very fast reactions at ambient conditions requiring only small
6 solvent amounts.
7 A new interesting possibility is the use of demixing solvents as in the DMXTM process
8 proposed by IFP Energies Nouvelles [63]. In this process, a liquid solvent is used that splits
9 onto two separate liquid phases after the heat exchanger between absorber and stripper, thus
10 building a water-rich phase, with a very high carbon dioxide loading, and an amine-rich
11 phase. Consequently, the amine-rich phase does not need to be sent to the stripper and the
12 energy requirements for solvent regeneration is lowered. Process simulations showed that the
13 reboiler energy can be reduced from 3.7 GJ/ton CO2 typical for a standard MEA process
14 down to 2.3 GJ/ton CO2 for the DMXTM process.
15
16 Improved integration
17 Capturing CO2 from flue gas streams requires cost-effective capture technology and energy-
18 efficient integration of the capture unit into the power plant. According to Pfaff et al. [64],
19 currently such processes are characterised by large heat requirements for the regeneration of
20 the solvent and auxiliary power for pumps, blowers and the final compression of the separated
21 CO2. Due to these energy demands, the net efficiency of the overall power plant process
22 decreases to about 9 to 13 %.
23 Pfaff et al. [64] analysed the integration of a CO2 capture process into a greenfield hard-coal-
24 fired power plant using the simulation software EBSILON Professional® from STEAG
25 Energy Services. This study shows that the integration of waste heat from the CO2 capture
26 unit into the water-steam-cycle of the power plant will minimise the overall net efficiency
27 loss. More specifically, the waste heat from the desorber overhead condenser and from the
28 CO2 compressor can be used.
29 Further studies on process integration of coal-fired power-plants were done by Stankewitz &
30 Fahlenkamp [65] and Lucquiaud & Gibbins [66]. In [65], heat sources and sinks were
31 quantified with the help of simulations (Aspen Custom Modeler® from AspenTech and
32 EBSILONProfessional® from STEAG Energy Services). Recovering of waste heat can
33 significantly reduce the loss of efficiency. Lucquiaud & Gibbins [66] proposed a method to
13
1 estimate electrical output penalty (EOP) values for CO2 capture and compression systems that
2 are integrated within the power plant. They designed a tool to assess solvent-based capture
3 technology integrated into the power cycle of new-build coal-fired plants. The integration of
4 supercritical coal-fired power plants with high temperature (580°C) and pressure (23 MPa)
5 were studied by Romeo et al. [67, 68] and Aroonwilas & Veawab [69].
6
7 Cement industry
8 Carbon capture plays also an important role in cement industry. Contrary to common flue
9 gases, here, the gases contain relatively large amount of CO2. A recent theoretical study in
10 [70] considers a process flow diagram for the integration of the carbon capture process in the
11 cement production plant. In the absorption step, aqueous MEA is applied. It could be shown,
12 that each tonne CO2 that can be avoided in a 1Mt/y European cement plant would cost 107€.
13 The corresponding cost for a 3Mt/y Asian plant would be 59€. Furthermore, these costs can
14 be reduced if other solvents are applied and the process is integrated into the adjacent power
15 plants.
16
17 2.2 NOx removal
18 Nitrogen oxides are gases with high reactivity containing varying amounts of nitrogen and
19 oxygen. Most of the NOx emissions are in the form of NO that is then oxidised to NO2 in the
20 atmosphere. All combustion processes are sources of NOx. During combustion, some N2 is
21 converted to NO at high temperatures and in the presence of oxygen, whereas the higher the
22 combustion temperature is, the more NOx is produced. Emissions of NOx remained more or
23 less constant in the past decades, with the major sources being the combustion in industrial
24 facilities, electric power generation, non-road engines and on-road vehicles. Figure 6 shows
25 the primary sources of nitrogen oxides. Remarkable, the transportation sector produces the
26 highest amount of NOx (61%), while the total emission of industrial activities is about 32%,
27 according to Chung et al. [71].
28 The applied NOx removal processes can be classified as dry and wet processes. Dry processes
29 are catalytic or non-catalytic denitrification processes, while the scrubbing of nitrogen oxides
30 by water or aqueous nitric acid belongs to the wet methods [71, 72]. The wet methods belong
31 to the class of RA processes [73].
32
33
14

2 The industrial NOx treatment is carried out by capturing NOx in water or aqueous nitric acid.
3 In addition to gas cleaning, the same RA process is also used for the manufacturing of nitric
4 acid. The latter technology is addressed in the subsequent section. Absorption of nitrous gases
5 is a highly complex process, due to the interaction of several components and chemical
6 reactions in both the liquid and gas phases. During the absorption of nitrogen oxides, the
7 following reactions may occur [73, 74]:
8
9 2NO + O2 → 2NO2 (gas phase) (11)
10 2NO2 → N2O4 (gas phase) (12)
11 NO + NO2 → N2O3 (gas phase) (13)
12 NO + NO2 + H2O→ 2HNO2 (gas phase) (14)
13 3NO2 + H2O → 2HNO3 + NO (gas phase) (15)
14 2NO2 + H2O → HNO3 + HNO2 (liquid phase) (16)
15 N2O3 + H2O → 2HNO2 (liquid phase) (17)
16 N2O4 + H2O → HNO3 + HNO2 (liquid phase) (18)
17 3HNO2 → HNO3 + H2O + 2NO (liquid phase) (19)
18
19 Note that absorption of NOx can further be enhanced by the addition of hydrogen peroxide
20 (H2O2), according to the following reaction mechanism:
21 2NO + 3H2O2 → 2HNO3 + 2H2O (liquid phase) (20)
22 HNO2 + H2O2 → HNO3 + H2O (liquid phase) (21)
23
24 Hydrogen peroxide reacts with HNO2 and NO from the liquid phase, and as a consequence it
25 enhances the formation of nitric acid [75]. The NOx gas is charged with a certain amount of
26 H2O2, and the gas mixture reacts on a solid catalyst to hydrogen nitrate that is either
27 withdrawn for further use or converted into nitric acid by condensation or by water scrubbing.
28 This process, patented by Degussa (now Evonik Industries), allows the removal of NOx (even
29 at low concentrations, below 2000 ppm) with high efficiencies above 90% [76], depending on
30 the NO2 concentration in total NOX – this aspect being discussed in [77]. Note that flue gases
31 and tail gases may have widely varying NO2/NOX-ratios and correspondingly varying
32 abatement efficiencies.
33 Several basic approaches are typically used to reduce the tail-gas NOx levels: improved RA,
15
1 chemical scrubbing, adsorption and catalytic tail-gas reduction [78]. Intense research and
2 development effort was invested in these methods during the past decades. In what follows,
3 we focus only on the methods related to RA.
4 The efficiency of absorption depends mainly on the operating pressure, temperature and the
5 number of stages. The temperature of the gas between stages is especially important because
6 it governs the progress of oxidation, the limiting stage for the entire absorption process [78].
7 In existing plants, the following improvement options can be used:
8 • Expand the absorption volume. The advantage of this option is that it does not require any
9 new technology. The absorption volume is added in the form of a second tower – new
10 absorption tower designs with very few stages have been devised. However, large
11 additional volumes only result in small reductions of tail-gas NOx levels, since the
12 oxidation of NO to NO2 proceeds very slowly when the NOx concentration is low. The
13 drawback is that added absorption volume in stainless steel is expensive [78].
14 • Lower the absorption temperature. The use of cooling energy in the absorption process
15 significantly accelerates the oxidation of NO to NO2. The disadvantage here is that the
16 required refrigeration equipment and piping means further investment. An alternative aid
17 to reduce the NOx level is to cool down the nitrous gas, so that more N2O4 is formed than
18 NO2. The N2O4 is then scrubbed with nitric acid at 0°C; in this way it can be stripped out
19 and converted to nitric acid (N2O4 + ½ O2 + H2O → 2HNO3) in an absorption reactor
20 operated in the range of 60-80°C. This technique is actually similar to that in concentrated
21 nitric acid production. However, the method is more suitable for investment in a new plant
22 than for the expansion / upgrading of an existing plant [78].
23 Chemical scrubbing is a generic technology by which several contaminants are removed from
24 the gas stream by means of a scrubbing liquid reacting with them. The chemical scrubbing of
25 NOx out of tail gas is covered in a number of patents and scientific publications [78]. It is
26 worth noting that all the scrubbing methods have problems related to the scrub liquor: e.g.
27 cost, regeneration, quantity, and environmental impact. These problems are always easier to
28 manage, if the NOx removal is part of an integrated chemical plant, what is typically the case
29 in practice. The following scrub liquors have been proposed so far [78]: aqueous suspension
30 of magnesium carbonate and magnesium hydroxide [79], solution of vanadium in nitric acid
31 [78], ammonium sulfide and bisulfide [80], milk of lime [81], ammonia [78], hydrogen
32 peroxide [82], and urea [78].
16
1 At industrial scale, ammonia scrubbing is used in the US by Goodpasture (Texas) who has
2 developed a safe process based on scrubbing the tail gas with ammonium nitrate solution. The
3 nitrite formation is suppressed by aeration and the presence of free acid. The tail gas is then
4 led through a scrub liquor containing ammonia (pH 7.5-8.5). The scrubbing product is a 30-
5 50% ammonium nitrate solution, while the tail gas has a residual level of ~200 ppm NOx [78].
6 The hydrogen peroxide scrubbing method is based on the following overall reactions:
7 NO + NO2 + 2H2O2 → 2HNO3 + H2O (22)
8 2NO2 + H2O2 → 2HNO3 (23)
9 The reactions are carried on sieve trays or in packed towers with recirculation of the hydrogen
10 peroxide solution. The benefit of this scrubbing process is that the reaction time is very fast.
11 However, the drawback is that the hydrogen peroxide scrub liquor is rather expensive.
12 Another process was developed by Norsk Hydro in Norway, with the advantage that urea is
13 readily available and quite inexpensive [78]. The process is carried out at 50°C using a
14 solution containing 20% urea and 10% free nitric acid for scrubbing tail gas to remove NOx.
15 By doing so, both nitrogen oxides are selectively reduced to N2 by urea that decomposes to
16 yield nitrogen and carbon dioxide. The resulting stack gas trail is colorless and heavily loaded
17 with water vapor.
18
20 The latest research activities were dedicated to aqueous alkaline solutions, the main reason
21 being the possibility to produce valuable substances, such as nitric acid and its salts – nitrates
22 and nitrites [83]. Pradhan and Joshi [84] used an aqueous NaOH solution as a solvent in a tray
23 column, in which sodium nitrite is produced selectively. This process can be also improved by
24 the addition of H2O2 and the use of structured packing as column internals [75]. Other
25 alkaline solutions were analysed and a model was developed by Patwardhan and Joshi [83],
26 who incorporated the HNO2 decomposition, as well as the neutralisation by alkali. This led to
27 a unified model for NOx absorption, which can be used for predicting process rates and
28 selectivity, for various gas compositions and liquid-phase pH-values [83].
29 BioDeNOx is a novel process – developed and tested at Wageningen University and TU Delft
30 [85, 86] – for the removal of NOx from industrial flue gas, in which the reactive absorption of
31 NO in aqueous solutions of Fe-II(EDTA) plays a key role resulting in the formation of a
32 nitrosyl complex Fe-II(EDTA)(NO). Basically, the BioDeNOx process combines the
33 principles of wet absorption of NO into an aqueous Fe-II(EDTA) solution with biologi-
17
1 cal regeneration of the scrubber liquor in a bioreactor. Note that the oxygen present in the
2 flue gas will also be absorbed and oxidise Fe-II(EDTA). This is in fact an undesired reaction,
3 since the resulting Fe-III(EDTA) does not react with NO.
4 Winkelman et al. [87] developed a rate-based model for the simultaneous RA of NO and O2 in
5 aqueous Fe-II(EDTA) solutions in a counter-current packed column, and evaluated the effect
6 of process conditions on the absorber performance (e.g. NO removal efficiency and
7 selectivity). The absorber performance was particularly dependent on the operating
8 temperature, while lower temperatures are in favor of both the NO removal efficiency and
9 selectivity [87]. Notably, over-designing the absorber may result in decreasing performance,
10 because, at certain process conditions, desorption of NO may occur resulting in lower NO
11 removal efficiencies at increasing column lengths.
12 More recently, Kenig and Seferlis [88] also demonstrated the ability of using rate-based
13 models in a compact form – by using the orthogonal collocation on finite elements (OCFE) –
14 to accurately predict the steady-state and dynamic behaviour of industrial and experimental
15 columns for NOx absorption. OCFE formulation reduces the overall size (total number of
16 equations) of the RA process model, while preserving its structure and accuracy. A
17 comprehensive description of the OCFE method is given by Dalaouti and Seferlis [89, 90].
18
19 2.3 Nitric acid production
20 Nitric acid – also known as aqua fortis or azotic acid – is an inorganic acid of major industrial
21 importance. Due to its properties as a very strong acid, a powerful nitration and oxidising
22 agent, nitric acid is crucial in the production of many chemicals, e.g., pharmaceuticals, dyes,
23 synthetic fibers, insecticides, and fungicides [91]. Remarkable, nitric acid is mostly used in
24 the production of ammonium nitrate for the fertilizer industry – about 70% of the global
25 production amounting 54.5 million tons in 2010 [92]. The world production of NH4NO3 is
26 largely concentrated in two regions, the former USSR (24.5%) and Western Europe (21.7%),
27 although USA, China and Central Europe are also large producers [93].
28 Nitrogen oxides (NOx) are formed not only as waste gases in many industrial processes, but
29 also during the oxidation of ammonia in the nitric acid production process. From the eco-
30 efficiency viewpoint, it is beneficial to combine the removal of NOx from waste gases with
31 the production of nitric acid by NOx absorption in water or diluted nitric acid. Overall, this is
32 a very complex process involving chemical reactions in both gas and liquid phase. A general
33 approach to the description of such processes was gradually developed in [73, 74, 88, 94].
18
1
3 Nitric acid is met in nature only in the form of nitrate salts, and sodium nitrate was used as
4 feedstock when the large-scale production of nitric acid started. Only in the beginning of the
5 20th century, when the sodium nitrate reserves were considered to approach exhaustion, other
6 processes were developed to replace nitrogen from nitrates with atmospheric nitrogen. The
7 three techniques used industrially were [78]:
8 1. Direct processes to produce NO by a reaction of atmospheric nitrogen with oxygen at
9 temperatures over 2000 °C. The direct combustion of air in an electric arc – developed
10 by Birkeland and Eyde (see [78]) – was abandoned due to its poor energy efficiency.
11 Other direct processes developed later – such as thermal NO synthesis with fossil fuels
12 or in nuclear reactors – did not gain widespread acceptance.
13 2. Production of ammonia by hydrolysis of calcium cyanamide under pressure – a
14 process of only transient value, until the Haber-Bosch process became available.
15 3. Production of ammonia from nitrogen and hydrogen, by the Haber-Bosch process – a
16 process used nowadays to produce ammonia feedstock for nitric acid production.
17 The crucial step in the nitric acid production is the catalytic combustion of ammonia, a
18 process developed by Ostwald and implemented at industrial scale in 1906 at Gerthe in
19 Germany [78]. The Ostwald process involves three key chemical steps:
20 • Catalytic oxidation of ammonia with atmospheric oxygen to yield nitrogen monoxide,
21 • Oxidation of NO product to nitrogen dioxide or dinitrogen tetroxide,
22 • Absorption of the nitrogen oxides to yield nitric acid.
23 The following exothermic reactions occur in the above mentioned process steps [91]:
24 4NH3 (g) + 5O2 (g) → 4NO + 6H2O (g) ∆HR = −226 kJ/mol (24)
25 2NO (g) + O2 (g) → 2NO2 (g) ∆HR = −114 kJ/mol (25)
26 3NO2 (g) + H2O (l) → 2HNO3 (aq) + NO (g) ∆HR = −117 kJ/mol (26)
27 4NO2 (g) + 2H2O (l) + O2 (g) → 4HNO3 (aq) ∆HR = −63 kJ/mol (27)
28 Note that the oxidation of nitrogen monoxide is a rare example of a homogeneous third-order
29 gas-phase reaction, while the absorption of NOx is a heterogeneous reaction [78]. The nitric
30 acid production processes are characterised by the way in which the three steps mentioned
31 above are implemented. In single-pressure processes, the ammonia combustion and NOx
32 absorption take place at the same working pressure (in the range of 1-14 bar) – with very few
33 plants currently employing only relatively low pressure (1-2.2 bar) for both oxidation and
19
1 absorption steps. In dual-pressure (split-pressure) processes, the absorption pressure (6.5-13

2 bar) is higher than the oxidation pressure (1-6.5 bar). The modern plants feature oxidation at
3 4-6 bar and absorption at 9-14 bar, while older plants still employ atmospheric combustion
4 and medium-pressure absorption – see Table 11 [95].
5 Most new plants work with the dual pressure process – illustrated in Figure 7 [95]. An air-
6 NH3 mixture, with a composition ratio of 9:1 is catalytically converted mainly to NO that is
7 afterwards oxidised and reacts with residual O2 to form NO2 and NO2-dimer. The mixture of
8 NO2/dimer is introduced into the bottom of the absorption tower, in counter-current with de-
9 ionised process water. Another air stream is introduced into the column to re-oxidise the NO
10 that is formed in reaction. The nitric acid is withdrawn from the bottom of the column.
11 Oxidation takes place in the free space between the trays, while absorption occurs on the trays
12 – usually sieve or bubble cap trays [95].
13 High-strength nitric acid (98-99%) is produced by dehydration followed by bleaching,
14 condensation and absorption in a weak nitric acid, while commercial grade nitric acid
15 solutions (52% and 68%) are produced via the Ostwald process [95]. Weak nitric acid (30-
16 70%) is produced by catalytic oxidation of ammonia, followed by condensation and
17 absorption in water. In the high-strength nitric acid process shown in Figure 8, an acid
18 concentration of 98-99% is obtained using extractive distillation. Weak nitric acid is
19 introduced into a distillation column with a dehydrating agent (e.g. sulfuric acid 60%). Both
20 acids are fed to the top of the column, at atmospheric pressure, in counter-current to the
21 ascending vapours. The vapour leaving the column is concentrated nitric acid (99%) that
22 passes to a bleacher and then to a condenser. The concentrated nitric acid is obtained in the
23 condenser, while the by-products (O2 and NO) are introduced into the absorption column that
24 produces weak nitric acid.
25 The design of the nitric absorption columns requires the individual tailoring of each tray
26 (typically bubble cap or sieve trays) for its cooling requirements and the gas volume rates
27 needed for oxidation of the nitric oxide. A good summary of absorber design aspects is
28 available in the book of Keleti [96]. Capacities of around 1800 t/d HNO3 were achieved in a
29 single RA column of up to 6 m in diameter, 80 m high, and containing as many as 30-50
30 trays. For abatement reasons, single absorption columns reach tail gas NOx compositions of
31 about 200 ppm, although the economic optimum for absorber efficiency would lead to higher
32 tail gas NOx concentrations (1500-2500 ppm). Various methods are used to reduce tail gas
33 NOx concentrations to an acceptable level for discharge to the atmosphere (200-230 ppm), the
20
1 most commonly employed being the extended absorption and (non-)selective catalytic
2 reduction (SCR and NSCR). Extended absorption uses an additional column for oxidation and
3 reaction of nitrogen oxides with water to form acid. Relatively few trays are required, but
4 large oxidation volumes – often employing refrigeration to promote the oxidation and to
5 minimize the column size. This method is most effective for high pressure (HP) absorption in
6 which abatement to less than 200 ppm NOx can be achieved in a single HP column [91].
7 Table 12 provides an overview of the main producers of nitric acid in US and Western Europe
8 – the capacities being given in thousands of metric tons per year on a 100% HNO3 basis, and
9 the market share as percent of the regional market [93]. Remarkable, on a country-by-country
10 basis, the Western European production of nitric acid is dominated by five countries
11 accounting for 73.3% of total nitric acid production in 2010: Germany 17.7%, France 17.0%,
12 Netherlands 16.4%, Belgium 12.0%, and United Kingdom 10.2%.
13

15 The current research activities are primarily driven by the main pollution problem in the nitric
16 acid manufacture, namely the abatement of NOx in the tail gases. There are only few options
17 to reduce the emissions to acceptable levels: to capture the NOx and convert it to additional
18 nitric acid or nitrate-nitrite salts, or to render the NOx harmless by converting it to non-
19 polluting compounds. A large number of processes have been developed and patented to
20 reduce the emissions. They can be classified into three main categories: absorption,
21 adsorption and catalytic reduction [93]. The absorption abatement deals with optimization of
22 the existing absorption system, or modifications aimed to increase the absorption capacity.
23 Tail gases are passed through an absorber containing either water or an aqueous solution of
24 ammonia, urea or NaOH. When water is used, the resulting weak acid is recycled leading to
25 slightly increased nitric acid yields (1-3% higher). When other absorbents are used, the
26 recovered NOx is usually consumed in the production of nitrogen solutions for fertilizer use. If
27 NaOH is used, pure sodium nitrite and sodium nitrate may be recovered [93].
28 The need to make the nitric acid processes more efficient, while meeting the much stricter
29 environmental regulations (e.g. 200 ppm in EU, or 1.5 kg NOx per metric ton of nitric acid in
30 USA), led to new advances in understanding the absorption chemistry. One such development
31 is the High Efficiency Absorption (HEA) technology developed by Rhône-Poulenc, which
32 can reduce the size of an absorber column by up to 35%. HEA is applicable when the gas-
33 phase NOx concentration is low (<8000 ppm) and the rate-limiting step for nitric acid
21
1 formation is typically the gas-phase oxidation of NO. By directly oxidising nitrous acid in the
2 liquid phase to nitric acid, the decomposition of nitrous acid is avoided and the large
3 oxidation volumes for NO2 regeneration from NO are greatly reduced [91].
4 Much effort has been put into the development of advanced rate-based models of NOx
5 absorption. Here, bulk reactions and film reactions have to be considered in both phases. A
6 comprehensive analysis of such models including their implementation in Aspen Custom
7 Modeller (AspenTech) and validation by comparison with experimental data for a pilot scale
8 packed column and an industrial sieve tray column is given in [73, 88, 97].
9 More recently, catalysts were developed for the selective reduction of NOx to N2 at relatively
10 low temperatures, using NH3 as reducing agent. Although additional NH3 is consumed, this
11 process may provide control of emissions in an efficient way due to low overall costs [93].
12
13 2.4 Desulphurisation
14 Sulphur compounds (e.g. SOx) are produced in several industrial processes, such as
15 combustion of organic fuels or reforming of oil. In the following sections, various “Flue Gas
16 Desulphurisation” (FGD) processes are presented, and the current industrial and academic
17 research activities are summarised.
18

20 There is a wide range of industrial processes for removal of sulphuric oxides from gases. The
21 applications can be classified into wet processes (limeston gypsum, sea-water washing,
22 ammonia scrubbing, Wellman-Lord), semi-dry (circulating fluidised bed, spray dry, duct
23 spray dry) and dry processes (furnace sorbent injection, sodium bicarbonate injection) [98,
24 99]. Out of these processes, only the wet processes are performed by RA.
25 The limestone gypsum process (see Figure 9) is the most common flue gas desulphurisation
26 (FGD) process, which is applied in different variants for over 30 years. This process is well
27 understood and applied by many companies. Most commonly an open spray tower is used, in
28 which the flue gas is flowing upwards. Marsulex, ABB, Lurgi Lentjes Bischoff (LLB),
29 Babcock Borsig, Kawasaki and IHI operate and sell this technology. Babcock and Wilcox
30 (B&W) and Babcock Hitachi have a very similar design. In this variant, a tray is located in the
31 bottom of the gas treatment zone. Mitsubishi Heavy Industries (MHI) uses a different design,
32 without an open spray tower. In this case, a layer of packing is used for an effective gas/liquid
33 surface [98].
22
1 Flue gas can be desulphurised using seawater that has a natural alkalinity. This is a relatively
2 new process (see Figure 10) and is provided by two suppliers only: ABB and LLB. However
3 it is expanding very quickly, due to major advantages. ABB has already built 21 plants [98].
4 Contrary to other FGD processes, no solid components are produced. Moreover, the plant
5 design is relatively simple. However, the technology is limited to coasted sites, due to the sea-
6 water requirements.
7 The ammonia scrubbing technology (see Figure 11) is similar to the limestone-gypsum
8 process. Here, ammonia is used as the absorbent and reacts with SO2. As a result, ammonium
9 sulphate is produced that can be used, for instance in the fertiliser industry [98]. This
10 technology has been applied for over 50 years, currently there are mainly two suppliers, LLB
11 and Marsulex [98, 99].
12 The Wellman-Lord process (see Figure 12) uses an aqueous sodium sulphite solution for the
13 removal of SO2. In this process, valuable products can be obtained, for instance elementary
14 sulphur, sulphuric acid or liquid SO2. The Wellman-Lord process has more than 40
15 implementations in Japan, USA and Germany. The main advantage of this process is that it
16 does not need significant amounts of sorbent. Moreover, there is little waste produced during
17 the process [98].
18 Note that some processes mentioned here use scrub liquors (e.g. milk of lime, limestone) with
19 a suspension of solid particles, thus involving a quite complex gas-liquid-solid system. A
20 phenomenological explanation for such three-phase systems is given elsewhere [100-104].
21
23 In the past decades, the research has focused on the wet processes analysis. The limestone
24 technology and the Wellman-Lord process are well-known, and many applications are
25 available. Newer technologies are the ammonia or seawater scrubbing, they are still in the
26 investigation stage.
27 A method presented by Ipek et al. [105] uses waste water ammonia for the absorption of SO2.
28 In this study, the behaviour of SO2 is analysed experimentally. An investigation of the
29 temperature impact on the SO2 removal can be found in [106].
30 Seawater absorption is analysed by several research groups. The solubility of SO2 in seawater
31 was investigated in [107, 108]. Measurements were carried out using a laboratory batch
32 reactor at 1bar and 298,15K. In a later study, the impact of different pressures and
33 temperatures was investigated [109]. Rodriguez-Sevilla et al. [108, 109] developed models for
23
1 the determination of solubility and activity coefficients. Using Aspen Plus® various
2 influencing parameters, e.g., pH value or SO2 concentration in the feed stream, were analysed
3 by Zhihua & Zhihong [110].
4
5 2.5 Sulphuric acid production
6 Sulphuric acid is the worldwide most produced chemical substance. The yearly production
7 amounts up to 150 million tonnes. North America, Japan and Western Europe produce nearly
8 the half of the total worldwide production. Sulphuric acid is mostly used as an ingredient, the
9 fertilizer industry being its largest single consumer, mostly for manufacturing phosphate
10 fertilizers. Also the (petro-)chemical and the oil refining industries make use of sulphuric
11 acid, e.g., as an acidic dehydrating agent [111].
12

14 A general process diagram for the sulphuric acid production is shown in Figure 13, the main
15 steps being the SO2 formation and conversion to SO3, followed by the RA of SO3 to yield
16 H2SO4. Note that actually there are various types of plants, but only two types produce
17 sulphuric acid using RA methods [112]. The two major processes used for the sulphuric acid
18 production are the lead chamber process and the current contact process [113]. Remarkable,
19 the contact process remained practically unchanged from its introduction in the late 1800s,
20 until the seventies when the double absorption process was introduced in order to reduce the
21 SOx emissions. The double absorption process is shown in Figure 14, while the process
22 flowsheet is given in Figure 15 [114]. However, the double absorption part only reduced the
23 SOx emissions – but it did not change significantly the nature of the process or the equipment
24 used. Nowadays, all modern plants use the double absorption technique that can lead to SO3
25 conversion rates up to 99.85 %, a significant improvement over single absorption processes
26 (up to 98 % only) [114]. Table 13 lists the new plants in Western Europe. Rhone-Poulenc
27 group has already built five plants producing 3600 t sulphuric acid per day.
28 Two fundamental steps are present in the production of SO3 and the absorption of SO3. SO3 is
29 produced by catalytical oxidation of sulphur dioxide (Eq. 28). Possible sources for producing
30 sulphur dioxide are sulphur burning, pyrites roasting, metal sulphide roasting and smelting,
31 sulphuric acid regeneration, metal sulphate roasting and some other processes [112]. The
32 main reaction in the absorber is highly exothermic, as shown by Eq. (29):
33 
→ SO3 (g)
SO2 (g) + ½ O2 (g) ←
 ∆HR = – 96.2 kJ/mol (28)
24
1 
→ H2SO4 (l)
SO3 (g) + H2O (l) ←
 ∆HR = – 132 kJ/mol (29)
2
3 The simplified flowsheet of such an industrial process consists of a sulphur burner, a multi-
4 pass converter (catalytic reactor), economisers, heat exchangers (HX), feed-effluent heat
5 exchangers (FEHE) and SO3 absorption towers (Abs) – as illustrated in Figure 15 [114]. SO2
6 conversion is further improved and tail gas emissions are reduced by an intermediate SO3
7 absorption step (Abs1) in which the production of sulphuric acid takes place. This absorption
8 step is placed after the fourth bed of catalyst in order to change the gas composition by
9 removing most of the SO3 and thus shifting the conversion equilibrium to higher values. The
10 absorption of SO3 is finalized in the second absorber (Abs2) which also purifies the outlet gas
11 emissions. Figure 16 shows typical temperature and composition profiles along the two
12 counter-currently operated absorbers [114]. SO3 concentration is reduced from 9.81% to
13 0.01% in the intermediate absorber, and from 0.44% to only ppm levels in the final step. Note
14 that the dimensionless column length is in fact the ratio between the real (actual) length and
15 the total absorber length.
16 The SO3 absorption towers are packed with ceramic saddles or structured packing, for
17 realising a maximum contact area, and are typically carbon steel vessels lined with acid proof
18 brick and mortar. As of early nineties, all metal towers – with no brick lining – were built
19 from high silicon stainless steel alloys such as SX, Saramet, or ZeCor. Well-designed
20 absorption columns operate at very high absorption efficiencies (>99.5%), typically from over
21 99.8%, and even over 99.9%. Teflon or glass packed fiber bed mist eliminators are typically
22 used in the interpass and final absorption towers, where high efficiency collection of the acid
23 mist is critical [113].
24

26 Sulphuric acid production is a mature industry and most of the developments in production
27 techniques were made in the last century. Hence, there seems to be little scope for
28 improvement [112]. Not surprisingly, the research activities are very scarce, as sulphuric acid
29 has been produced for many decades at the highest world production rate of any chemical.
30 The main developments are in reducing (accidental) pollution. For example, there are
31 improvements in the materials used in the construction of the plants or their design, such as
32 the use of double shell vessels [112]. Currently, the need is to optimise sections in the
33 different process stages depending on site requirements and local conditions [112, 114]. Other
25
1 developments are carried out with respect to energy recovery from primary energy and
2 demisters with very high efficiency.
3 Some studies are related to the presence of NOx in acid plants that can appear through a
4 number of mechanisms in the upstream operations – mainly by oxidation of nitrogen from air
5 (thermal NOx), as nitrogen containing impurities in the feed (feed NOx), or as the organic
6 bound nitrogen present in some fuels during the combustion step (fuel NOx). Usually,
7 nitrogen oxides have to be destroyed and any remaining SO2 has to be stripped with air in
8 order to improve the product quality and avoid emission problems for the customer [112].
9 Depending on the plant design, the concentration of NOx in the feed gas is limited to 5-15
10 ppm in order to produce an acid that would require no additional treatment.
11 Wet sulphuric acid plants that directly convert hydrogen sulphide to sulphuric acid were also
12 proposed as a way to reduce the effort, energy and capital input [113]. More recently, Uhde
13 GmbH presented the development of a new type of wet sulphuric acid plant (Emission Free
14 Sulphuric Acid Plant) covering the key idea of the process, the development stages of lab
15 scale experiments up to the realisation of the individual process steps in a mobile pilot plant.
16 This technology is aimed to replace sulphuric acid plants with backup combustion system and
17 to reduce the SO2 emissions from coke oven plants in order to comply with legislation [115].
18
19 3. Concluding remarks
20 This article presents a comprehensive review on current applications of reactive absorption
21 (RA), covering both industrial processes and the corresponding research activities. A major
22 application of RA is the sweetening of sour gases by removing CO2 and/or H2S from various
23 industrial streams. As these components often appear in the gas streams simultaneously, their
24 removal is considered in the same section using the same absorption technologies – mainly
25 based on aqueous amine or alkaline solutions. In some applications, CO2 and H2S have to be
26 removed selectively. Selective CO2 absorption can be found in the fossil fuel combustion or
27 in different production processes, as in ammonia and hydrogen production plants. Selective
28 H2S removal is mainly applied in the coke oven gas purification, in hydro-desulphurisation
29 and in tail gas treatment of the Claus process. In many applications, CO2 and H2S are
30 removed simultaneously with other components, such as HCN, CS2 or COS – by applying
31 amines that are non-selective towards just one of the components. The main bottleneck in gas
32 sweetening by RA is the high energy requirement – most of it being used for the regeneration
26
1 of the solvent. Therefore, significant research effort is being made towards the development
2 of new solvents, such as amine blends or hindered amines.
3 Nitrogen oxides can be removed using RA in water or aqueous acid solutions. The same RA
4 process is also applied for the production of nitric acid – which can be further optimised by
5 adding H2O2. In the nitric acid manufacturing, nitrogen dioxide is produced from ammonia
6 which reacts with water in a RA column.
7 Reactive absorption is also applied for the desulphurization (i.e. sulphur oxides removal). The
8 most common process is the limestone gypsum process. Ammonia and seawater are also used
9 as solvents in industry, but these processes are rather in the investigation stage. Another
10 important industrial application of RA is in the production of sulphuric acid. Plants producing
11 sulphuric acid employ three key steps: SO2 synthesis by e.g. burning of sulphur, followed by
12 SO2 oxidation to SO3 that is afterward converted to sulphuric acid in absorption columns. The
13 major target here is to achieve very high SO3 conversion, in order to reduce the SOx emissions
14 and to achieve high energy recovery.
15 In future, RA is expected to gain increasing importance for carbon capture and storage or
16 conversion. Furthermore, RA can be applied for the removal of gases produced in the
17 purification of biogas. For the design and optimisation or RA processes, advanced rate-based
18 models are recommended.
19
20 Abbreviations
21
22 ABB Asea Brown Boveri
23 AEEA N-(2-aminoethyl)ethanolamine
24 aMDEA activated methyldiethanolamine;
25 AMP 2-Amino-2-Methyl-1-Propanol
26 B&W Babcock and Wilcox
27 CCS Carbon Capture and Storage
28 DEA diethanolamine
29 DEEA N,N-diethyl ethanolamine
30 DETA diethylenetriamine
31 DGA diglycol amine
32 DIPA di-isopropanolamine
33 DMEA N,N-dimethylethanolamine
27
1 DMP N,N’-dimethylpiperazine
2 DTI Department of Trade and Industry
3 EDTA ethylenediaminetetraacetic acid
4 EEA N-ethyl ethanolamine
5 EFMA European Fertilizer Manufactures Association
6 EOP electrical output penalty
7 EPA U.S. Environmental Protection Agency
8 FGD flue gas desulphurisation
9 HEA high efficiency absorption
10 HETP height equivalent to a theoretical Plate
11 HTU height of transfer units
12 LNG liquefied natural gas
13 LPG liquefied petroleum gas
14 LLB Lurgi Lentjes Bischoff
15 MDEA methyldiethanolamine
16 MEA monoethanolamine
17 MHI Mitsubishi Heavy Industries
18 MMEA N-methylmonoethanolamine
19 NTU number of transfer units
20 NGCC natural gas combined cycle
21 OCFE orthogonal collocation on finite elements
22 PZ piperazine
23 RA reactive absorption
24 SCOT Shell Claus Off-gas Treating Process
25 TEA triethanolamine
26 TGT tail gas treatment
27 TMEDA N,N,N’,N’-tetramethylethylendiamine
28
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44 equilibria in aqueous HCl and NaCl solutions at 298.15 K, J. Chem. Eng. Data 47 (2002)
45 1339-1345.
46 [109] J. Rodriguez-Sevilla, M. Alvarez, M.C. Diaz, M.C. Marrero, Absorption equilibria of
47 dilute SO2 in seawater, J. Chem. Eng. Data 49 (2004) 1710-1716.
48 [110] Z. Zhihua, Z. Zhihong, The study of influence factor to desulphurization efficiency in
49 seawater, in: 2nd International Conference on Bioinformatics and Biomedical Engineering,
50 iCBBE 2008, Shanghai, 2008, pp. 3731-3733.
33
1 [111] EPA, AP 42 compilation of air pollutant emission factors - Sulfuric acid, website:
2 http://www.epa.gov/ttn/chief/ap42/ch08/final/c08s08.pdf (10.05.12).
3 [112] EFMA, Production of sulphuric acid, in: Best available techniques for pollution
4 prevention and control in the european fertilizer industry, European fertilizer manufacturers’
5 association, Brussels, 2000.
6 [113] H. Müller, Sulfuric acid and sulfur trioxide, in: Ullmann's encyclopedia of industrial
7 chemistry, Wiley-VCH Verlag GmbH & Co. KGaA, 2000.
8 [114] A.A. Kiss, C.S. Bildea, J. Grievink, Dynamic modeling and process optimization of an
9 industrial sulfuric acid plant, Chem. Eng. J. 158 (2010) 241-249.
10 [115] J.C. Schöneberger, H. Thielert, A new process concept for an emission free sulphuric
11 acid plant, 8th European Congress of Chemical Engineering, Berlin, 2011.
12
34
1 Figures
2 Figure 1. Modelling approaches for reactive absorption (adapted from [3])
3 Figure 2. Molecule structure of amines
4 Figure 3. Process flow diagram of an absorption / desorbtion process
5 Figure 4. CO2 origin and process flow (adapted from [27])
6 Figure 5. Selection of appropriate gas purification process for simultaneous H2S/COS and CO2
7 removal (adapted from [21])
8 Figure 6. Primary sources of NOx emission in global scenario (adapted from [71])
9 Figure 7. Nitric acid production - Dual pressure plant (adapted from [95])
10 Figure 8. Flow diagram of high-strength nitric acid production from weak nitric acid (adapted
11 from [95])
12 Figure 9. Schematic of a limestone gypsum FGD process (adapted from [98])
13 Figure 10. The Seawater washing process (adapted from [98])
14 Figure 11. The ammonia scrubbing process (adapted from [98])
15 Figure 12. The Wellman-Lord process (adapted from [98])
16 Figure 13. General diagram of sulphuric acid production (adapted from [112])
17 Figure 14. Sulphuric acid plant (double absorption) based on sulphur combustion (adapted from
18 [112])
19 Figure 15. Flowsheet of a modern sulfuric acid production plant [114].
20 Figure 16. Temperature (above) and composition profiles (below) along the two SO3 absorption
21 columns
35
1
2
3
4 Figure 1. Modelling approaches for reactive absorption (adapted from [3])
5
6
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 N CH3 HO C C O C C N
NH
C CC H
CC OH HO
Diisopropanolamine Methyldiethanolamine 2 (2-aminoethony) ethanol
7
8 Figure 2. Molecule structure of amines
9
36
1
2
3 Figure 3. Process flow diagram of an absorption / desorbtion process
4
N 2 /O2
Post-combustion
Separation by
Power CO2 CO 2
Gas, Biomass
absorption
plant separation
Gasification CO / H 2
H2 H2 N 2 /O 2
CO2 Power CO2
Natural
Shift plant
CO 2
separation compression
CO / H 2
Reforming Pre-combustion
Oil,
CO 2
Coal,
Power
plant Oxy-combustion
O2
N2
Air Air separation
5
6 Figure 4. CO2 origin and process flow (adapted from [27])
7
37
CO2 content, ppm (mL/m³)

10 100 1000 10000
30
Physical
Rectisol Sulfinol and
10 ZnO Purisol MDEA chemical
Partial pressure of H2S/COS and
Spasolv DEA solvents

Rectisol Selexol
1
CO2 in gas feed, bar
Chemical solvents
Sulfinol Hot pot

Amisol
Benfield- Benfield
Hi-pure DGA
0,1
ZnO
Molecular sieves
0,01
0,1 1 5 10 100 1000
Sulfur in product gas, ppm (mL/m³)
1
2 Figure 5. Selection of appropriate gas purification process for simultaneous H2S/COS and
3 CO2 removal (adapted from [21])
4
5
61%
18%
Transportation
14%
Industry-energy
Industry-producton
6%
1%
Energy
Others
6
7
8 Figure 6. Primary sources of NOx emission in global scenario (adapted from [71])
9
10
38
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
1
2
3 Figure 7. Nitric acid production - Dual pressure plant (adapted from [95])
39
H2SO4
HNO3, NO2, O2 Cooling Water
50-70%
HNO3
Condenser
Air
Absorption
Dehydrating Bleacher O2, NO Column
Column
Strong
Nitric Acid
Weak
Nitric Acid
1
2 Figure 8. Flow diagram of high-strength nitric acid production from weak nitric acid (adapted
3 from [95])
4
5
6
7
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
8
9
10 Figure 9. Schematic of a limestone gypsum FGD process (adapted from [98])
11
40
Flue
By-pass
damper
Flue gas
Inlet damper Outlet

damper
Booster fan
Absorber
Reheater
Sea water from
condenser
Packing
Oxidation air
Return to sea
2
3 Figure 10. The Seawater washing process (adapted from [98])
4
Precipitator
Flue gas Flue
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
5
6 Figure 11. The ammonia scrubbing process (adapted from [98])
7
41
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
1
2 Figure 12. The Wellman-Lord process (adapted from [98])
3
4
5
6
7
8
9 Figure 13. General diagram of sulphuric acid production (adapted from [112])
42
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
1
2 Figure 14. Sulphuric acid plant (double absorption) based on sulphur combustion (adapted
3 from [112])
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
4 88°
5 Figure 15. Flowsheet of a modern sulfuric acid production plant [114].
43
1
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 / [-]
2
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 / [-]
3
4 Figure 16. Temperature (above) and composition profiles (below) along the two SO3
5 absorption columns
44
1 Tables
2 Table 1. Industrial applications of absorption [2]
3 Table 2. Reactive absorption units [3]
4 Table 3. Qualitative characteristics of the amines for the removal of CO2 (adapted from [21])
5 Table 4. Main properties for the most common amines (adapted from [22])
6 Table 5. CO2 removal application in major industrial processes (adapted from [24])
7 Table 6. Desired quality of treated syngas for various downstream application (adapted from
8 [15])
9 Table 7. Typical exhaust gas composition (adapted from [29])
10 Table 8. Reactive absorption processes for the capturing of CO2 (adapted from [28])
11 Table 9. Reactive absorption processes for the capturing of H2S (adapted from [28])
12 Table 10. Reactive absorption processes for the capturing of CO2/ H2S and other components
13 (adapted from [28])
14 Table 11. Pressures of single and dual pressure processes [95]
15 Table 12. Main producers of nitric acid in the United States and Europe
16 Table 13. List of plants build after 1990 in Western Europe (adapted from [112])
17
45
1
2 Table 1. Industrial applications of absorption [2]
Gas dehydration
The gas industry Removal of CO2 and H2S
Selective absorption of H2S
Hydrocarbon absorbers for lean oil
H2S absorption
Refineries
Various types of stripping columns
Sour water strippers
Synthesis gas processing
Gas saturation
The petrochemical industry
Ethylene oxide absorption
Acrylonitrile absorption
Synthesis gas processing (CO2 removal)
Chlorine drying
The chemical industry
HCL and ammonia absorption
Absorption of nitrous gases
Sulphur dioxide absorption
The cellulose industry Chlorine dioxide absorption
Flue gas scrubbing with sulphur recovery
Stripping various components producing odors
Food processing Processing fatty acids
Hexane absorption and stripping
Absorption of triethylamine (in foundries)
The metal & packaging
Absorption of lube & cooling oils
industries
Absorption and recovery of solvent vapors
Removal of acid components (wet- and dry-scrubbing of SOX &
NOX)
Exhaust air scrubbing
Removal of base components
Removal & recovery of organic solvents
Air stripping of chlorinated hydrocarbons
Wastewater/sewage treatment
Desorption and recovery of ammonia
and pollution control
Effluent neutralization
Deaeration of seawater
3
46
1
2 Table 2. Reactive absorption units [3]
Unit group criterion Unit type
Both phases in a continuous form • packed columns
• thin film contactors
• wetted-wall columns
• contactors with flat surface
• laminar jet absorber
• disc (sphere) columns
A disperse gas phase and a continuous • plate columns
liquid phase • plate columns with packing
• bubble columns
• packed bubble columns
• mechanically agitated columns
• jet absorbers
A disperse liquid phase and a continuous • spray columns
gas phase • venturi scrubber
3
4
5 Table 3. Qualitative characteristics of the amines for the removal of CO2 (adapted from [21])
Amines
primary secondary tertiary
MEA DEA TEA, MDEA
high enthalpy of reaction low
high enthalpy of evaporation low
high reaction rate low
high corrosivity low
low loading high
6
7
8
47
1
2 Table 4. Main properties for the most common amines (adapted from [22])
Property | Amine MEA MDEA AEEA DETA AMP PZ
Chemical formula C2H7NO C5H13NO2 C4H12N2O C4H13N3 C4H11NO C4H10N2
MW (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
Vapor pressure, 293 K (kPa) 0.0085 0.0013 0.00015 0.02 0.1347 0.1066
Vapor pressure, 393 K (kPa) 15.9 - 0.969 - - 41.66
Solubility at 293 K Soluble Soluble Soluble Soluble Soluble 14 %wt
st
Pseudo 1 order rate constant 7000 3.5 12100 49740 681 53700
at 298 K (m3/kmol/s)
Activation energy (kJ/mol) 46.7 44.3 - - 41.7 35
Absorption capacity 0.5 1.0 1.0 1.0 1.0 1.0
(mol CO2 / mol amine)
3
4 Table 5. CO2 removal application in major industrial processes (adapted from [24])
Process Common cleanup targets
Hydrogen manufacture < 0.1% CO2
Ammonia manufacture < 16 ppm CO2
Natural gas purification:

Pipeline gas < 1% CO2
LNG feedstock < 50 ppm CO2
Synthesis gas for chemical (H2/CO) < 500 ppm CO2
Coal gasification ~ 500 ppm CO2
Ethylene manufacture (steam cracker gas

~ 1 ppm CO2
treating)
Power plants:
NGCC power plant < 0.5 % CO2
Coal fired power plant < 1.5% CO2
48
1
2 Table 6. Desired quality of treated syngas for various downstream application (adapted from
3 [15])
Downstream use Power Hydro-processing Chemical
Sulfur (wppm) 10–15 <1 < 0.01–1
CO2 (vol.%) – < 0.1 0.05–2.0
CO – < 50 wppm H2/CO control as per
requirement
4
5
6 Table 7. Typical exhaust gas composition (adapted from [29])
mol-%
Water
N2 CO2 O2 NOx SO2 Ash
vapor
Coal-fired up to
70-75 12-16 3-4 6-7 400 ppm 150 ppm
powerplant 30 ppm
Gas-fired
70-75 3-5 10-12 7-10 < 50 ppm < 10 ppm -
powerplant
7
8
49
1 Table 8. Reactive absorption processes for the capturing of CO2 (adapted from [28])
2
Process Licensor solvent Installations
Amine Guard UOP LLC Ucarsol • 500+ units worldwide

FS (MDEA-based) • mostly treating natural gas, ammonia
syngas and hydrogen 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 gasification and
petrochemical applications
Kerr- Randall Gas ME A • 4 on coal-fired boiler flue gases
McGee/ABB Technologies, • 2 produce gaseous chemical-grade
Lummus Global ABB Lummus CO2
Absortion/stripp Global Inc. • 2 produce food-grade liquid.
ing technology
Fluor Fluor MEA >30% • 24 units worldwide
Econamine FG Enterprises, Inc. • Recover CO2 from low-pressure, O2
Plus process containing streams: burner flue gas,
combined cycle gas turbine flue gas
and coal-fired power plant flue gas
streams
LRS 10 – CO2 Advantica Ltd. DEA promoted • 30 plants worldwide
removal potassium • mainly retrofits in the ammonia,
carbonate hydrogen, natural gas and chemicals
industries
3
50
1
2 Table 9. Reactive absorption processes for the capturing of H2S (adapted from [28])
Lurgi tail-gas Lurgi Oel- MDEA • Six LTGT units for processing Claus tail
treatment process Gas-Chemie gases in operation or under design
(LTGT) GmbH
Fluor Fluor - • Three plants engineered or constructed
hydrogenation/ Enterprises,
amine Claus tail Inc.
gas treating
Process
HCR (high Claus SIIRTEC - • First commercial plant started in
Ratio) NIGI November 1988
• Since then 10 plants under construction
3
51
1
2 Table 10. Reactive absorption processes for the capturing of CO2/ H2S and other components
3 (adapted from [28])
Resulf CB&I TPA MDEA or • 45 Resulf Units

formulated • 3 Resulf-10 units
MDEA • 2 Resulf-MM units
• Purification of sulfur recovery unit (SRU) tail gas for
incineration.
ADIP Shell Global Secondary amine • 400+ ADIP units in operation or under construction.
Solutions DIPA or MDEA • Removal from natural gas, refinery gases and synthesis
International Amine % 50 gases.
B.V. • Removal of H2S, CO2, COS from liquefied petroleum
gas or natural gas liquids
ADIP-X Shell Global MDEA + additive • Applied in one natural gas application
Solutions • Removes products from natural gas, refinery gas and
International synthesis gas H2S can be reduced to low-sulfur levels.
B.V.
Advanced Prosernat-IFP High load DEA • 120+ units
amines Group Selective MDEA • amine based process to sweeten natural gases.
Technologies Activated MDEA • Cover all types of acid gas removal applications.
aMDEA BASF AG MDEA • 200+ plants operating
process • 30+ under design or construction, mostly treating
synthesis gas, natural gas and hydrogen streams
Amine UOP LLC Ucarsol (MDEA- • 500+ units worldwide
Guard FS based solvent) • mostly treating natural gas, ammonia syngas and
hydrogen streams
Benfield UOP LLC Hot potassium • 700+ units worldwide
carbonate • 65+ treat natural gas
• 200+ treat ammonia syngas
• 110 in hydrogen plants
• Other applications: in SNG, partial oxidation, coal
gasification and petrochemical applications
Fluor Fluor DGA • 55+ Econamine plants
improved Enterprises, • 7 improved Econamine plants
Econamin Inc.
e
52
1 Table 11. Pressures of single and dual pressure processes [95]

Single pressure process Dual pressure process
Oxidation pressure 1 - 14 bar 1 - 6.5 bar

Absorption pressure 1 - 14 bar 6.5 - 13 bar
2
3
4 Table 12. Main producers of nitric acid in the United States and Europe
Company and location Capacity Regional market share
(thousands of (% in 2010)
metric tons)
CF Industries (incl. Terra) 2,635 30.7 (US)
PCS Nitrogen 1,565 18.2 (US)
LSB Industries 1,240 14.5 (US)
Dyno Nobel, Inc. 655 7.6 (US)
Invista Inc. 470 5.5 (US)
Yara Internat. (incl. 50% GrowHow UK) 6,760 45.8 (West EU)
BASF (incl. 50% Prod. Eng. Chim. Rhin) 2,500 16.9 (West EU)
Grande Paroisse (+ Prod. Eng. Chim. Rhin) 1,290 8.7 (West EU)
Fertiberia S.I. (incl. Adubos du Portugal) 925 6.3 (West EU)
OCI Nitrogen (formerly DSM Agro B.V.) 755 5.1 (West EU)
5
6
7
53
1
2 Table 13. List of plants build after 1990 in Western Europe (adapted from [112])
Capacity
Location Process type Costs Company Year Emission level
t H2SO4.d-1
Cu Smelter acid
Hamburg, Norddeutsche < 800mg
(5-8.4% SO2) 1M EUR 918t.d-1 1991
Germany Affinerie SO2.Nm-3
Helsingborg, Sulphur burning 36M < 0.9kg SO2.t-1

Kemira Kemi 1,000t.d-1 1992
Sweden (17.5% SO2) EUR H2SO4
Copper and nickel

Harjavalta, 33M Outokumpu
based smelter acid 2,430t.d-1 1995 < 4,500t SO2.y-1
Finland EUR extension
(7-12% SO2)
Tessenderlo, Sulphur burner Tessenderlo

n/a 1,000t.d-1 1992 300ppm SO2
Belgium (11.5% SO2) Chemie
Leuna, 99.9%
Sulphur burner n/a Domo n/a 1996
Germany conversion rate
Huelva, Cu Smelter acid 39M Atlantic
1,270t.d-1 1996 >99.6%
Spain (5-10.2% SO2) EUR Copper
Ludwigs-
0.65kg SO2.t-1
hafen, Sulphur burner n/a BASF 900t.d-1 n/a
H2SO4
Germany
Le Havre, Sulphur burner 2.6kg SO2.t-1
n/a Millennium 800t.d-1 1992
France (11.5% SO2) H2SO4
Huelva,
n/a n/a Fertiberia 2,400t.d-1 2000 n/a
Spain
Spent acid
Worms, 53M
regeneration; Rhöm GmbH 500t.d-1 1994 n/a
Germany EUR
H2SO4 (NH4)2 SO4
3
4
54
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Reactive absorption in chemical process industry: A review on current

Article in Chemical Engineering Journal · December 2012

Ömer Yildirim Anton A. Kiss

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Nicole Hüser Eugeny Y. Kenig

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1 Reactive absorption in chemical process industry:

7 Ionization of dissolved H2S H 2 S ↔ H + + SH − (2)

8 Hydrolysis and ionization of dissolved CO2: CO2 + H 2O ↔ HCO3− + H + (3)

9 Protonation of alkanolamine: RNH 2 + H + ↔ RNH 3+ (4)

10 Carbamate formation: RNH 2 + CO2 ↔ RNHCOO − + H + (5)

9 CO2 + OH − ↔ HCO3 − (fast) (7)

10 HCO3− + OH − ↔ CO32 − + H 2O (instantaneous) (8)

11 Mechanism 2. Reaction of CO2 with water and dissociation of HCO3:

12 CO2 + H 2O ↔ H 2CO3 (slow) (9)

13 H 2CO3 + OH − ↔ HCO3− + H 2O (instantaneous) (10)

1 [33] as well as in LPG (liquefied petroleum gas) production [40].

18 2.1.2 Research activities

1 2.2.1 Industrial applications

1 absorption steps. In dual-pressure (split-pressure) processes, the absorption pressure (6.5-13

14 2.3.2 Research activities

19 2.4.1 Industrial applications

13 2.5.1 Industrial applications

25 2.5.2 Research activities

1 [43] M. Wang, A. Lawal, P. Stephenson, J. Sidders, C. Ramshaw, Post-combustion CO2

1 [65] C. Stankewitz, H. Fahlenkamp, Integration of a subsequent CO2 scrubbing in the coal-

CO2 content, ppm (mL/m³)

Spasolv DEA solvents

Sulfinol Hot pot

Air Filtration Evaporation Ammonia

Cold tail gas Heat recovery

Power NOx compression Hot tail gas

Process water Absorption Expander

Inlet damper Outlet

Booster fan Ammonia

By-pass damper Condenser

Air Sulphur Feedwater

Inter- Oleum Converter bed 1

Heat Converter bed 4

H2SO4 96-98% Oleum 20-37%

Furnace SO2 1 HX1

5 Figure 15. Flowsheet of a modern sulfuric acid production plant [114].

Molar fraction / [-]

Process Common cleanup targets

Hydrogen manufacture < 0.1% CO2

Ammonia manufacture < 16 ppm CO2

Natural gas purification:

Synthesis gas for chemical (H2/CO) < 500 ppm CO2

Coal gasification ~ 500 ppm CO2

Ethylene manufacture (steam cracker gas

Amine Guard UOP LLC Ucarsol • 500+ units worldwide

Benfield UOP LLC Hot potassium • 700+ units worldwide

Resulf CB&I TPA MDEA or • 45 Resulf Units

1 Table 11. Pressures of single and dual pressure processes [95]

Oxidation pressure 1 - 14 bar 1 - 6.5 bar

Helsingborg, Sulphur burning 36M < 0.9kg SO2.t-1

Copper and nickel

Tessenderlo, Sulphur burner Tessenderlo

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