Tung yağının 1,3 spesifik enzim ile hidroliz koşullarının incelenmesi
Investigation on enzymatic fat splitting conditions of tung oil with 1,3 spesific enzyme
- Tez No: 46381
- Danışmanlar: PROF.DR. TUNCER ERCİYES
- Tez Türü: Yüksek Lisans
- Konular: Kimya Mühendisliği, Chemical Engineering
- Anahtar Kelimeler: Belirtilmemiş.
- Yıl: 1995
- Dil: Türkçe
- Üniversite: İstanbul Teknik Üniversitesi
- Enstitü: Fen Bilimleri Enstitüsü
- Ana Bilim Dalı: Belirtilmemiş.
- Bilim Dalı: Belirtilmemiş.
- Sayfa Sayısı: 34
Özet
ÖZET Enzimler, kimyasal reaksiyonların daha ılımlı koşullarda gerçekleşmesini sağlayan katalizörlerdir[l]. Günümüzde yağ asitlerinin üretiminde kullanılan prosesler, yüksek sıcaklık va basınç altında çalışmaktadır. Bu ise; fazla enerji sarfiyatına, yüksek ürün maliyetine ve yüksek ekipman giderlerine sebep olmaktadır. Bu da üreticileri oda sıcaklığında ve atmosferik basınç altında hirolizi sağlayan enzimatik hidroliz konusu üzerinde çalışmaya yöneltmiştir. Ayrıca bazı konjuge çift bağlı ve yüksek iyot değerine sahip yağların hidrolizi normal hidroliz koşullarında gerçekleşmemektedir. Bu nedenle enzimatik hidroliz üzerinde durulmaktadır. Tung yağının da çok sayıda konjuge çift bağ içermesi ve %80'inin a-eleostearik asitten oluşması yüksek sıcaklıkta polimerleşmesine neden olmaktadır. Bu yüzden tung yağının 1,3-spesifik enzim ile hidroliz koşullan incelenmiştir. Deneysel çalışmada 30-35-40 °C'de, 0.5:10 ve 0.5:20 yağ:su(gr:ml) oranlarında, değişen enzim miktarlarıyla çalışılmış ve bu koşullar altında enzimin maksimum aktivite gösterdiği hidroliz koşullan tespit edilmiştir.
Özet (Çeviri)
SUMMARY INVESTIGATION OF ENZYMATIC FAT SPLITTING CONDITIONS OF TUNG OIL WITH 1,3 SPESIFIC ENZYME Organic fatty acids and their derivates are findings an everincreasing application in the chemical, soap, rubber and other industries. The main source for the manufacture of these products is animal fats, and the most widely used industries processes are: - Fat splitting or fat hydrolysis - Distillation of crude fatty acids - Fractination of hydrogenation of distilled fatty acids On observing the chemical formula of a trigliseride where R is a fatty acid radical CH2-0-OC-R CH2-OH COOH-R I - i CH-O-OC-R +3HzO> CH-OH + COOH-R I I CHrO-OC-R CH2-OH COOH-R it can be seen that the addition of three molecules of water to one molecule of trigliseride yields one molecule of glycerol and three molecules of fatty acids. This reaction is reversible and hence it is of interest to observe the conditions which cause it to go in a direction from left to right. The formula itself shows that since water is to be added, the reaction must be conducted in the presence of a large excess of this element and under pressure. In fact, for splitting to occur the following conditions are requared:- Excess of water - Pressure of 30 kg/cm2 -Temperature in the range of 225-230 °C These conditions are essential if the reaction is to occur without the aid of catalysts. In the presence of catalysts, the reaction is accelerated and is seen to occur at a pressure of the order of 7 kg/cm and at a temperature of 160-170 C. At one time, fat splitting was carried out in autoclaves operating at a pressure of 7 kg/cm2 and consequently catalysts were essential. The resulting products are extremely dark fatty acids and discolored dilute (% 10) aqueous solutions of glycerol. The fatty acids are unusable as obtained and need to be redistilled to remove color and by-products. The glycerol layer after concentration usually is distilled to remove color and impuritiesThese process are enrgy intensive and give rise to a variety of undesirable side reactions. For example, highly unsaturated fatty acids can polymerize and if the temperature rises about 230 °C, anhydrides form that, if heating continues, decompose to yield ketones and hydrocarbons. In the interest of conserving energy and to minimize thermal degradation, set out to study enzymatic hydrolysis of triglyserides. This approach would lead to little or no additional color development, cause no chemical degradation and a more consentrated glycerol solution might also be achieved. A variety of lipases of different origins have been studied in the biochemical literature. Although pancreatic lipase has been available commercialy for some time, it is only recently that purified preparations of microbial lipases have been produced industrially. It is therefore likely inthe foreseeable future, industurial processes will be developped for enzymatic hydrolysis of triglyserides and possible for the enzymatic esterification.In the experimental study, Lipozim 20 catalyzed hydrolysis reaction of tung oil and olive oil were investigated- Olive and tung oils were obtanined from the local industry. Main characterization of these oils are given in Table 1. Table 1. Main characterization of these oils in the study. Tung oil is obtained from the kernels (oil content, about 17.5 %) of the fruit of the tung tree. The oil is a pale yellow or darker liquid with valuable drying and polimerization properties because of the high content of eleostearic acid. The oil is used mainly in quick drying enamels and varnishes and in combination with other drying oils to improve overall properties such as water- and alkali-resistance. An half of gram of given oil and different U/meg. of lipase suspansion were weighted into a stoppedred flask. The flasks were placed in a water bath at the reaction temperature. The reaction was carried out under stirring and each flask was removed from the bath after the predetermined time intervals. 50 ml of alcohol-ether (1 : 1 by volume) was added immediately to the flask to deactivate the enzyme. Free falty acid content was determined by alkali titration. Remaining ester percantage was calculated from free acid percentage corrected according to the initial acid content by using mean moleculer weight of the acid mixture of the corresponding oil. In the experimental study, Figure 1 shows the acid value vs time the linear scale in 10 ml of buffer solution of tung oil. To determine the maksimum activity of enzymes, acid value vs temperature was plotted at 30 °C, 40 °C, and 45 °C with 10 ml of buffer solution and olive oil and it was shown Figure 2.There is no advantage to increase the buffer solution. Figure 3 shows acid value vs time with 10 and 20 ml of buffer solution and tung oil. Acfd Value -“”"- 20 U/meg yag ~s~ 70 U/meg yao 150 200 Time (min.) 35 U/meg yag 80 U/meg yag 250 300 350 56.2 U/meg yag Figüre 1 Acid value of Tung Oil with 1 0 ml of Buffer Solution at 40 °C Acid Value 50 100 150 200 Time (min.) 250 300 350 - 70 U/meg yag -+~ 70 U/meg yag - *- 70 U/meg yag Figure 2 Acid Values at 30 and 40 and 45 °C of Olive Oil VII70 60 50 40 30 20 Acid Value 150 200 Time (min.) 250 300 350 -&- 70 U/meg yag -*- 70 U/meg yag Figure 3 Acid Values With 10 and 20 ml Buffer Solution of Tung Oil Table 1. Hydrolysis % Value of Tung Oil and Olive Oil at the end of % Hours These results show that: 1. Maksimum activity of Lipozim 20 Enzyme is at 40 °C. Vllt2. There is no effectivity to increase the volume of the buffer solution, so that 10 ml of buffer solution was chosen. 3. As optimum quantity of enzyme, 56.2 UAneg oil was established. Although inreasing the quantity of enzymes rises hydrolysis %, there is no advantage as economically. 4. Conjuge double bonds resist to the hydrolysis reaction with catalysis of enzyme, so hydrolysis % of tung oil is lower than hydrolysis of olive oil.
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