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Review
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
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
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]) .
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
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
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]).
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-
Ö. Yildirim et al. / Chemical Engineering Journal 213 (2012) 371–391 377
Table 9
Reactive absorption processes for the capturing of H2S (adapted from [28]).
Table 10
Reactive absorption processes for the capturing of CO2/H2S and other components (adapted from [28]).
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
Ö. Yildirim et al. / Chemical Engineering Journal 213 (2012) 371–391 379
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 pro- of 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.
2.2.1. Industrial applications
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]).
380 Ö. Yildirim et al. / Chemical Engineering Journal 213 (2012) 371–391
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].
Ö. Yildirim et al. / Chemical Engineering Journal 213 (2012) 371–391 381
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
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
382 Ö. Yildirim et al. / Chemical Engineering Journal 213 (2012) 371–391
Air Filtration
Power compression
Heat Heating
Filtration
Mixing
Steam export
Catalytic
reactor
Superheated
steam
Boiled feed water Heat recovery Steam turbine
Heat recovery
Cooling water Cooler
Condenser
Atmosphere Power
Nitric acid
production
Fig. 7. Nitric acid production – dual pressure plant (adapted from [95]).
H2SO4
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]).
Ö. Yildirim et al. / Chemical Engineering Journal 213 (2012) 371–391 383
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
Flue
By-pass
damper
Flue gas
Absorber
Reheater
Sea water from
condenser
Packing
Oxidation air
Return to sea
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
Ö. Yildirim et al. / Chemical Engineering Journal 213 (2012) 371–391 385
Precipitator
Flue
Flue gas
By-pass damper
Fly ash
ID Fan
Pre-scrubber
Hydrocyclone
Centrifuge
Compactor Air
Bleed
Dryer
Bleed
Precipitator
Flue gas Flue
Sodium carbonate /
hydroxide
Blowdown
Water Sulphate
EDTA solids
Sodium carbonate or
hydroxide make-up Regenerated liquor
Tank Tank
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].
386 Ö. Yildirim et al. / Chemical Engineering Journal 213 (2012) 371–391
Fig. 13. General diagram of sulphuric acid production (adapted from [112]).
Main blower
Waste heat
Dryer Sulphur burner Stream
boiler
Water
Final
absorber Heat exchanger
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
Ö. Yildirim et al. / Chemical Engineering Journal 213 (2012) 371–391 387
430°
Air
Steam
50° 610°
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°
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
388 Ö. Yildirim et al. / Chemical Engineering Journal 213 (2012) 371–391
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 / [-]
Abs1_H2O Abs2_H2O
0.08 0.08
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
Ö. Yildirim et al. / Chemical Engineering Journal 213 (2012) 371–391 389
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