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研究生:劉昌樹
研究生(外文):Chen-Shu Liu
論文名稱:鮪魚眼窩油之超臨界二氧化碳萃取及其氧化安定性之探討
論文名稱(外文):Tuna Orbital Oil Extracted by Supercritical Carbon Dioxide and Its Oxidative Stability
指導教授:孫璐西孫璐西引用關係
指導教授(外文):Lucy Sun Hwang
學位類別:碩士
校院名稱:國立臺灣大學
系所名稱:食品科技研究所
學門:農業科學學門
學類:食品科學類
論文種類:學術論文
論文出版年:1999
畢業學年度:87
語文別:中文
論文頁數:105
中文關鍵詞:鮪魚眼窩油超臨界二氧化碳氧化安定性水煮法萃取DHA收率儲藏安定性
外文關鍵詞:tuna orbital oilsupercritical carbon dioxideoxidative stabilitywet-renderextractDHAyieldstorage stability
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多元不飽和脂肪酸中的二十二碳六烯酸(docosahexaenoic acid,DHA)被證實具有多種生理功能,鮪鰹等魚類之眼窩脂肪中則發現含有高量的DHA。鮪魚為我國的大宗漁獲物,魚頭為加工後的廢棄物,本論文以鮪魚魚頭的眼窩脂肪為原料,以超臨界二氧化碳(SC-CO2)萃取其中富含DHA的油脂,並進一步與水煮法所得的魚油比較,以探討兩者之油脂品質與儲藏安定性。
鮪魚眼窩脂肪組織之主要成分為水分(40.99-42.93%)、粗脂肪(46.24-49.24%)、粗蛋白(7.82-8.78%)和灰份(0.72-0.9%)。鮪魚眼窩油中所含的多元不飽和脂肪酸佔總脂肪酸的40.06%;而DHA佔總脂肪酸的30.57%,為鮪魚眼窩油中含量最高的脂肪酸。
以水煮法萃取鮪魚眼窩粗油,其萃油率占原脂肪含量之56.65%。以SC-CO2萃取鮪魚眼窩油,在30℃-60℃的範圍內,定溫下,鮪魚眼窩油之萃出率隨壓力上升而增加,於4000psi 60℃時可達最大收率85.95%。低壓時(2000及2500psi),萃油率隨溫度之升高而下降,例如2000psi下,30、40、50、60℃的萃油率分別為41.66%、23.68%、8.07%、0.7%。高壓時(3000-4000psi),萃油率隨溫度之變化可分為兩個區間,在40℃-50℃的區間,萃油率隨溫度之上升而增加;其他溫度區間則與低壓時相似,萃油率隨溫度之上升而減少。
鮪魚眼窩脂肪組織中的DHA含量為16.52 g/100g oil(以Folch溶劑萃取),經水煮得到的鮪魚眼窩粗油中DHA僅為7.36(g/100g oil),其他脂肪酸也有含量降低的情形,且DHA收率只有25.24%。經去除雜質的精製油,其DHA含量可提高到14.14(g/100g oil),但是DHA的回收率也只能達到40.86%。在2000psi-4000psi,30℃-60℃下,SC-CO2萃取得到的鮪魚眼窩油中DHA含量在13.12-21.18(g/100g oil)之間,甚至高於原料(眼窩脂肪)。不同SC-CO2萃取條件萃得的魚油其DHA含量並沒有顯著的差異。
水煮法粗油(含有1.23 mg/g的磷脂質)可不經脫膠步驟,而直接進行脫酸、脫色及脫臭。水煮粗油的酸價為0.96(mg KOH/g oil),過氧化價為19.93(meq/kg oil),經過精製後酸價為0.08(mg KOH/g oil),過氧化價為11.67(meq/kg oil)。鮪魚眼窩脂肪組織於SC-CO2萃取前磷脂質含量為1.76(mg/g),萃取後磷脂質已檢測不出,且鮪魚眼窩油的過氧化價會從萃取前的8.25(meq/kg oil)降至6.35(meq/kg oil),但是酸價卻會從0.8(mg KOH/g oil)上升到1.12(mg KOH/g oil)。
鮪魚眼窩油的萃取方法會影響所得油脂的儲藏安定性。於37℃避光透氧的儲藏試驗中,以SC-CO2萃取、水煮及水煮精製所得的鮪魚眼窩油其POV與TBA皆在第八天達到最大值,接著便開始下降。從POV與TBA上升的趨勢看來,油脂氧化安定性為水煮粗油的安定性最差,其次是以SC-CO2萃取的油,而水煮精製油最好。
Orbital adipose tissues of tunas (Thunnuss sp.) and bonitos (Auxis sp., Euthynnus sp. and Katsuwonus sp.) contain considerable quantities of docosahexaenoic acid (DHA) which was confirmed to have various beneficial physiological functions. Tuna is a major catch of marine fish in Taiwan and its head is a seafood processing waste. The objectives of this study were to extract the DHA-rich oil from tuna orbital adipose tissue with supercritical carbon dioxide (SC-CO2) and compare its oxidative stability with oil obtained from wet rendering of the tuna orbital adipose tissue.
The proximate composition of tuna orbital adipose tissue was moisture (40.99-42.93 %), crude fat (46.24-49.24 %), crude protein (7.82-8.78 %) and ash (0.72-0.9 %). Polyunsaturated fatty acids of tuna orbital adipose tissue constitute 40.06 % of the total fatty acids, and DHA is the most abundant one which constitutes 30.57 % of the total fatty acids.
The extracting yield of tuna orbital crude oil with wet rendering was 56.65 % of original lipid content. When extracting with SC-CO2 in the temperature range of 30~60oC, the extracting yield of tuna orbital oil increased with pressure at constant temperature, the maximum yield was 85.95 % at 4000 psi and 60 oC. At low pressures (2000 and 2500 psi), the yields of tuna orbital oil decreased with temperature. For example, at 2000 psi and 30、40、50 and 60 oC, the yields were 41.66, 23.68, 8.07 and 0.7 %, respectively. At high pressure (3000~4000 psi), the changes of yields of tuna orbital oil with temperature can be divided into two regions. At the region of 40~50oC, the extracting yields of tuna orbital oil increased with temperature; while at other temperature regions, the yields followed the same trend as low pressure conditions that is yields decreased temperature.
The DHA content of tuna orbital adipose tissue was 16.52 g/100g oil (determined by Folch method). With wet rendering, the DHA content of tuna orbital adipose tissue decreased to 7.36 (g/100g oil) and the yield was only 25.24 %, other fatty acids also decreased. The DHA content of refined wet-rendered oil raised to 14.14 (g/100g oil) due to the removed of impurities, however the recovery of DHA only raised to 40.86 %. In the SC-CO2 extraction of tuna orbital oil, the yields of DHA content were 13.12~21.18 (g/100g oil), even higher than the raw material (tuna orbital adipose tissue). There were no significant difference in DHA content at different conditions of SC-CO2 extraction.
Crude oil from wet rendering (phospholipid content was 1.23 mg/g oil) can be directly refined by alkali refining、bleaching and deordorization without degumming. The acid value (AV) of crude oil from wet-rendering was 0.96 (mg KOH/g oil) and peroxide value (POV) was 19.93 (meq/kg oil); after refining the AV was 0.08 (mg KOH/g oil) and POV was 11.67 (meq/kg oil). Before SC-CO2 extracting, phospholipids content was 1.76 (mg/g) and POV was 8.25 (meq/kg oil). After SC-CO2 extraction, phospholipids content was not detectable and POV decreased to 6.35 (meq/kg oil). But AV increased from 0.8 (mg KOH/g oil) before SC-CO2 extraction to 1.12 (mg KOH/g oil) after SC-CO2 extraction.
The extraction methods of tuna orbital oil could affect the oil storage stability. In the storage stability study at 37 oC under dark and in the pressure of oxygen, the POV and thiobarbituric acid (TBA) values of tuna orbital oil from SC-CO2 extraction, wet rendering without refining and wet rendering with refining all reached maximum value at 8 days, then slowed down. Judging from the increase trend of POV and TBA, the refined wet-rendered oil had the best storage stability, followed by SC-CO2 extracted oil. Crude wet-rendered oil had the least storage stability.
中文摘要Ⅰ
英文摘要Ⅲ
目錄Ⅴ
圖次IX
表次XI
壹、前言1
貳、文獻整理3
一、水產加工廢棄物之再利用3
(一)水產加工廢棄物之現況3
(二)魚油中多元不飽和脂肪酸DHA之簡介3
二、超臨界流體之簡介5
(一)超臨界流體之發展趨勢5
(二)超臨界流體之基本性質6
(三)超臨界二氧化碳之溶解度行為11
(四)溶質在超臨界流體中之相平衡量測及溶解度預測13
1. 狀態方程式17
2. 統計法18
3. 狀態方程式與統計法之比較19
(五)超臨界二氧化碳萃取在食品工業上之應用20
1. 咖啡與茶之咖啡因的去除21
2. 啤酒花苦味及香味成分萃取21
3. 香料及植物精油萃取21
4. 油脂的萃取純化21
(1)黃豆油脫膠與純化的應用22
(2)黃豆油脫酸及脫臭的應用22
5. 其他油脂之應用23
6. 天然色素萃取23
7. 膽固醇去除24
8. 酵素反應應用25
9. 機能性成分萃取25
三、魚油之萃取26
(一)一般方法26
(二)超臨界二氧化碳萃取法27
四、從水產油脂中濃縮三酸甘油酯型態之DHA28
(一)低溫溶劑區分法29
(二)酵素法29
(三)超臨界二氧化碳萃取法29
五、超臨界二氧化碳萃取對油脂氧化安定性之影響30
(一)不同操作條件(壓力溫度)超臨界二氧化碳31
(二)傳統萃取法與超臨界二氧化碳萃取法31
參、材料與方法33
一、實驗材料33
(一)原料(1)33
(二)原料(2)33
二、化學藥品34
三、儀器設備35
(一)超臨界二氧化碳萃取裝置35
(二)氣相層析儀37
(三)薄層層析-火焰離子化檢測器37
(四)示差掃描熱分析儀37
(五)掃描式電子顯微鏡37
四、本論文之實驗流程38
五、實驗方法39
(一)鮪魚眼窩脂肪之一般成分分析39
(二)油脂分析項目39
1.油脂氧化程度分析39
(1)酸價39
(2)TBA值39
(3)A26840
(4)過氧化價40
2.脂肪酸組成41
(1)酯化方法41
(2)脂肪酸定量之GC條件41
3.磷脂質含量分析42
(三)油脂萃取42
1.溶劑萃取法42
2.水煮法42
(1)水煮43
(2)脫酸43
(3)脫色43
(4)脫臭43
3.超臨界二氧化碳萃取法45
(1)以不同壓力及溫度條件萃取鮪魚眼窩脂肪45
(2)鮪魚眼窩脂肪溶解度計算與表示方法46
(四)掃描式電子顯微鏡47
(五)示差掃描熱分析47
六、統計分析47
肆、結果與討論48
一、鮪魚眼窩脂肪組織之一般成分分析48
(一)一般成分組成分析48
(二)脂肪酸組成48
(三)兩批原料之間的差異52
二、鮪魚眼窩油脂之萃取52
(一)水煮萃取52
1.水煮52
2.化學精製53
3.萃油率53
(二)超臨界二氧化碳萃取54
1.超臨界二氧化探萃取範圍之選定54
2.壓力溫度對萃出率之影響57
3.密度對萃出率之影響64
4.Chrastil方程式66
三、萃取方法對鮪魚眼窩油脂肪酸組成之影響66
(一)水煮法所得鮪魚眼窩油之脂肪酸組成66
(二)超臨界二氧化碳萃取法所得鮪魚眼窩油之脂肪酸組成70
(三)超臨界二氧化碳萃取條件對鮪魚眼窩油脂肪酸組成之影
響72
四、萃取方法對鮪魚眼窩油氧化安定性之影響72
(一)剛萃取出油脂之品質72
(二)37℃儲藏試驗下之氧化安定性80
1.過氧化物之測定80
2.紫外光268nm吸光值之變化80
3.TBA值之變化83
伍、結論89
陸、參考文獻90
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