Production of Tartaric Acid From Pomace of Some Anatolian Grape Cultivars

Transcription

1 Prductin f Tartaric Acid Frm Pmace f Sme Anatlian Grape Cultivars C. NURGEL ~* and A. CANBAS 2 Prductin f tartaric acid frm pmace f sme Anatlian grape cultivatrs was investigated. Tw different extractin methds based n either ht water r dilute acid were used. Based n the chemical analysis the amunts f CaCO 3 and CaCI 2 t be added int the extract were calculated and, the tartaric acid salts were precipitated as calcium tartrate. Calcium tartrate was first cnverted int tartaric acid by sulfuric acid treatment then, the tartaric acid was declrized by means f active carbn and finally, crystallized under vacuum at 70 C. It was fund that the calcium tartrate cntents using dilute acid extractin were 1.3%, 1.7%, and 2.0% whereas in ht water extractin they were 2.1%, 2.5%, and 3.1% frm Emir, Okuzgzu, and Bgazkere pmaces respectively. Tartaric acid cntents crrespnding t these calcium tartrates were 43.9%, 43.8%, and 44.1% frm Emir, Okuzgzu, and Bgazkere grape pmaces, respectively. Tartaric acid amunts recvered frm Emir, Okuzgzu, and Bgazkere grape pmaces prcessed with dilute acid extractin were 0.4%, 0.5%, and 0.6% and frm ht water extractin were 0.6%, 0.8%, and 1.1%, respectively. Of tw extractin methds ht water extractin was mre efficient. KEY WORDS: grape pmace, calcium tartrate, tartaric acid prductin, Emir, Okuzgzu, Bgazkere Utilizatin f winemaking residue is imprtant because f decreasing resurces and increasing ease f dispsal f industrial slid wastes. Furthermre, extractin f tartaric acid frm pmace is recvering a valuable cmmdity frm a waste prduct. Anatlian grape cultivars have nt been evaluated fr the recvery f tartaric acid. Turkey, with tns f grape prductin per year is the fifth biggest grape prducer in the wrld [27]. Emir, frm Nevsehir-Urgup regin (Cappadcia) f Turkey is an imprtant variety fr prductin f white wine. Okuzgzu and Bgazkere are frm Elazig regin and are used fr prductin f red wine. Several studies have dealt with the prductin f tartrate and/r tartaric acid. By-prducts frm winery wastes, including tartrates, grape seed il, tannin, stck feed, and fertilizer,were reviewed by Amerine et al [4]. Anthcyanins as dietary supplements are prduced in France [22]. Many researchers have studied their natinal varieties in rder t prduce such byprducts [5,9,10,15,16,19,21,26]. Methds fr prductin f tartaric acid have been reviewed by Amerine et al. [4]. These methds culd be used fr big and small wine plants. Ht water and dilute acid have been used fr the extractin f tartaric acid fr sme time and ffer sme advantages. Fr instance, fr a small winery, n high technlgy is needed [4]. A new technique that depends n electrchemical transfrmatin was described by Audins and Paci [3]. In the prductin f tartaric acid, factrs affecting calcium tartrate cntent in the extract such as CaCO3, 1Research Assistant, Mersin University, Engineering Faculty, Fd Eng. Dept, Mersin, Turkey; 2Prfessr, Cukurva University, Agricultural Faculty, Fd Eng. Dept, Adana, Turkey. *Crrespnding authr. Manuscript submitted fr publicatin 17 Octber1996. Cpyright 1998 by the American Sciety fr Enlgy and Viticulture. All rights reserved. 95 CaC12, ph, and mixing time must be cnsidered [1,11,13,14]. The aim f this study was t prduce tartaric acid frm the pmace f sme Anatlian grape varieties and t cmpare tw different methds used in the prductin. Materials and Methds Grape f the cultivars Emir, Okuzgzu, and Bgazkere were analyzed at randm befre being prcessed in the winery f the Fd Engineering Department f Cukurva University. Cluster weight, cluster length and width, berry numbers f a cluster, stem weight, and stem/cluster rati were determined fr all varieties. After pressing, pmaces were analyzed t determine seed, skin, stem, and pulp cntent. Misture and tartrate cntents f pmaces were als determined. A flwchart diagram f tartaric acid prductin frm pmace is shwn in Figure 1. In rder t extract tartaric acid frm pmace ht water and dilute acid extractin methds were used. Fr bth extractins tank vlumes were 60 L. In ht water extractin, 10 kg pmace was weighed. In the first extractin, 3 parts f water t 1 part f pmace by weight were filled int tanks and heated until the biling pint. The pmace was kept at this temperature fr 15 minutes t extract the tartaric acid. During heating, pmace and water were mixed cntinuusly. The free-run liquid was drained ff and filled int a precipitatin tank. Ttal acidity and ph were determined. In the secnd extractin, 2 parts f water t 1 part f riginal pmace were filled int the extractin tanks and heated fr 30 minutes. The secnd extract was drained ff and pured int the precipitatin tank. After the extractin, pmace was remved frm the extractin tank and pressed.

2 ~ NURGEL and CANBAS Bentnite CaCI 2 and CaCO3 (Precipitatin) Adjusting f ph H2SO4 Active Carbn I Pmace lii [ Extractin li I Clarificati n lii... ;... i ;.entn,te I Calcium Tartrate li -Residue... i... '....CaSO4 Raw Tartaric Acid Slutin [ R,,ra,,n } i... l... C ';[' es;, ut[taric lii i [ Tartaric Acid li"i li li =Active Carbn Fig. 1. A flw chart f tartaric acid prductin used in the current study. In dilute acid extractin, 10 kg pmace and 30 kg f 1% HC1 slutin were put int the extractin tanks. They were kept fr five hurs withut mixing. Then, extracts were drained ff t the precipitating tanks. Fr the secnd extractin, pmaces were cvered with the required amunt f water (2:1 by weight) and kept fr 16 hurs. At the end f this perid, the secnd extract was cmbined with first extract in the precipitating tank. The impurities that were fund in bth extractins were precipitated with bentnite (0.5 g/l) at 13 C. In rder t precipitate tartaric acid as calcium tartrate, the ph f extracts in all experiment was adjusted t apprximately 3.5. Based n the reactin equatins and analytical results (ttal acidity and ph), the calculated amunts f CaCO 3 and CaC12 were mixed in a tank by small impellers at 52 rpm. Mixing was cntinued until unifr- Cultivar mity in physical and chemical cnditins were reached (ca. 1 hr). In rder t precipitate calcium tartrate white efficiently, the slutin was kept in a Emir precipitating tank fr ne night at Red +4 C. After precipitatin, the super- Okuzgzu natant liquids were racked ff and Bgazkere discarded. The calcium tartrate was resuspended in water that cntained 200 mg/l SO 2 t remve impurities and prevent bacterial spilage. Purity f calcium tartrates was determined by the methd described by Yaziciglu, and Karaali [26]. Sulfuric acid was used t cnvert calcium tartrate int tartaric acid. The amunts f sulfuric acid were changed with the purity f calcium tartrate. The calculated amunts f sulfuric acid were diluted with water 1:6 rati by weight and then mixed with calcium tartrate. T cmplete the reactin calcium tartrate and sulfuric acid were heated fr ne hur at biling pint. After cling, the calcium sulfate cake was washed and the wash liqurs were cmbined with strng liqurs. Then, it was filtered and declrized with active carbn (1 g/100 ml). Active carbn was filtered using the Whatman 42 ~m filter paper and Gch filter. Tartaric acid was crystallized n a rt-vapr under vacuum at 70 C. Slubility, specific rtatin, melting pint, ph and efficiency f tartaric acids were determined. Results and Discussin Cmpnents f Emir, Okuzgzu, and Bgazkere grape varieties differed frm each ther as shwn in Table 1. The differences between cluster structures f Emir, Okuzgzu, and Bgazkere were striking. The stem cntent f Emir was higher than fr the ther varieties. Althugh Okuzgzu's berry number was less than thers its clusters were heavier. The results btained in this study were clse t the results btained by ther researchers with ther grape cultivars [2,6,7,8,25]. In cluster cmpnents, stems and pulp have the lwest tartaric acid cntent. Fr this reasn, varieties that have lw stem/cluster rati have a high cntent f tartaric acid. The results fund were clse t the results f Rib~reau-Gayn et al's study [24]. Grape berry cmpsitin was als analyzed (Table 2). The highest berry weight and pulp amunts in grapes were fund in Okuzgzu and skin amunt was highest in Bgazkere. This pint is critical in prductin f tartaric acid, because tartrate is present as small crystals f cream tartar adhering t the skin [4]. Tartaric and malic acids are the majr acids in grapes, the frmer being quantitatively the mst imprtant. High cntent f tartaric acid leads t excessive titratable acidity in grapes [20]. Fr this reasn, acidity Table 1. Cmpnents f Emir, Okuzgzu, and Bgazkere clusters. Cluster Stem Stem/Cluster Cluster Cluster Berry wt wt rati width length n. (g) (g) (%) (cm) (cm)

3 TARTARIC ACID FROM POMACE- 97 Table 2. Berry structure f cultivars. Cultivar Berry wt Pulp Seed Skin N. f (g/berry) (%) (%) (%) seeds/cluster Emir Okuzgzu Bgazkere Table 3. Maturity f cultivars. Cultivar Sugar Acidity Maturity cntent* (g/l)** index Emir Okuzgzu Bgazkere *Oechsle = (density-i) xl 000 **Tartaric acid. f grapes is very imprtant in the prductin f tartaric acid. The tartaric acid cntent f grapes changes with maturity [19]. Maturity f grapes was determined by sugar and acid value f must (Table 3). The highest acidity was fund in Bgazkere variety. The pmace was randmly sampled thrughut crushing. The cmpsitins f pmace slids are shwn in Table 4. Because f the prductin technique fr white wine, Emir pmace stem cntent was very high cmpared t the red wines. Because Okuzgzu have large seeds, its seed cntent (%) was very high cmpare t the ther varieties. As shwn in Table 2, skin cntent f Bgazkere was the highest in pmaces. Burdiers [5] in 1973 reprted that 100 kg wet pmace f France grape cultivars cnsisted f 25% seeds, 20% stems, 30% pulp, and 25% skin. The misture cntents f Emir, Okuzgzu, and Bgazkere were 63.3%, 59.3%, and 60.4%, respectively. When misture cntents f white and red grape pmaces are cmpared, small difference can be seen. The misture cntent depends n variety and pressing technique. Misture cntent is imprtant in strage f pmace and tartaric acid yield. Mrales et al. [19] fund that misture cntent f pmace ranged between 50% and 60%, and Rice [23] reprted that misture cntents f white and red pmace were 52.5% and 58.2%, respectively. Misture cntents f Emir, Okuzgzu, and Bgazkere pmaces were in ranges f values reprted in the literature. The tartrate cntents f pmace in dry base f Emir, Okuzgzu, and Bgazkere were fund as 4.5%, 8.07%, and 13.82%, respectively. Amerine et al. [4], reprted that white wine pmace cntained 4.2% t 11.1% and red wine (fermentedn-the-skins) pmace cntained 11.1% t 16.1% tartrate. Kseglu [17] fund that the tartrate cntent f Hasandede pmace was 12% and f Kalecik Karasi was 1.7%. In anther study, Yaziciglu [26] reprted that Adakarasi and Yapincak pmaces cntained 7.05%, and 5.27% tartrate, respectively. The maximum tartrate efficiency was fund in Bgazkere pmace as shwn in Figure 2, because f its high skin cntent and high acidity. The wine prductin technique als influenced the efficiency. Amerine [4] reprted that pmace frm dry red wine making was richer in tartrates than pmace frm dry white wine making, because mst f the cream tartar separates during fermentatin f red must n the skins; whereas, white grapes were nearly always pressed befre fermentatin and there is n fermentatin n the skins. The extractin methd was als efficient. Between the tw methds, the ht water extractin yielded mre tartrate than the dilute acid extractin. In additin t these factrs, variety, prductin regin and maturity are als imprtant in tartaric acid cntent f grapes [24]. Cappelleri [9] prduced tartrate with different methds and fund calcium tartrate efficiency in red pmace as 2.5% t 3.5% and in white pmace as 1.5% t 2%. Tartrate efficiencies in different cuntries were reprted as 3% in Argentina [19], 2.5% in Spain [10], ~ 200 1= E 150 ~3. m = m t~ Extractin Ht Water Dilute Acid lii Iii fli Table 4. Cmpsitin f pmace slids (wet weight, 1994). 50 Cultivar Emir Okuzgzu Bgazkere Skin (%) Seed (%) Stem (%) Pulp (%) Cultivars Fig. 2. Amunts f calcium tartrate (g/10 kg) btained frm different cultivars by ht water and dilute acid extractin.

4 ~ 98 ~ NURGEL and CANBAS Extractin Iii Ht Water i! Dilute Acid I~ Extractin Ht Water Dilute Acid A 8O } " "~ 60 A 7O 60 "" Cultivars Fig. 4. The amunts f tartaric acid btained frm different cultivars. and 1.9% in Bulgaria [16]. The tartrate efficiency f Emir, Bgazkere, and Okuzgzu were similar t that reprted fr the ther V. vinifera cultivars. Figure 3 reveals that calcium tartrates prduced by ht water extractin shwed higher purity than calcium tartrates prduced by dilute acid extractin. High purity in a finished prduct is necessary t btain a high price. The highest purity ccurred at ph apprximately 4.5 rather than ph apprximately 7.0 the latter being required fr the highest yield. Diffusin f buffer cmpunds in ht water culd be mre than in the dilute acid. In precipitating the calcium tartrate in ht water extractin, the ph changed slwly, but in dilute acid ph changed rapidly. Iselectric pint f cllids in liquids is at ph apprximately 6.2, fr this reasn, they cntaminate tartrate and lwer the tartrate purity f calcium tartrates which are prduced with dilute acid extractin [4]. In rder t increase the tartrate purity filtratin, bentnite clarificatin r settling vernight can be applied [12]. The tartrate purity fund in varius investigatins were reprted as 52% t 55.7% and 51% [10,16]. Efficiency f tartrate extractin frm the varius cultivars is cmpared in Figure 4. Efficiency f recvery acid was based n the rigi- Fig. 3. The purity f calcium tartrate. Cultivars nal pmace cntent, i.e., 10 kg. The highest efficiency was btained in Bgazkere pmace prcessed by ht water extractin. This tartaric acid efficiency depends n calcium tartrate cntent and methd f tartaric acid prductin. The prperties f tartaric acid btained are listed in Table 5. The specific rtatin f pure tartaric acid at 20% cncentratin is and tartaric acid f winery byprduct is dextrrtary. And als slubility f tartaric acid at 20 C is 139 g/100 ml and the melting pint is 157 C t 159 C [18]. Because the rafinatin was nt efficiency applied, the specific rtatins were fund higher and slubility lwer than the pure nes. Presumably this was caused by impurities. Cnclusins The present study revealed that the pmaces f Emir, Okuzgzu, and Bgazkere, which are widespread grape varieties in Anatlia, culd be used t prduce tartaric acid. Methds used in this study are applicable in small wine plants. Ht water extractin is simpler and mre efficient. Explratin f the subject n an industrial scale will be beneficial. Table 5. Prperties f tartaric acids prduced. Ht water extractin Dilute acid extractin Cultivar Emir OkOzg6zLi Bgazkere Specific rtatin [a] Slubility [g/100 ml] ph Melting Specific pint rtatin ( c) [a] Slubility ph Melting [g/100 ml] pint (c)

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