Research article Received: 5 April 2018 Revised: 11 January 2019 Accepted: 15 January 2019 Published online in Wiley Online Library (wileyonlinelibrary.com) DOI 10.1002/jib.560 Batch distillation of spirits: experimental study and simulation of the behaviour of volatile aroma compounds Adrien Douady,1 Cristian Puentes,1 Pierre Awad1,2 and Martine Esteban-Decloux1* This paper focuses on the behaviour of volatile compounds during batch distillation of wine or low wine, in traditional Charentais copper stills, heated with a direct open flame at laboratory (600 L) and industrial (2500 L) scale. Sixty-nine volatile compounds plus ethanol were analysed during the low wine distillation in the 600 L alembic still. Forty-four were quantified and classified according to their concentration profile in the distillate over time and compared with previous studies. Based on the online re- cording of volume flow, density and temperature of the distillate with a Coriolis flowmeter, distillation was simulated with ProSim® BatchColumn software. Twenty-six volatile compounds were taken into account, using the coefficients of the ‘Non- Random Two Liquids’ model. The concentration profiles of 18 compounds were accurately represented, with slight differences in the maximum concentration for seven species together with a single compound that was poorly represented. The distribution of the volatile compounds in the four distillate fractions (heads, heart, seconds and tails) was well estimated by simulation. Fi- nally, data from wine and low wine distillations in the large-scale alembic still (2500 L) were correctly simulated, suggesting that it was possible to adjust the simulation parameters with the Coriolis flowmeter recording and represent the concentration pro- files of most of the quantifiable volatile compounds. © 2019 The Institute of Brewing & Distilling Keywords: batch distillation; copper still; spirits; volatile aroma compounds; simulation Introduction desired. For instance, full-bodied, single malt whiskies are pro- duced with a batch method in traditional pot stills, while lighter The diversity of distilled spirits consumed around the world is grain whiskies are produced in multistage distillation columns (5). large. In Europe, the definition, description, labelling and protec- According to Ferrari et al. (6), the behaviour of volatile compounds tion of geographical indications of spirit drinks are specified in reg- is different during distillation in pot stills and rectification columns. ulation 110/2008 (1). The standard unit for ethanol concentration is Indeed, in contrast to esters, it was observed that larger quantities the alcoholic strength by volume (annex I point 11), or ABV (alco- of higher alcohols were recovered in the distillate in continuous hol by volume) in % v/v. The distillation process concentrates the distillation than in the simple batch process. ethanol and volatile aroma compounds from the fermented must, This study focused on the behaviour of volatile compounds dur- as well as those formed in situ through chemical reactions (2).The ing simple batch distillation. This method is generally conducted in quality and specific characteristics of a spirit beverage are highly a traditional copper still, known as an ‘alambic charentais’ (Fig. 1) dependent on the nature and concentration of the volatile (3,7–9). Distillation is carried out in two successive cycles. During compounds and, to a lesser extent, its ethanol concentration. the first cycle, known as ‘wine distillation’, the wine is introduced The volatile compounds responsible for the overall aroma percep- into the boiler. An initial small fraction of distillate (‘heads’)iscol- tion of spirit beverages belong to many chemical families, such as lected and separated. Distillation then continues until the ABV of alcohols, carboxylic acids, esters and aldehydes (2).Theprecise the distillate reaches ~2% v/v. This second fraction constitutes relationship between volatile compounds and aroma perception the low wine, with ethanol concentration between 27 and 30% is still difficult to assess, owing to the variable nature of volatile v/v. The second cycle is the low wine distillation. In analogy with compounds, concentration relative to sensory threshold and wine distillation, the first fraction of distillate (‘heads’)withthe possible synergies. The diversity of volatile compounds and differ- highest ethanol concentration is removed. The ‘heart’ is collected ences in concentration is mainly due to the raw materials, fermen- and separated once the ethanol concentration of the distillate tation method and the distillation process, which includes both the apparatus and the method (3,4). Three main methods are commonly used with a typical distilla- * Correspondence to: Martine Esteban-Decloux, AgroParisTech. 1 av des tion apparatus: (a) continuous distillation in a multistage distilla- Olympiades 91300 Massy, France. E-mail: [email protected] tion column (e.g. rum, vodka, Armagnac, Calvados, neutral 1 alcohol), (b) batch (simple discontinuous) distillation involving Unité Mixte de Recherche Ingénierie Procédés Aliments, AgroParisTech, INRA, recycling (e.g. Cognac, Armagnac, Auge, Calvados, rum) and (c) Université Paris-Saclay, F-91300, Massy, France batch distillation in a column involving recycling (fruit brandies). 2 Unité Mixte de Recherche Génie et Microbiologie des Procédés Alimentaires, The preferred method depends on the organoleptic qualities AgroParisTech, INRA, Université Paris-Saclay, 78850, Thiverval-Grignon, France J. Inst. Brew. 2019 © 2019 The Institute of Brewing & Distilling A. Douady et al. Table 1. Classification volatile compounds during batch distil- lation by Cantagrel (7) Type Classification of compounds during wine distillation 1 Acetaldehyde, 1,1-diethoxy-ethane, 1,1-diethoxy- methyl-2-propane, ethyl acetate, ethyl propanoate, ethyl butanoate, ethyl caproate, ethyl caprylate, ethyl caprate, ethyl laurate, ethyl myristate, ethyl palmitate, ethyl stearate, ethyl oleate, ethyl linoleate, ethyl linolenate, isoamyl acetate, isoamyl caprate 2 Furfural 3 Methanol 4 1-Propanol, 2-methyl-1-propanol, 1-butanol, 2-methyl-1- butanol, 3-methyl-1-butanol, 2-phenylethyl acetate 5 2-Phenylethanol 6 Ethyl lactate, diethyl succinate Figure 1. Diagram of a traditional Charentais copper still. Classification of compounds during low wine distillation reaches ~60% v/v. The average ethanol concentration of the heart 1 Acetaldehyde, 1,1-diethoxy-ethane, 1,1-diethoxy- must be <72.4% v/v for Cognac (10). The last two fractions are the methyl-2-propane, ethyl acetate, ethyl propanoate, ‘seconds’ and ‘tails’. The heart constitutes the spirit (or eau-de-vie) ethyl butanoate, hexyl acetate, ethyl caproate, ethyl and is placed in an oak barrel for aging. All the other distillate frac- laurate, ethyl myristate, ethyl palmitate, isobutyl tions are recycled back into the process. Several methods exist but caprate, isoamyl acetate, isoamyl caprylate, isoamyl heads and tails are usually recycled in the wine and seconds in the caprate, isoamyle myristate low wine. After the tails, when the gas burner is turned off, a small 2 2-Phenylethanol fraction of distillate, known as ‘petites-eaux’, is sent directly to the 3 Methanol distillation residue storage. 6 Furfural, 2-phenylethyl acetate, ethyl lactate, diethyl Despite its long history, batch distillation is still poorly under- succinate, caprylic acid, capric acid, lauric acid stood. In order to acquire knowledge about the behaviour of vola- 7 1-Propanol, 2-methyl-1-propanol, 1-butanol, 2-methyl-1- tile compounds, the National Interprofessional Committee of butanol, 3-methyl-1-butanol, ethyl stearate, ethyl oleate, Cognac conducted experimental investigations in 1989. Both distil- ethyl linoleate, ethyl linolenate lations (wine and low wine) were sampled in an operational plant. 8 Ethyl caprylate, ethyl caprate. Fifty-seven volatile compounds were analysed and 39 concentra- tion profiles in the distillate were drawn as a function of decreasing 8 were representative of highly volatile compounds that concen- ABV and classified in different types (7), as shown in Fig. 2 and trate in the first running of distillate. Types 3 and 4 were present Table 1. Types 1, 2, 3 and 6 were present in both wine and low wine in all fractions of distillate. Types 2, 5 and 6 corresponded to low distillations, while types 4 and 5 were specific to the wine distilla- volatile compounds, which increased in concentration with de- tion and types 7 and 8 to the low wine distillation. Types 1, 7 and creasing alcohol strength. Unfortunately, neither the composition Figure 2. Concentration profiles of volatile compounds during distillation. Adapted from (7,8). [Colour figure can be viewed at wileyonlinelibrary.com] wileyonlinelibrary.com/journal/jib © 2019 The Institute of Brewing & Distilling J. Inst. Brew. 2019 Batch distillation of spirits: experimental study and simulation of the liquids introduced into the boiler (ABV, volatile compound solution. In fact, when data predicted by this UNIFAC model were concentrations), the distillation parameters (heating power profile, compared with experimental findings of Athès et al. (25),the volumes, cut criteria) nor the concentrations of the volatile com- predicted volatility was overestimated and, consequently, the pounds in the distillates were reported in this study. More recently, predicted concentration in the heart. Lukić et al. (11) investigated the distribution of 155 volatile com- A good knowledge