As concerns the final oil conversion, the ethanolysis reaction seems
to stop at almost complete conversion (99.8%) at the highest alcoholto-
oil molar ratio used (24:1), at about 98% oil conversion for a ratio
of 12:1 and 84% for the lowest initial alcohol-to-oil molar ratio of 6:1.
These large differences cannot be attributed to the possible influence
of the alcohol in excess on the oil equilibrium conversion. In fact, at
40 °C, atmospheric pressure and initial alcohol-to-oil molar ratio of
6:1, the equilibrium oil conversion is well-above 99% for both
methanolysis and ethanolysis [57]. Interestingly, Tsuji et al. [64] have
found that not the thermodynamic limitation on the oil conversion
but the catalyst depletion by side reactions is the main reason for the
positive effect of using alcohol-to-oil molar ratios above the stoichiometric
value. According to these authors, the main side reaction is the
saponification of the triglycerides by reaction with the hydroxide ions
leading to the formation of soaps. Data on soaps formation in this
work are provided in the next section. In this way, the consumption of
hydroxide shifts the equilibrium (Eq. (4)) to the consumption of
ethoxide ions, thus lowering the rate of the ethanolysis reactions and,
eventually stopping themif the initial alkali metal hydroxide concentration
is low. This allows explaining the strong positive effect on the final
conversion of using high ethanol-to-oil ratios. The excess of alcohol favors
the transesterification due to their direct influence on the forward
transesterification steps (Eqs. (1)–(3)) and also on the formation of the
catalytically active ethoxide species (Eq. (4)). Moreover, it negatively affects
the concentration of hydroxide and therefore, the progress of the
saponification reactions, as also found by Černoch et al. [24]. But an excessively
high value of the ethanol-to-oil molar ratio is not interesting
due to the difficulties introduced in the recovery of the reaction products
[27,65] as well as to the high cost associated to the ethanol purification
for reuse in the reactors. It should be noted that due to the
homogeneous character of the reaction mixture it is necessary to remove
the non-reacted ethanol at the end of the reaction for allowing
the separation of the produced biodiesel and glycerol by settling or centrifugation
[20,66,67]. As a result of the opposite effects described, the
value of the initial ethanol-to-oil molar ratio should be established in
each case after an optimization process. In the literature, optimal values
of this variable between 5:1 and 20:1 can be found depending on the triglycerides
source, the catalyst used, and the values of the remaining variables.
Generally, the optimal initial ethanol-to-oil molar ratio increases
as the reaction temperature increases [2] and the catalyst concentration
decreases [3]. In our case, a lowvalue of 0.10wt.% NaOHwas selected for
these experiments thus explaining the necessity of a high (24:1) initial
ethanol-to-oil ratio in order to achieve final conversions close to the
equilibriumvalue. A low catalyst concentration was used in order to facilitate
data acquisition at short reaction times as well as to the interest
in studying the ethanolysis system under conditions more favorable
from the point of view of the purity of the final products [68].
As concerns the final oil conversion, the ethanolysis reaction seemsto stop at almost complete conversion (99.8%) at the highest alcoholto-oil molar ratio used (24:1), at about 98% oil conversion for a ratioof 12:1 and 84% for the lowest initial alcohol-to-oil molar ratio of 6:1.These large differences cannot be attributed to the possible influenceof the alcohol in excess on the oil equilibrium conversion. In fact, at40 °C, atmospheric pressure and initial alcohol-to-oil molar ratio of6:1, the equilibrium oil conversion is well-above 99% for bothmethanolysis and ethanolysis [57]. Interestingly, Tsuji et al. [64] havefound that not the thermodynamic limitation on the oil conversionbut the catalyst depletion by side reactions is the main reason for thepositive effect of using alcohol-to-oil molar ratios above the stoichiometricvalue. According to these authors, the main side reaction is thesaponification of the triglycerides by reaction with the hydroxide ionsleading to the formation of soaps. Data on soaps formation in thiswork are provided in the next section. In this way, the consumption ofhydroxide shifts the equilibrium (Eq. (4)) to the consumption ofethoxide ions, thus lowering the rate of the ethanolysis reactions and,eventually stopping themif the initial alkali metal hydroxide concentrationis low. This allows explaining the strong positive effect on the finalconversion of using high ethanol-to-oil ratios. The excess of alcohol favorsเพิ่มเนื่องจากอิทธิพลของพวกเขาโดยตรงไปข้างหน้าเพิ่มขั้นตอน (Eqs (1)–(3)) และยังการก่อตัวของการcatalytically งาน ethoxide พันธุ์ (Eq. (4)) นอกจากนี้ มันส่งผลเสียต่อความเข้มข้นของไฮดรอกไซด์ และ ความคืบหน้าของการปฏิกิริยาสะพอนิฟิ เป็นยัง พบ โดย Černoch et al. [24] แต่มีมากเกินไปค่าสูงของอัตราส่วนเอทานอลน้ำมันสบไม่น่าสนใจเนื่องจากความยากลำบากในการกู้คืนผลิตภัณฑ์ปฏิกิริยา[27,65] รวมทั้งเป็นค่าใช้จ่ายสูงสัมพันธ์กับการทำให้บริสุทธิ์ของเอทานอลสำหรับนำมาใช้ใหม่ในเตาปฏิกรณ์ ควรสังเกตที่ครบกำหนดตัวละครเหมือนของปฏิกิริยาส่วนผสมจำเป็นต้องเอาออกเอทานอลไม่ใช่ปฏิกิริยาที่เกิดขึ้นเมื่อสิ้นสุดปฏิกิริยาเพื่อให้แบ่งแยกการผลิตไบโอดีเซลและกลีเซอรชำระหรือ centrifugation[20,66,67] จากผลตรงกันข้ามอธิบาย การค่าของอัตราส่วนสบเอทานอลน้ำมันเริ่มจะก่อตั้งขึ้นในแต่ละกรณีหลังจากกระบวนการปรับให้เหมาะสม ในวรรณคดี ค่าสูงสุดของตัวแปรระหว่าง 5:1 และ 20:1 นี้สามารถพบได้ตามระดับไตรกลีเซอไรด์แหล่งที่มา catalyst ที่ใช้ และค่าของตัวแปรที่เหลือโดยทั่วไปแล้ว ดีที่สุดเริ่มต้นเอทานอลน้ำมันสบอัตราส่วนเพิ่มเพิ่มอุณหภูมิของปฏิกิริยา [2] และความเข้มข้นของ catalystลดลง [3] ในกรณี lowvalue ของ 0.10wt.% NaOHwas เลือกthese experiments thus explaining the necessity of a high (24:1) initialethanol-to-oil ratio in order to achieve final conversions close to theequilibriumvalue. A low catalyst concentration was used in order to facilitatedata acquisition at short reaction times as well as to the interestin studying the ethanolysis system under conditions more favorablefrom the point of view of the purity of the final products [68].
การแปล กรุณารอสักครู่..
