Non-Alcoholic Beer—a New Industrial Process

Separation and Purication Technology 79 (2011) 342 351

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Separation and Purication Technology

jou rn al h om epa g e: www.elsev ier .com

Non-al

MargaridLEPAE, Chemic as, 420

a r t i c l

Article history:Received 10 JuReceived in reAccepted 4 Ma

Keywords:DealcoholizatiAroma recoveBeerPervaporationSpinning cone

procpoung polrmeand th

of a contcomp

and wood

clos

1. Introdu

The marimprovemeing/drinkinthe available non-alcoholic beverages present a poor avour prolethat is not accepted by the consumers. Hence, it becomes impor-tant to adjust the avour of non-alcoholic beverages to the typicalalcoholic ones, to ll the lack in this market supply. Typical non-alcoholic brfermentatioDuring the fas higher athe aroma amentation, towards thecesses for pethanol feryeasts as wnatively, nothe ethanolseparation erages dealprocesses [and distillat[5,6], whilenanoltrati

CorresponE-mail add

trifuing eon ofsign uid

(e.g. water vapour) extracts the ethanol from the beverage [15].The spinning cone column is made of spinning cones, attached toa central rotating shaft, intercalated with xed cones, attached tothe column wall. SCC operates as a pure stripping column because

1383-5866/$ doi:10.1016/j.ews, such as beer or wine, are produced interrupting then of sugars from the cereals or grapes juice to ethanol.ermentation process, yeast produces by-products, suchlcohols and esters, which have a great contribution tond taste of the brew. As a result, interrupting the fer-the avour of the non-alcoholic brew does not improve

typical avour of the alcoholic brews [1]. Other pro-roducing non-alcoholic beverages, by restricting the

mentation, include the use of special or immobilizedell the use of low sugar raw materials [13]. Alter-n-alcoholic beverages can be produced by removing

from a completely fermented beverage, using severalprocesses. Most common separation processes for bev-coholization are heat treatment or membrane-based14]. Heat treatment processes comprise evaporationion or vapour stripping, both under vacuum conditions

membrane-based processes include reverse osmosis,on, dialysis and pervaporation [714].

ding author. Tel.: +351 22 5081695; fax: +351 22 5081449.ress: [email protected] (A. Mendes).

the beer is fed on the top of the column and there is no recti-cation or enrichment as in typical distillation. This technologyhas been applied for dealcoholizing wine with aroma compoundsrecovery, for adjusting ethanol content of high alcohol wines andfor removing ethanol from beer. SCC distillation is also appliedfor recovering avour compounds from fruit juices, tea or coffee[3,5,6,1618].

The main advantages of SCC distillation comprise low residencetime, high contact area between liquid and vapour, low pressure-drop in the column and moderate temperatures, which minimizesthe thermal impact on the beverage [3,19]. However, as in mostof the dealcoholization processes, SCC has also some drawbacksrelated to the decrease in the quality of the nal product avour,mainly because some of the volatile aroma compounds are removedtogether with the ethanol [5] and, on the other hand, ethanol itselfcontributes to the beverage avour.

Regarding the loss of aroma compounds during beveragesprocessing, the recovery of natural aroma compounds plays animportant role in brews industry because of their high com-mercial value [2022]. In order to improve the avour proleof the treated beverages, the aroma compounds can be recov-ered from the alcoholic stream of the dealcoholization process or,

see front matter 2011 Elsevier B.V. All rights reserved.seppur.2011.03.020coholic beerA new industrial process

a Catarino, Adlio Mendes

al Engineering Department, Faculty of Engineering, University of Porto, Rua Roberto Fri

e i n f o

ne 2010vised form 3 March 2011rch 2011

onry

column

a b s t r a c t

This paper studies a new industrial ural avour prole. The aroma comoperating conditions of this unit, usinmembranes, are investigated. High pefor maximizing the permeation ux astream is then added to the feed streamcoholization. In this unit, the beveragethe ethanol and other volatile aroma with the extracted aroma compounds(ethanol lower than 0.5 vol.%) with a ga dealcoholized beer with a taste very

ction

ket of non-alcoholic brews has experienced a signicantnt during the past years, mainly because new driv-g rules, health and religious reasons. However, most of

Cenremovvariaticial degasliq/ locate /seppur

0-465 Porto, Portugal

ess for producing non-alcoholic beer with a corrected nat-ds are obtained by pervaporation of the original beer. Theyoctylmethylsiloxane/polyetherimide (POMS/PEI) compositetion temperature and low feed owrate are the most effectivee equilibrium of the avour prole. The aroma depleted beern industrial unit of spinning cone column distillation for deal-acts counter-currently with a water vapour stream that stripsounds from beer. After dealcoholization, the beer is blendedith a fraction of original beer to achieve a non-alcoholic beeravour prole. This new industrial process proved to originate

e to the original one. 2011 Elsevier B.V. All rights reserved.

gal distillation is a worldwide popular method forthanol from alcoholic beverages. This process is a

vacuum distillation, which uses a column with a spe- the spinning cone column (SCC). SCC consists in acounter-current device where the stripping medium

M. Catarino, A. Mendes / Separation and Purication Technology 79 (2011) 342 351 343

Fig. 1. Block dSCC distillatio

instead, thethe dealcohMembrane-ery before band dealcohadvantagestheir energof chemicalperatures, wintended tobrane proceabove-menare very selebeverages aprocess wasfrom fruit jconcentratiapplied forbeverages [by pervaporesponse suoperating cMoreover, tbeverages asequent add

This papalcoholic beThe beer dedistillation,dealcoholizural extracobtained bymembranesthe pervapotions were equilibrated

2. Materia

Fig. 1 shnon-alcohoing aroma cfor removintion of non-the aroma ction unit isIn the SCC

vapour stream that strips ethanol (and other volatile compounds).Finally, the aroma compounds from the pervaporation unit and afraction of fresh alcoholic beer are added to the dealcoholized beerfor balancing its lack of aroma compounds.

oma

extrustrireamzed iame

40 mum ate) branger

pu undransfd therane

cond. A condene cir

is co in coout

arommultimenrostirmas way

carbhe re

corrholiz

innin

bertection oratger (SCC ig vecoluiagram of the industrial process for producing non-alcoholic beer byn and pervaporation of a regular alcoholic beer.

y can be extracted from the original beverages beforeolization and added back to the dealcoholized brews.based processes proved to be effective for aroma recov-everage processing (e.g. pasteurization, concentrationolization) [23,24]. Membrane processes show several

over traditional heat or solvent extraction processes;y consumption is normally lower and there is no need

additives. Otherwise, they can be operated at low tem-hich is essential when sensitive aroma compounds are

be separated [2527]. One of the most effective mem-sses for aroma recovery is pervaporation. Besides thetioned advantages, suitable pervaporation membranesctive for several chemical groups that constitute typicalroma proles [2831]. During last years, pervaporation

successfully applied for recovering aroma compoundsuices for subsequent addition to the same juice, afteron by evaporation [3237]. Pervaporation has been also

ethanol removal and aroma recovery from alcoholic13,14,38,39]. The extraction of beer aroma compoundsration was recently studied by the authors, using therface methodology (RSM) for evaluating the effect ofonditions on the membrane ux and selectivity [40].he integrated process that considers the extraction ofroma compounds before the dealcoholization and sub-ition to the treated beverage was patented [41].er studies the industrial process for producing non-er (ethanol < 0.5 vol.%) with improved avour prole.alcoholization is performed by spinning cone column

according to the process described elsewhere [42]. Theed beer is blended with fresh alcoholic beer and nat-ted aroma compounds. These aroma compounds are

pervaporation of the original beer, using POMS/PEI

2.1. Ar

Thean indbeer storganiand-frarea ofmaxim(retentof memexchanvacuumule setmass tside anmembof two85 Cthat cois madwhichstoredworks tion ofused siembodthe defthe theing thisuch asvent. Twhichdealco

2.2. Sp

The(Flavouvaporapervapexchan(SCC). rotatinto the . The effect of feed temperature and feed owrate onrated aroma prole was assessed. The operating condi-selected to originate dealcoholized beer with the most

avour prole.

ls and methods

ows the block diagram of the process for producinglic beer by integrating pervaporation (PV) for extract-ompounds and spinning cone column (SCC) distillationg ethanol. In the rst step of the process, a stream frac-carbonated alcoholic beer is pervaporated for extractingompounds. The retentate stream from the pervapora-

added to the feed stream of the SCC distillation unit.unit, the feed contacts counter-currently with a water

cones, undedue to the The strippiows up thand other vtaining ethof the colum(PHE5). Thein a tank. Tby means odown the ca pump (P5exchanger through a sthe temper extraction by pervaporation (PV)

action of aroma compounds from beer is performed inal plant as illustrated in Fig. 2. A fraction of the original

is pumped continuously to four membrane modulesn two sets of two modules (MM, cf. Fig. 2), using plate-POMS/PEI composite membranes with a total effective2. The feed pump (P1) controls the inlet owrate to a

pressure difference between the inlet (feed) and outletof membrane module of 2 bar. Before the inlet of the sete modules, the feed stream passes through a plate heat

(PHE1) for controlling the temperature. A rotary vanemp (P2) keeps the permeate side of the membrane mod-er sub-atmospheric pressure. The vacuum provides theer of aroma compounds from the beer to the permeate

subsequent evaporation at the downstream side of thes. The permeate stream is then conducted to the rst setensers (PC1 and PC2), where it is condensed at aroundoling/heating circulator (CH) supplies the thermal uidses the permeate. After the extraction step, hot water

culating in the condensers for defrosting the permeate,llected in the aroma tank (PR) and then discharged andntainers. The second set of condensers (PC3 and PC4)

of phase in order to allow a semi-continuous produc-a compounds. The two sets of condensers can also be

aneously for condensing the aroma compounds. In thist, besides hot water being fed to the condensers duringng cycle, the condensers are also fed with a hot stream ofl uid from the cooling/heating circulator (CH), increas-

the defrosting rate. The non-condensable compounds,on dioxide, are expelled through the vacuum pump (P2)tentate stream (stage cut of approximately 0.11.1%),

esponds to semi-depleted beer, is then fed to the SCCation unit.

g cone column (SCC) distillation

er dealcoholization is performed in a SCC planth) sketched in Fig. 3. The retentate stream from the per-plant and a fraction of the original beer (not fed to theion unit) are pumped continuously through a plate heatPHE3, cf. Fig. 3) to the top of the spinning cone columns a stripping unit made of spinning cones attached to artical central shaft, intercalated with static cones, xedmn wall. The feed beer ows down through the xedr gravity force, and ows up through the spinning cones,centrifugal force, forming always a thin layer of liquid.ng stream, which consists in deaerated water vapour,e column in turbulent regime and collects the ethanololatile aroma compounds from beer. The vapour con-anol and other volatiles is carried out through the top

n and then it is condensed in a plate heat exchanger condensate passes through a cyclone (C) and is storedhe distillate and vapour line are kept under vacuumf a vacuum pump (P6). The dealcoholized beer travelsolumn and is discharged from the column bottom by). The dealcoholized beer passes through the feed heat(PHE3), where it is cooled by the feed beer, and thenecond heat exchanger (PHE4) for a nal adjustment ofature.

344 M. Catarino, A. Mendes / Separation and Purication Technology 79 (2011) 342 351

The deal(around 50.3 vol.%) frThe blendedclose to the

2.3. Analyti

The expebeer contaiof ca. 3.5 g Lcompoundsthe dealcohIt was used4500 and Aoriginal andpervaporatemine the aris describedselected vo(Pr), isobutaacetate (iAA

3. Results

The efcterms of prFig. 2. Flow diagram of the pervaporation indu

coholized beer is then blended with fresh alcoholic beer10 vol.%) and the extracted aroma compounds (aroundom the pervaporation unit, and nally it is carbonated.

beverage is a non-alcoholic beer with an aroma prole original beer.

cal methods

riments were performed with an alcoholic Pilsner typening ca. 5.5 vol.% of ethanol and residual carbon dioxide1. The original extract, real extract, ethanol and aroma

concentrations were quantied in the original beer, inolized beer, in the extracted aroma and in the nal beer.

a densitometer coupled to an ethanol analyser (DMAlcolyzer Plus, Anton Paar) to measure the density, the

real extract of beer and the ethanol content of beer andd samples. A gas chromatograph was used to deter-oma compounds concentrations. The analysis method

elsewhere [40]. Table 1 shows the properties of thelatile aroma compounds studied: ethanol (E), propanolnol (iB), amyl alcohols (AA), ethyl acetate (EA), isoamyl) and acetaldehyde (Ac).

and discussion

iency of the pervaporation process was evaluated inoductivity (permeate ux) and quality of the extracted

aroma (memlibrium bet

At stead

Jp =mpAt

where mp ieffective m

The selecompound

i/E =wp,i/

wf,i/

where wp,iof the aromthe mass fra

The enricomputed u

i =Cp,iCf,i

where Cp,i aon the permstrial plant.

brane selectivity, concentration of permeate and equi-ween aroma compounds on the permeate).y-state, the permeate ux (Jp) is given by:

(1)

s the permeate mass collected after defrosting, A is theembrane area and t is the time of the permeation cycle.ctivity of the membranes (i/E) towards a generic aromai compared to ethanol (E) was obtained from:

wp,Ewf,E

(2)

and wp,E are the condensed permeate mass fractionsa compound and ethanol, respectively; wf,i and wf,E arections of the aroma compound and ethanol on the feed.chment factor (i) of a generic aroma compound i wassing:

(3)

nd Cf,i are the concentrations of the aroma compoundeate and feed side, respectively.


The equing the totaon the colle

A/E = ChighCe

where A/E ithe concent

3.1. Operat

It was coables of theowrate an

Table 1Properties of b

Compound

Ethanol Propanol Isobutanol Amyl alcohoEthyl acetateIsoamyl acetAcetaldehyd

a Beer thresFig. 3. Flow diagram of the SCC industrial p

ilibrium of the extracted permeate was assessed divid-l amount of higher alcohols by the total amount of esterscted permeate:

alcohols

sters(4)

s the ratio between higher alcohols and esters and C isration of the species on the permeate.

ion of the industrial plant of pervaporation

ncluded elsewhere [40] that the critical operation vari- pervaporation plant are the feed temperature, feed

d permeate pressure. In this study, the feed temperature

was investirange of 50tion time beside hold-uules was 2.38 mbar. Theproduces aing the pethe feed temcondensatioand condenture; as thalso increasure (Fig. 4

eer volatile compounds.

Molecularformula

Molecularweight(g mol1)

Boilingpoint (C)

Beethre(pp

C2H6O 46 78 140C3H8O 60 98 8C4H10O 74 108 2

l C5H12O 88 132 C4H8O2 88 77 ate C7H14O2 130 149 e C2H4O 44 20

hold (minimal concentration for detecting or identifying the compound) [43].lant [42].

gated in the range of 725 C and the feed owrate in the01500 L h1, which corresponds to a retentate reten-tween 114 s and 340 s. The ratio between the retentatep volume and membrane area of the membrane mod-7 L m2. The permeate pressure was maintained below

industrial unit uses a cooling/heating circulator that refrigeration stream at ca. 90 C used for condens-rmeate stream. Figs. 4 and 5 show the inuence of

perature and owrate on the permeate pressure andn temperature, respectively. The permeate pressuresation temperature increase with the feed tempera-

e feed temperature increases, the permeate owrateses which leads to an increase of the permeate pres-). The increase of permeate owrate also inuences the

rsholda

m)

Concentration inbeer (ppm)

Typical avour

00 5.67 vol.% Alcohol00 20.30 Alcohol00 12.87 Alcohol68 83.86 Alcohol, banana30 20.27 Fruity, solvent1.2 1.37 Banana

25 5.06 Green apples


Fig. 4. Permeate pressure (Pp) as a function of feed temperature (Tf) for three dif-ferent feed owrates (Qf).

performance of the condensers, leading to a smaller contact timeand then to a decrease of the condensation rate. This originatesthe condensing temperature to increase with the feed temperature(Fig. 5).

It was obfeed owrabon dioxideother hand,sation temp

3.2. Inuen

As mentporation plaowrates. Date pressurethe inuenselectivity ameate streaand is mostcates a smaother hand,constant aswhile the sperature anowrate (1ity, it increFig. 10 plot

Fig. 5. Condenthree different

Fig. 6. Permeate ux (Jp) as a function of feed temperature (Tf) and owrate (Qf).served that the permeate pressure increased with thete (Fig. 4). This should be related to the increase of car-

permeation, as concluded using degassed beer. On the the feed owrate has a minor inuence on the conden-erature (Fig. 5).

ce and selection of feed temperature and owrate

ioned before, the experiments in the industrial perva-nt were performed at different feed temperatures andespite the inuence of these conditions on the perme-, all runs were operated below 8 mbar. Figs. 610 show

ce of the feed temperature and owrate on the ux,nd equilibrium between aroma compounds on the per-m. The permeate ux increases with feed temperaturely not affected by the feed owrate (Fig. 6); this indi-ll or negligible concentration polarization effect. On the

the selectivity towards higher alcohols remains almost a function of the feed temperature and owrate (Fig. 7),electivity towards esters decreases with the feed tem-d it shows a maximum for the middle value of feed000 L h1, cf. Fig. 8). Concerning acetaldehyde selectiv-ases with the feed temperature and owrate (Fig. 9).s the ratio between higher alcohols and esters on thesation temperature (Tc) as a function of feed temperature (Tf) for feed owrates (Qf).

Fig. 7. Higher alcohols selectivity as a function of feed temperature (Tf) and owrate(Qf): (a) propanol; (b) isobutanol and (c) amyl alcohols.


Fig. 8. Esters sethyl acetate a

permeate aing that A/Efeed owraand low feePilsner beer

CatarinoIn this studthe membrthe other hliquid nitroally, the higof the feed perature. In

Fig. 9. Acetald(Qf).

Fig. 10. Higher alcohols and esters ratio (A/E) as a function of feed temperature (Tf)and owrate (Qf).

selectivity with the feed temperature [40], due to the transport acti-vation energy of the higher alcohols being higher than of water [20]and also because ethanol concentration is less sensitive to the tem-perature than the permeate (water) ux. Higher alcohols selectivity

creasrmed by at hcreasities)

indu cooencekes tmporial punit,electivity as a function of feed temperature (Tf) and owrate (Qf): (a)nd (b) isoamyl acetate.

s a function of the feed temperature and owrate, show-

also inless peaffectelevel thsure involatilIn theusing ais inuthis maiest coindustratory increases with the temperature and decreases with thete. It can be observed that for high feed temperatured owrate, the A/E ratio is closer to the typical value ofs, which is placed between 4 and 6 [44].

et al. [40] reported a similar study at laboratory level.y, the beer was stored in a tank, recirculating throughane cell originating the rapid degassing of the beer. Onand, the pervaporated stream was condensed using agen trap. Comparing with the results obtained industri-her alcohols selectivity behaves similarly as a functionowrate and differently as a function of the feed tem-

the lab unit, there is an increase on higher alcohols

ehyde selectivity as a function of feed temperature (Tf) and owrate

feed tempein this casetivity towaFinally, it sof the highshould be tthat the feeselectivity.

Concernthe esters sthe lab one

Fig. 11. Histoduring 8 monimproving reaes slightly with feed owrate since higher alcohols areable compared to esters and, as a result, they are lessthe concentration polarization [40]. It was veried at labigher alcohols selectivity decreases with permeate pres-e [40], due to their low saturated vapour pressures (low

[20]. This trend was not observed in the industrial plant.strial plant, the condensing temperature is obtainedling/heating circulator and the condensing temperatured by the feed temperature, increasing with it (cf. Fig. 5);he condensing system to selectively condense the heav-nents. On the other hand, as the vacuum pump in thelant is proportionally smaller than the one in the labo-

the permeate pressure increases signicantly with therature (cf. Fig. 4), since the permeate owrate increases;

an increase on the feed temperature makes the selec-rds the heaviest permeating components to decrease.hould be expected an increase on the permeating uxer alcohols with the feed temperature. The nal trendhe balance of these three effects and it was observedd temperature mostly does not affect the higher alcohols

ing the effect of the feed temperature and owrate onelectivity, the industrial results are in agreement withs. According to lab results, esters selectivity increasedry of permeate owrate (Qp) and enrichment factor of ethanol (E)ths of beer aroma compounds extraction (lines were introduced fordability).


Fig. 12. SEM mfresh membra

with feed through theare more sebrane selectemperaturbeing closetion is less a(water) uxincrease [40However, inthe condenesters decretemperaturobserved bselectivity wbrane selecfeed owrathe feed oalso increasdensers is atimes), whiwas observefor 1000 L h

Comparireported byle is less cand acetaldcentration ithe selectiv

Effect of cleaning solutions (at specied concentrations) in the removal of0 reference and 4 maximum fouling).

alcoand d bef

batal cothe cfecteiduandendes (ost table , du

the res hiFig. 13. fouling (

higheresters referredensedthe totplant, it is afthe restive coaldehytively lpermedensedresult,becomicrographs of selective surface of POMS/PEI membrane samples: (a)ne and (b) aged membrane in PV runs.

owrate increase. Esters present higher permeability membrane compared to higher alcohols and thus theynsitive to polarization concentration [40]. The mem-tivity towards esters should decrease with the feede increase [40] due to their transport activation energyr to the water [20] and also because ethanol concentra-ffected by the temperature increase than the permeate. Esters selectivity increases with the permeate pressure] due to their higher saturated vapour pressures [20].

the industrial unit as the feed temperature increases,sing temperature increases and selectivity towardsases; as the permeate pressure increases with the feede, the selectivity towards esters should increase. Thealance of these effects resulted in a decrease of estersith the feed temperature. On the other hand, the mem-

tivity towards esters was expected to increase with thete [40]. Also, as the permeate pressure increases withwrate (cf. Fig. 4), the selectivity towards esters shoulde [40]. On the other hand, the performance of the con-ffected by the increase of feed owrate (shorter contactch reduces the condensation efciency. At the end, itd that the selectivity towards esters shows a maximum

1 of feed owrate.ng the industrial permeate aroma prole with the one

the same authors for a lab unit [40], the industrial pro-oncentrated in aroma compounds, especially in estersehyde Table 2. It was observed that ethanol con-s slightly lower in the industrial plant also. Regardingity towards aroma compounds, the selectivity towards

of the condux, which

As it caux and arand 500 L htemperatur(higher permore equiloriginal beebeer obtain25 C of feebest one.

3.3. SCC op

The maithe ethanolquality are

Table 2Comparison b

Characterist

Jp (105 kg mCp,E (vol.%) Pr/EiB/EAA/EEA/EiAA/EAc/EA/E

a Results puhols is similar in both cases, while selectivity towardsacetaldehyde are lower, compared to the lab study. Asore, in the lab unit, the permeate was collected and con-ch-wise with liquid nitrogen at 196 C, which allowsndensation of the aroma compounds. In the industrialondensation system works at higher temperatures andd by the permeation owrate and the permeation ofl carbon dioxide present in the feed. This less effec-sing system makes light compounds, mostly esters andsuch as ethyl acetate and acetaldehyde), to be selec-hrough the vacuum pump. On the other hand, the mostcompounds, such as isoamyl acetate, are poorly con-e to the short contact time in the condensers. As aatio between higher alcohols and esters concentrationgher in the industrial plant (see Table 2). The limitationsensation system also affects the permeate condensing

is lower than the one obtained for the lab unit Table 2.n be seen from Figs. 6 and 10 the highest permeateoma ratio was obtained for 25 C of feed temperature1 of feed owrate (stage cut of ca. 1.1%). For high feedes and low feed owrates the membrane productivitymeate owrate) is higher and the aroma prole becomesibrated (higher alcohols and esters ratio closer to ther value). Besides, the taste of the blended non-alcoholiced by adding the pervaporation extract produced atd temperature and 500 L h1 of feed owrate was the

erating conditions

n operating parameters of SCC distillation that affect removal from beer and hence the dealcoholized beer

the feed owrate, the internal stripping ratio (ratioetween lab and industrial results of beer pervaporation.

ics Lab resultsa Industrial results

Min Max Min Max

2 s1) 1.53 8.56 1.35 3.8422.00 29.50 12.75 21.251.03 1.45 1.14 1.462.08 2.97 2.18 2.582.01 3.60 2.55 3.07

11.51 24.76 3.27 8.2012.02 35.78 5.63 20.502.91 5.37 0.13 0.330.46 1.63 1.25 3.20

blished elsewhere [40].


Table 3Composition of beer and pervaporated aroma during the process of dealcoholization and aroma recovery.

Characteristics Originalbeer

Dealcoholizedbeer

Pervaporatedaroma

Non-alcoholicbeer

Originalbeer Ri/E

Non-alcoholicbeer Ri/E

CE (vol.%) 5.67 0.02 19.50 0.45Original extract (wt.%) 14.65 6.24 6.79Real extract (wt.%) 6.22 6.21 0.00 6.21

CPr (mg L1) 20.3 n.d. 72.64 1.54 3.58 3.45CiB (mg L1) 12.87 n.d. 106.36 1.16 2.27 2.59CAA (mg L1) 83.86 n.d. 841.70 7.99 14.79 17.88CEA (mg L1) 20.27 n.d. 249.67 2.07 3.57 4.63CiAA (mg L1) 1.37 n.d. 39.82 0.21 0.24 0.47CAc (mg L1) 5.06 2.17 6.24 2.37 0.89 5.31A/E 5.41 3.53 4.69

n.d., not detected.

between vapour and feed owrate) and the vacuum pressure. Inthis study, the beer dealcoholization was performed at 2200 L h1

of feed owrate, 18% of stripping ratio and 50 mbar of vacuumpressure. The temperature of SCC for these conditions was 45 Con the column top and 55 C on the bottom. Table 3 shows thecomposition of the original beer (before any processing), dealco-holized beer (product from SCC, with an ethanol concentration ofca. 0.0 vol.%) and non-alcoholic beer (product from SCC blendedwith pervaporated aroma and fresh alcoholic beer, with an ethanolconcentration < 0.5 vol.%). In the SCC unit, water vapour strips theethanol as well as a great fraction of volatile aroma compounds.By adding fresh original beer and the permeate from the perva-poration unit, the aroma prole improves within the maximumallowable etion of aromthan in thetration andMoreover, aof this non-

3.4. Membr

After sefor extractiporation ploperation,

concentration. Fig. 11 shows the history of permeate owrateand permeate concentration of ethanol during these 8 months. Toregenerate the original performance it was decided to test severalcleaning solutions and cleaning conditions. First, it was developeda laboratory method to simulate this ageing phenomenon. Mem-brane samples were immersed in various ageing solutions, namelyin ultrapure water, aqueous ethanol solutions (about 10 vol.%) andPilsner type beer (about 5.5 vol.%) Table 4. Besides the immersionof membranes in the ageing solutions, membrane samples weresubmitted to several pervaporation lab cycles with beer. The per-formance of aged membranes were then assessed by determiningthe pervaporation permeate ux and selectivity of an ethanol aque-ous solution of ca. 10 vol.% Table 4. The results from Table 4 show

merid no). Thd in se ofrane

beerraner care pewas rvapombr

Table 4Effect of agein

Runs # Jp (1

a 7.1b 7.0c 7.0d 7.2e 6.6f 10.5g 7.5h 7.4i 7.7

Table 5Characteristics

Solution

TFD4 Actinet Decal Divos 120CLDivos 123 BoosterDivos 98PE thanol concentration of 0.5 vol.%. Despite the concentra-a compounds in the non-alcoholic beer being smaller

original one, the ratio between each aroma concen- ethanol (Ri/E) is close to the original beer Table 3.

trained taste panel considered that the avour prolealcoholic beer is similar to the original one.

ane ageing

lecting the optimum feed temperature and owrateng aroma compounds from beer, the industrial perva-ant was set to work continuously. After 8 months ofit was veried a decrease on permeate owrate and

that imbeer dc and dresultedecreamembtion of(memb

Aftethat thdry. It the pethe me

g conditions on POMS/PEI membranes ux and ethanol selectivity.

Ageing conditions Ageing time (days)

Fresh membrane Milli-Q ultrapure water 30 Ethanol 10 vol.% 30 Beer 5.5 vol.% of ethanol 30 Beer PV runs 30 Membrane e after dry 30 Beer PV and kept in ultrapure water 30 Beer PV and kept in beer 45 Beer PV and kept in beer 80 of cleaning solutions.

Type of solution Supp

Alkaline FranSurfactant ImpoAlkaline surfactant ImpoChlorinated alkaline JohnAlkaline JohnHydrogen peroxide additive JohnEnzimatic Johnsing membranes in ultrapure water, ethanol solution ort result in signicant ageing of the membranes (runs b,e use of membranes in pervaporation cycles with beera slight decrease of the permeate ux and a signicant

the ethanol selectivity (run e). It was also observed that samples (originally white) submitted to the pervapora-

showed an intense brown coloration in both surfaces fouling).efully analysing the industrial procedure, it was veriedrvaporation membranes when not in used were let tothen assessed in the laboratory unit the role of dryingration membranes periodically. It was concluded that

anes showed a signicant decrease in ethanol selectivity

05 kg m2 s1) Jp (%) E/W E/W(%)

0 0.00 5.24 0.007 0.32 5.54 5.829 0.11 5.24 0.029 2.75 5.29 0.912 6.75 4.56 12.86

47.97 3.36 35.820 2.73 5.23 0.649 2.82 5.36 3.080 0.18 5.33 2.52lier Concentration(wt.%)

klab 1.00rqumica 5.00rqumica 1.00son Diversey 1.00son Diversey 1.50son Diversey 0.25son Diversey 1.00


and an increase of membrane ux (see Table 4, run f). This ageingshould be related to micro ruptures in the membrane selective lm,which become more fragile. On the other hand, maintaining themembranes in water or beer between pervaporation runs resultedin a negligibgi).

Fig. 12 sbrane samamount of aing solutionrestoring thsamples weperature anshows the ccentration solutions inwas evaluathe contactwhite), beforesults wersamples. ThBooster (Johfouling. Onselectivity oafter memb

4. Conclus

In this stbeer (ethanThe processextracts thetillation undealcoholizthe extractprole.

SCC distethanol fro(50 mbar, astream for ption also str

The pervmodules of8 mbar of pcondensingperformed owrate onthese operacondensatiowere 25 C ocut of ca. 1good equiliextract andbeer to balaconcentrati

During beer it wascentration reproducedbrane ageinOn the othpervaporatiforming solthis solutiovaporation

List of symbolsA membrane effective area (m2)A/E higher alcohols and esters ratioC concentration (vol.%, wt.% or mg L1)

umoratetimm

ettermen

pts aamaccoetetfegeisisprperew

wled

Catarnd TeRH/a (Unirs arime

nces

Kunze. Lewi

Picke00) 12Catarireversmezolizatensm. Beliez, Dpoun

rylhydabandogy fo

TechnLpezle cid. Piliposis, iban,

dy for 311 (Petkov

with(4) (19skoseltratierhoancetionsle ageing effect after 80 days of operation (Table 4, runs

hows electronic pictures of a fresh and an aged mem-ples. Aged membrane sample shows an increasingdsorbed particles at the selective surface. Several clean-s were tested for reducing the membrane fouling ande original properties of the membranes. The membranere submersed in the cleaning solutions at room tem-d concentrations as specied by the suppliers. Table 5haracteristics of cleaning solutions, as well as the con-applied. Fig. 13 shows the behaviour of the cleaning

the removal of membrane fouling. The fouling removalted based on the intensity of the brown coloration and

angle of the membrane samples surface (originallyre and after immersing in the cleaning solution. The

e compared with fresh (reference) and aged membranee solution of alkaline reagent Divos 123 plus additivenson Diversey) showed the best removal of membrane

the other hand, the pervaporation ux and ethanolf a 10 vol.% aqueous solution of ethanol did not changerane immersion on this cleaning solution.

ions

udy it was investigated the production of non-alcoholicol concentration < 0.5 vol.%) using an industrial plant.

comprises two technologies: a pervaporation unit that aroma compounds from the feed beer and a SCC dis-it that removes the ethanol, after pervaporation. Theed beer is then blended with original fresh beer and withed aroma compounds, in order to improve its avour

illation proved to be an effective process to removem beer. This extraction unit operates under vacuumverage temperature of 50 C) and uses a water vapourromoting the ethanol removal. However, SCC distilla-ips the beer feed from other aroma compounds.aporation unit uses four plate-and-frame membrane

POMS/PEI (40 m2) and operates between 1 mbar andermeate pressure and between 75 C and 85 C of

temperature. Several pervaporation experiments wereto assess the inuence of the feed temperature and

the aroma compounds extraction. It was found thatting variables affect the permeate pressure and then temperature; the obtained best operating conditionsf feed temperature and 500 L h1 of feed owrate (stage.1%), allowing the maximum permeate delivery and abrium of the aroma prole. Around 0.3 vol.% of aroma

510 vol.% of fresh beer are added to the dealcoholizednce the lack of aroma, without overcoming the ethanolon limit of 0.5 vol.%.the industrial extraction of aroma compounds from

observed a decline in the permeate owrate and con-after 8 months of operation. This ageing process was

at laboratory level. It was concluded that the mem-g could be prevented if membranes were not let to dry.er hand, various cleaning solutions for removing theon membranes fouling were evaluated. The best per-ution was Divos 123 with Booster (Johnson Diversey);n showed no detrimental effect on the membrane per-ux and selectivity.

J m Q R T t w

Greek l

SubscriAA Acc EEA fi iAAiB Prp *W

Ackno

M. ence a(Ref. SFFerreirG. Quein expe

Refere

[1] W. [2] M.J[3] G.J.

(20[4] M.

by [5] E. G

cohLeb

[6] Y.YGmcompic

[7] J. LnolSci.

[8] M. app

[9] M.Vosm

[10] N. DstuSci.

[11] M. tion75

[12] I. Ledia

[13] A. Vformsolux (kg m2 s1)ass (kg)wrate (L h1)tio between aroma compounds and ethanolmperature (C)e (s, min or days)

ass fraction (wt.%)

sembrane selectivityrichment factor

nd superscriptsyl alcohols

etaldehydendensationhanolhyl acetateedneric aroma compoundoamyl acetateobutanolopanolrmeatelative to condensed formater

gements

ino acknowledges the Portuguese Foundation for Sci-chnology (FCT) and Unicer Bebidas S.A. the PhD grant

BDE/15564/2005). The authors acknowledge Antnio A.icer) for the fruitful discussion of the work and Joanand Jorge Moutinho from Unicer for their collaborationntal work at the industrial plant.

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Non-alcoholic beerA new industrial process1 Introduction2 Materials and methods2.1 Aroma extraction by pervaporation (PV)2.2 Spinning cone column (SCC) distillation2.3 Analytical methods

3 Results and discussion3.1 Operation of the industrial plant of pervaporation3.2 Influence and selection of feed temperature and flowrate3.3 SCC operating conditions3.4 Membrane ageing

4 ConclusionsAcknowledgementsReferences

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Non-Alcoholic Beer—a New Industrial Process