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表 二 丙 酸 異 丙 酯 蒸 氣 壓 量 測 與 計 算 結 果
T (K) Pexpt(kPa) Pcalc(kPa)a Dev P (%)b △P/P AAD (%)c 337.66 24.60 24.44 -0.64 0.41 342.61 29.50 29.69 0.64
347.62 35.68 35.74 0.16 352.67 42.43 42.62 0.44 357.58 50.12 50.10 -0.03 362.57 59.00 58.55 -0.78 382.65 101.3 101.5 0.20
aAntoine 方程式的計算結果。
mixture area testa
isopropyl propionate + isopropanol 6.0 % (+) propionic acid + isopropyl propionate -0.1 % (+)
aTolerance for the area test is 10 %; (+): pass the consistency test.
表四 恆壓汽液相平衡數據關聯結果
NRTL-HOCa UNIQUAC-HOCa
mixtureb b12 M1b -211.06 504.42 0.3 0.10 0.0017 0.029 0.0094 -3.01 -72.34 0.10 0.0018 0.029 0.0098 M2b -186.72 586.47 0.3 0.26 0.0032 0.089 0.0183 204.03 -420.93 0.28 0.0036 0.095 0.0190
aNRTL model: ij bij
bM1: isopropyl propionate (1) + i-propanol (2); M2: propionic acid (1) + isopropyl propionate (2).
cM AAD =
表五 三成份系統水+丙酸異丙酯+異丙醇計算結果
NRTL-HOC prediction
323.24 5 0.45 5.91 0.0677 0.0132 0.0633 348.15 5 0.38 2.14 0.0556 0.0138 0.0643 373.15 5 0.67 0.54 0.0480 0.0126 0.0468
UNIQUAC-HOC prediction
323.24 5 0.56 6.38 0.0599 0.0129 0.0617 348.15 5 0.28 2.10 0.0497 0.0116 0.0610 373.15 5 0.46 0.42 0.0363 0.0070 0.0361
NRTL-HOC correlation
323.24 6 0.11 2.56 0.0171 0.0128 0.0279 348.15 5 0.38 1.25 0.0155 0.0039 0.0298 373.15 5 0.75 0.41 0.0185 0.0024 0.0182
UNIQUAC-HOC correlation
323.24 6 0.12 1.81 0.0154 0.0022 0.0322 348.15 5 0.25 0.75 0.0099 0.0022 0.0286 373.15 5 0.70 0.35 0.0151 0.0036 0.0187
angis the number of calculated data points. The deviations consider only the data points which are in the predicted immiscible region; that is, ngmay not be equal to the number of experimental data points.
bT AAD (K) =
, where npis the number of data points.
cP/P AAD (%) =
, where ncis the number of components
表六 丙酸異丙酯合成反應實驗結果
T (K) 323 328 333 338 343 333 333 333 333
醇酸比 Bo 1 1 1 1 1 0.2 0.5 5 10
KX 1.103 1.204 1.283 1.395 1.425 6.396 1.428 0.940 0.712 k1a 0.755 1.168 1.681 2.444 3.533 3.940 2.433 0.839 0.750 k2a 0.684 0.970 1.311 1.753 2.480 0.616 1.704 0.892 1.053 XAADD (%)b 4.0 3.8 1.8 2.0 1.6 4.0 1.8 4.1 4.9
XAe 0.512 0.523 0.531 0.541 0.544 0.193 0.359 0.826 0.881
ak : 反應動力常數，cm6/(g min mol)。
0 0.2 0.4 0.6 0.8 1 x1, y1
340 360 380 400 420
T/K
isopropyl propionate + isopropanol propionic acid + isopropyl propionate calc. (NRTL-HOC)
calc. (UNIQUAC-HOC)
圖 4 恆壓系統汽液相平衡圖
0.7 0.85 1 x2I
320 340 360 380
T/K
0 0.002 0.004 x2II
0.3 0.45 0.6 y2
expt.
calc. (NRTL-HOC) calc. (UNIQUAC-HOC)
圖 5 水(1)+丙酸異丙酯(2)之汽液液平衡的量測值與計算值的比較
0.0026 0.0027 0.0028 0.0029 0.003 0.0031 T-1/ K-1
10 100 1000
P/kPa
expt.
calc. (NRTL-HOC) calc. (UNIQUAC-HOC)
圖 6 水+丙酸異丙酯之汽液液平衡壓力對溫度的關係圖
0.00 0.25 0.50 0.75 1.00 0.00
0.25
0.50
0.75
1.00 0.00
0.25 0.50 0.75 1.00
liquid phase vapor phase expt. tie-lines
UNIQUAC-HOC prediction UNIQUAC-HOC correlation
water
isop rop
ano l
isopropyl propionate
圖 7 水+丙酸異丙酯+異丙醇在 348.15 K 下的汽液液三相平衡組成圖
-3 -2 -1 0 1 ln [(1-w2I) / w2I]
-4 -3 -2 -1
ln[(1-w1II )/w1II ]
323.24 K 348.15 K 373.15 K
Othmer-Tobias correlation
圖 8 水 + 丙酸異丙酯 + 異丙醇系統之一致性測試結果
圖 9 使用 40 mesh 之 Amberlyst 35，Bo= 1 及不同反應溫度狀況之丙酸異丙酯合 成反應動力實驗結果與擬均相-理想溶液動力模式擬合結果。
圖 10 進料酸醇莫耳比效應
圖 11 觸媒填充量的影響
圖 12 觸媒粒徑的影響
圖 13 反應平衡常數與溫度關係圖
圖 14 正逆向反應常數與溫度關係圖