v Sewrdsan eo Novel energy efficient process for acetic acid production by methanol carbonylation Alexandre C. Dimian,"" Anton A. Kiss? ! Polytechnic University of Bucharest, Polizu 1-7, 011061 Bucharest, Romania ? Department of Chemical Engineering and Analytical Science, The University of Manchester, Sackville Street, Manchester, M13 9PL, United Kingdom * Corresponding author: ac_dimian@chim.upb.ro Keywords Acetic acid; process design; process simulation; sustainable process; energy efficiency Highlights + Low-energy sustainable process (< 1 MJ/kg) for manufacturing green acetic acid + Full valorisation of reaction heat by steam generation and electricity made by ORC © Heat pumping by vapor compression for energy efficient acetic acid purification Abstract Acetic acid is an essential chemical product. The need for ‘green’ acetic acid has spurred new research in developing more sustainable processes. This paper presents an original conceptual design of a low-energy and low-emissions sustainable process for acetic acid manufacturing by methanol carbonylation, The emphasis is set on energy efficiency, since the exothermic reaction releases a large amount of energy that may be more effectively used. Two processes are investigated by rigorous simulation, based on homo- and heterogeneous catalysis. The latter reveals as innovative feature the full valorisation of the energy released in the reaction section, along with reducing the separation sequence to only two distillation columns. The first dewatering column is driven by low-pressure steam generated by the reactor cooling. The second purification column uses heat pumping, in which the energy rejected in condenser is upgraded for reboiler heating by vapor compression (VC), using water as working fluid. The electricity for the vapor compression is ensured by applying an Organie Rankine Cycle (ORC) for waste heat recovery by the reactor cooling. In this way, the new green process needs very little energy (below 1 MJ/kg product). This eco-efficient process shows also superior sustainability metrics (e.g. low emissions of 40 gCOze/kg) as compared to the homogeneous catalyst process.nw Sewer asn nw [Novel energy offiont process for acetic ac production by methanol carbonytation Dimian & Kiss 1. Introduction Acetic acid is a major essential chemical product, being an important chemical reagent used primarily in the production of cellulose acetate, vinyl acetate monomer and polyvinyl acetate, acetic anhydride, monochloroacetic acid, acetate esters, terephthalic acid, and synthetic fibres and fabries (Le Berre et al., 2014), It is often used in descaling agents, or as food additive. ‘The global market size was 16.3 million tons in 2018, and it is further expected to reach a volume of about 20.3 million tons by 2024 (Marketwatch, 2019). Asia-Pacific has currently the highest market share, followed by North America, Europe, Middle East and Africa. Amidst growing environmental awareness and more stringent regulations worldwide, there is s (Pal and Nayak, 2017), The development and advances in acetic acid processes and catalysts aim am imminent shift of acetic acid production strategy in favour of greener process: primarily to reduce the raw material consumption, energy requirements, and investment costs (Yoneda et al., 2001). The most important processes for acetic acid production are the carbonylation of methanol, vapor phase-oxidation (ethane and ethene), liquid-phase oxidation (n-butane and naphta), acetaldehyde oxidation, oxidative and anaerobic fermentation (Yoneda id by methanol carbonylation takes the largest market share (about 75%), in continuous growth. et al., 2001; Le Berre et al., 2014). Among them, the manufacturing of acetic a Research strategies to improve the catalyst performance and process economies of methanol carbonylation resulted in both rhodium- and iridium-catalyzed systems that operate with high activity at reduced water concentration (Haynes, 2010). More sustainable catalysts have been explored, such as immobilized rhodium and iodide species on cross-linked copolymers (Li et al., 2013), heterogeneous rhodium-incorporated graphitic carbon nitride (Nam et al., 2017), a halide-free and noble metal-free catalyst based on pyridine-modified H-mordenite zeolite (Ni et al., 2017). The trend of using methanol carbonylation is favourable from a sustainability viewpoint, as both raw materials can be obtained from any feedstock leading to syngas, such as biogas and biomass. For this reason, acetic acid can be a 100% green product, and on this basis promotes the synthesis of other bio-based chemicals. For example, the vinyl acetate monomer (VAM) manufactured from acetic acid and ethylene (Dimian and Bildea, 2008) becomes a bio-based product, as well as the valuable vinyl paints. In this way traditional petrochemicals can be replaced by green products obtained from a syngas bio-refinery platform (Dimian, 2007; Dimian et al., 2019). Other processes based on renewable materials include hydrothermal processing of biomass waste (Jin et al., 2007), integrated production in a pyrolysis oil-based biorefinery (Vitasari et al,, 2015), and the fermentation of sugar residue solutions driven by suitable bacteria (Vidrahoe Sewr dann "Novel energy offiont process for acetic ac production by methanol carbonytation Dimian & Kiss and Nemeth, 2018). Despite the ecological interest, the economic efficiency is penalized by high energy use in the separation and purification operations (Kiss et al., 2016). The result is that the fermentation process is limited nowadays to only 10% of the market, A novel route reported recently involves the hydro-carboxylation of methanol with CO, and Hz (Qian et al., 2016). The reaction can be efficiently catalysed by Ru-Rh bimetallic catalyst using imidazole as ligand and Lil as promoter in 1,3-dimethyl-2-imidazolidinone (DMI) solvent with outstanding reaction results. This method could open a road to fix CO; into bulk chemicals, but it is questionable whether the hydrogen manufacturing price could be competitive enough, This might be the case if hydrogen is produced by electrolysis using renewable energy, while methanol is used for energy storage. This study focuses on the conceptual design of a novel low-energy sustainable process for acetic acid manufacturing by methanol carbonylation, using heterogeneous catalysis. This key feature is obtained by full valorisation of the energy released by the exothermal reaction, The energy efficiency is improved by steam generation (by reactor cooling), as well as using vapour compression (VC) coupled with an Organic Rankine Cycle (ORC) that recovers the cid reactor’s effluent enthalpy. The plant capacity considered in this work is 200 ktpy a with a target purity of 99.7 %wt. The analysis and design is performed by employing the rigorous process simulator Aspen Plus v9.0. 2. Production processes and technologies The methanol carbonylation can be described by the following stoichiometric equation, with a theoretical carbon yield of 100%: (CHs-OH + CO — CH;-COOH (with AHj,298 = -135.6 kJ/mol) a The reaction is moderately exothermic and thermodynamically favoured by lower temperature. The industrial operation range is usually 15 to 200 °C and pressures of 30 to 60 bar (Le Berre, 2014), Although the overall stoichiometry is simple, the chemistry is complex considering the catalytic reaction mechanism. 2.41 Catalysis and technology issues Methanol carbonylation may involve rhodium catalyst (Monsanto process) or iridium-base catalyst (Cativa™ process) as homogeneous catalysts (Jones, 2000; Le Berre et al., 2014) The reaction takes place in liquid phase at 150-200 °C and 30-60 bar. Methyl acetate is used as solvent for the catalytic complex. The elementary reactions are (Moulijn et al., 2013): CH;-OH + HI CHsI + HO AH, 298 =-53.1 kJ/mol 2)hoe Sowa dan nw "Novel energy offiont process for acetic ac production by methanol carbonytation Dimian & Kiss CH3I+ CO + CH;COL AH,295 = -66.9 kJ/mol @) 15.6 ki/mol @) Details about the reaction mechanism and implications on kineties may be found in Jones CH;COI + HO > CH;COOH + HI AH,208, (2000). The key stage reaction (3) involves a metallic complex, with Rh or Ir. In the first case, the metallic complex [Rh(CO)zl:] reacts initially with CHs1 giving [Rh(CO)Meb]. This intermediate undergoes a molecular rearrangement leading to the formation of an acyl group [Rh(CO)(CO-Me)hs]. Further, the addition of a CO molecule leads to an unstable intermediate [Rh(CO):(CO-Me)ls]. It follows the expulsion of the acyl iodide CHsCOI and the hydrolysis reaction (4) that produces the acetic acid and HI. The initial catalytic complex is rebuilt, as well as HI that re-joins the cycle. CHsl, HI and H,0 implied in the catalytic eycle are recovered and recycled. Controlling the amount of water is a key factor in process design. Water is formed directly by the esterification of the acetic acid with methanol, but it comes mainly by recycling from the separation section, When the water content is higher than 8 % wt, the rate determining step in is the addition of CHsI to the Rh centre: Reascoon = kX{Rh]<[CHsI] ©) The reaction rate is essentially first order in both catalyst and methyl iodide concentrations, but independent of the reactants concentrations, CH;OH and CO. Therefore, high conversions can be obtained even in a CSTR of small volume (Moulijn et al., 2013). If the water content is less than 8% wt., the rate determining step is the reductive elimination of the acyl species. Keeping the integrity of the catalyst is essential. The main cause of catalyst loss by precipitation is the reaction of rhodium-acyl species with HI that leads to acetaldehyde and the complex [Rh(CO)L,]’. The latter may cause a catalyst loss by precipitation of the inactive and insoluble Rhls, when the CO concentration is insufficient. [Rh(CO)(CO-CH;)k] +H —> CHs-CHO + [Rh(CO)L] > Rls + + CO © Although rhodium-catalysed carbonylation of methanol is highly selective, it suffers from some disadvantageous side reactions, as for example the water-gas shift reaction. Further methane appears by reaction of hydrogen with methanol: CO+HH,O > CO2+ Hp a CHOH + Hp CH: + 20 8) ‘These side reactions may reduce the amount CO available for reaction down to a point where the catalyst integrity is threatened. Another unwanted reaction is the formation of acetal- dehyde, The reaction with hydrogen gives ethanol, which by carbonylation forms propionic acid as the main heavy impurity. High boilers can be formed by aldol condensation reactions.ea ans [Novel energy offiont process for acetic ac production by methanol carbonyfation Dimian & Kiss CH:-CHO “5 CHy-CH:-OH 5 CHs-CH:-COOH O} The alternative of using iridium as coordinating metal is justified by its price, 17 times lower than that for rhodium (Jones, 2000). Moreover, this brings a significant modification in the reaction mechanism with strong impact on the process performance. The oxidative addition of methyl iodide to the iridium centre is about 150 times faster compared to thodium, and thus does not determine the reaction rate. The slowest step becomes the methyl migration to form the acyl complex. This step involves substitution of iodide centre with CO. Thus, the reaction rate dependence is totally different from that for the Rh catalysed process: kx (Ir][CO] AT] (10) The inverse dependence on the ionic iodide concentration implies that removing it increases Reuscoot the reaction rate. This operation is done by promoters, such as iodide complexes of zine, cadmium, mercury, gallium and indium, as well as carbonyl-iodide complexes of tungsten, rhenium, ruthenium and osmium. The use of promoters can increase considerably the reaction rate, up to 20 times by a molar ratio In/Ru of 5. The Japanese company Chiyoda (www.chiyodacorp.com) developed the CT-ACETICA™ process that uses a heterogeneous catalyst in which the rhodium complex is immobilized on a vinyl-pyridine resin. In this way the catalyst remains in the reaction space and its integrity is preserved. Since the amount of water drops under 2%, the energy for dehydrating the acetic acid is drastically reduced. The same type of reaction system is used in the new integrated process proposed here, which has the additional advantages of improved overall efficiency due to effective energy integration and waste heat recovery by vapor compression and ORC. 2.2 Reactor technology Figure 1 depicts the type of industrial reactors employed by methanol carbonylation, Processes based on homogeneous catalyst makes use of CSTR-type reactor with mechanically stirring or gas injection device, working at pressures of 30-40 bar and temperatures of 180- 250 °C (Jones, 2000), as depicted in Figure 1 left-hand. The reactor is provided with external heat exchanger for cooling by s generation (SG). A slurry gas-liquid tower reactor was developed for using heterogeneous catalyst (Yoneda et al., 2001), as illustrated by Figure 1 right-hand. ‘The gas is injected at the bottom through an efficient distribution device to saturate the liquid phase in CO. An external loop for liquid-phase circulation is created by the density difference caused by the CO consumption. The reaction takes place in the riser, while the downcomer ensures catalyst recycle and heat transfer through an external exchanger.when [Novel energy offiont process for acetic ac production by methanol carbonytation Dimian & Kiss Gaz Product venting a Catalyst t Ne t ° L pes ° ‘ : Je MeOH og toe és] f MeOH —*/ Recycle Figure 1. Chemical reactors for methanol carbonylation (left: homogeneous process, right: heterogeneous process) 2.3 Process design A generic flowsheet is available regarding the technology employed by the Monsanto process (Le Berre, 2014), This employs a three columns separation sequence: the first two handle the removal of light-ends and water, while the third the acetic acid purification. By this approach the species involved in the catalyst complex, as described before, are fully recycled to reactor: The same conceptual flowsheet is used by Cativa and CT-ACETICA processes. However, no details about the process design were given in terms of design and performance of reactor and separators, as well as energy integration of units This paper presents the first approach of analysis and design of such process, which is based ‘on computer simulation, The energy released by reaction, considering kinetic industrial data, reveals substantial capabilities for sustaining the energetic needs of the separation section. ‘Two flowsheet altematives are proposed, based on homogeneous and heterogeneous catalysis. The first is closed to the actual industrial flowsheet, but proposes a quantitative assessment of the reaction section, the evaluation of the separations, as well as a first energy integration level. This is also the reference case in the sustainability analysis. The second alternative employs only two distillation columns and incorporates advanced energy integration methods, as heat pumping and on-site electricity production by Organic Ranking Cycle (ORC). The comparison of alternatives by sustainability analysis reveals that the second one demonstrates very low energy consumption, CO2 emissions and process water usage. To put it in a nutshell,wwe Seward Hwa i 12 13 [Novel energy offiont process for acetic ac production by methanol carbonytation Dimian & Kiss this work reports the best process design performance to date, to the best of our knowledge, 3. Process design and simulation based on homogencous catalyst ‘The plant capacity corresponds to a production rate of 25,000 kg/h or 416.3 kmol/h, The 9 inary plant material balance based on industrial stoichiometric amounts of raw materials are both 416.3 kmol/h methanol and CO, or 1 kg/h and 11,661 kg/h, respectively. A pr. data for Rhodium catalyst (Le Berre, 2014), the yield estimates the yield as 98% for methanol, and 95% for CO. The lower value for CO may be explained by secondary reactions leading to impurities and gases as CO2, H and CHy. ‘The analysis and simulation work was done by employing the process simulator Aspen Plus v9.0, The thermodynamic modelling involves highly non-ideal mixtures, namely acetic acid/water, and polar supercritical gases, for which suitable models are given in Appendix. 3.1 Reaction section Since the reaction is fast it achieves practically full CO conversion with excellent yield. In the workable regime, the reaction rate can be mastered by keeping constant the composition of the catalytic complex, including co-catalyst and promoters, since the reaction is zero-order with respect to the concentration of reactive species. For the purpose of this paper a practical kinetic approach is assumed by considering industrial reaction rate data. As indicated in Table ‘A-I (see Appendix) by experiments 5 to 7, a reaction rate R of about 20 kmol/m’sh is assumed as achievable for a mixture composition with methyl iodide as 6-10 %wt., methyl acetate 16- 20 %wt., and water 4-5 %wt. This requirement is solved by a separate input stream that considers the above species recovered by recycles. In addition, this approach offer a realistic description of the reaction mixture involved further in separations (Sunley and Watson, 2000), ‘A first design issue is recovery and recycling all the components of the catalyst recipe carried out to the separation section, namely the volatile methyl iodide and methyl acetate, as well as controlling the amount of water in reactor. The use of on-line FTIR spectrometry allows monitoring the amounts of species mentioned before, as well as quantifying the production rate (Keit company, 2019). A second issue is keeping constant the temperature in reactor and managing the large amount of heat released by reaction. This requirement is achieved by building efficient cooling and energy recovery procedures, as presented in this paper. Figure 2 presents the flowsheet of the reaction section, This comprises the reactor RSTOIC modelling the reaction, followed by a flash unit FL-1 introduced for describing the vapor- liquid equilibrium. The gas stream is condensed at 5 °C, the liquid being recycled to thehoe nh we 15 16 7 18 19 20 2 22 "Novel energy offiont process for acetic ac production by methanol carbonytation Dimian & Kiss reactor, while the gas leaves as vent stream, The liquid reaction mixture is split further in a process stream and a liquid recycle stream that enters the cooling loop. The reactor effluent is depressurized and vaporized in the FLASHER unit in view of separating the catalyst, recycled as bottom stream to the reactor. Figure 2. Simulation flowsheet of the reaction section. The reactor modelling is based on stoichiometry. The main reaction has a fractional conversion of 0.98, Secondary reactions describe the formation of by-products and impurities: + Formation of gaseous impurities (relations 7 and 8), lumped in the reaction: CO + CH;OH = CO) + CHy (molar extent of reaction 2 kmol/h) (11) + Esterification of acetic acid with methanol: (CH;-COOH + CH;-OH = CH3;-COOCH3 +H,0 (molar extent of reaction 2 kmol/h) (12) * Formation of propionic acid: (CH}-COOH + CHs-OH = CHs-CH;-COOH +H;0 (molar extent of reaction 4 kmol/h) (13) ‘The reactant inputs are methanol (424.8 kmol/h= 13612 kg/h) and CO (438.2 kmol/h= 12,274 kg/h), according to the preliminary material balance formulated before. Methanol is preheated at 100 °C, while the CO stream is compressed at 35 bar in a four-stage compressor with inter- mediate cooling at $0 °C except the last adiabatic stage where the temperature rises at 152 °C. In addition, a recycle stream from separations is considered containing acetic acid (1,000 kg/h), methyl acetate (2,000 kg/h), methyl iodide (2,000 kg/h), and water (1,500 kg/h). The metal catalyst is not introduced explicitly in simulation due to obvious modelling constraints.