草酸二乙酯新合成过程的热力学分析和实验验证

万思玉; 石磊

doi:10.19906/j.cnki.JFCT.2021007

草酸二乙酯新合成过程的热力学分析和实验验证

doi: 10.19906/j.cnki.JFCT.2021007

万思玉^{1, 2, 3},
石磊^{1, 2, ,}

1.
沈阳化工大学资源化工与材料教育部重点实验室，辽宁沈阳 110142
2.
沈阳化工大学能源与化工产业技术研究院，辽宁沈阳 110142
3.
沈阳化工大学理学院，辽宁沈阳 110142

基金项目: 辽宁省教育厅重点攻关和服务地方项目(LDB2019005)，高水平创新团队国（境）外培养重点项目(2018LNGXGJWPY-ZD002)，国家自然科学基金(21303106)和辽宁省高等学校创新人才(LR2016015)项目资助

详细信息

通讯作者:
E-mail：shilei@syuct.edu.cn

中图分类号: O642.1
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出版历程
- 收稿日期: 2020-08-26
- 修回日期: 2020-10-16
- 刊出日期: 2021-01-29

Thermodynamic analysis and experimental verification of a new route for direct diethyl oxalate synthesis

WAN Si-yu^{1, 2, 3},
SHI Lei^{1, 2
, ,}

1.
Key Laboratory on Resources Chemicals and Materials of Ministry of Education, Shenyang University of Chemical Technology, Shenyang 110142, China
2.
Institute of Industrial Chemistry and Energy Technology, Shenyang University of Chemical Technology, Shenyang 110142, China
3.
College of Science, Shenyang University of Chemical Technology, Shenyang 110142, China

Funds: The project was supported by the Key Task and Local Project in Science & Technology of SYUCT, China (LDB2019005), High-Level Innovation Team Overseas Training Project of Liaoning, China (2018LNGXGJWPY-ZD002), National Natural Science Foundation of China (21303106) and Innovative Talents in University of Liaoning Province (LR2016015)

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Corresponding author: E-mail：shilei1982@dicp.ac.cn

摘要

摘要: 报道新颖的草酸二甲酯（DMO）与乙醇（EtOH）通过酯交换路径一步合成高品质草酸二乙酯（DEO）。采用基团贡献法及Watson公式估算过程中各物质的热力学参数，并通过经典热力学公式计算在常压和温度323−368 K时合成DEO各步反应的焓变、熵变、吉布斯自由能及平衡常数。通过实验测定不同温度和原料比例下DMO转化率、产物组成和反应平衡常数并与理论估算值比较。发现实测DMO转化率与估算值误差在1%内，实测平衡常数与估算值基本一致。经过严格的实验验证，证明经热力学方法估算的热力学参数比较可靠。模拟真实催化精馏条件，以塔釜DEO纯度达99.9%为目标计算353 K时塔釜的初始原料和最终产物组成，当塔釜EtOH含量高于2.59%，初始n_(EtOH)/n_(DMO)大于2.10时可使DEO纯度达到指标，并显著降低整体工艺能耗，是一个高效绿色的DEO生产工艺。
- 草酸二甲酯 /
- 草酸二乙酯 /
- 酯交换 /
- 热力学 /
- 基团贡献法 /
- 催化精馏
Abstract: The synthesis of high quality diethyl oxalate (DEO) via transesterification of dimethyl oxalate (DMO) and ethanol (EtOH) was reported. The thermodynamic data of each substance involved in the reaction were estimated by Benson and Joback's group contribution method and Watson formula, and the enthalpy change, entropy change, Gibbs free energy and equilibrium constant of each step of DEO synthesis were calculated by classical thermodynamic formula under atmospheric pressure and in the temperature range of 323−368 K. The DMO conversion, product composition and reaction equilibrium constant at different temperatures and raw material ratios were measured by experiments and compared with the theoretical data. It is found that the error between the measured DMO conversion and the estimated value is less than 1%, and the measured equilibrium constant is basically consistent with the estimated value. After strict experimental verification, it is proved that the thermodynamic data estimated by thermodynamic analysis are reliable. The actual catalytic distillation conditions were simulated, and the composition of the initial raw materials and the final products at 353 K was calculated with the hypothesis of 99.9% DEO purity at the bottom. When the content of EtOH in the bottom was higher than 2.59% and the molar ratio of initial EtOH to DMO was higher than 2.10, the purity of DEO could reach the target, and the overall process energy consumption was significantly reduced. It would be an efficient and green route for DEO synthesis.
- dimethyl oxalate /
- diethyl oxalate /
- transesterification /
- thermodynamics /
- group contribution method /
- catalytic distillation

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表 1 估算标准摩尔生成焓的Benson基团贡献值

Table 1 Group contribution value based on Benson method for standard molar formation enthalpy

Group	n_i（DMO）	n_i（MEO）	n_i（DEO）	${\Delta _f }H_{298}^\Theta$ / (kJ·mol⁻¹)
C－(O)(H)₃	2	1	0	−42.19
O−(C)(CO)	2	2	2	−180.41
CO−(O)(CO)	2	2	2	−122.65
C−(C)(H)₃	0	1	2	−42.19
C−(O)(C)(H)₂	0	1	2	−33.91

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表 2 Joback估算理想气相比热容的基团贡献值

Table 2 Group contribution value of the specific heat capacity in gas phase derived from Joback method

Group	Group contribution value / (J·mol⁻¹·K⁻¹)
Group	$\Delta {a_i}$	$\Delta {b_i} \times {10^2}$	$\Delta {c_i} \times {10^4}$	$\Delta {d_i} \times {10^6}$
−CH₃	19.5	−0.808	1.53	−0.0967
−CH₂−	−0.909	9.50	−0.544	0.0119
−OH（alcohol）	25.7	−6.91	1.77	−0.0988
−COO−	24.5	4.02	0.402	−0.0452

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表 3 Joback and Reid法估算Δ_vH_b的基团贡献值

Table 3 Group contribution value of Δ_vH_b calculatied by Joback and Reid method

Group	n_i（DMO）	n_i（MEO）	n_i（DEO）	Δ_i
−CH₃	2	2	2	2.373
−CH₂−	0	1	2	2.226
−COO−	2	2	2	9.633

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表 4 计算的各物质在不同温度下的蒸发焓

Table 4 Vaporization enthalpy values at different temperatures

T/K	Δ_vH_T / (kJ·mol⁻¹)
T/K	DMO	MEO	DEO	MeOH	EtOH
323	47.60	49.89	56.27	36.38	40.55
338	46.44	48.66	54.80	35.26	39.26
353	45.64	47.81	53.78	34.08	37.91
368	44.41	46.92	52.21	32.82	36.47

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表 5 计算的各物质在不同温度下的气或液态标准摩尔生成焓和标准熵

Table 5 Calculated standard molar enthalpy of formation and entropy for either gas or liquid phase at different temperatures

	T/K	DMO	MEO	DEO	MeOH	EtOH
${\Delta _f}H_{{\rm{g}},T}^{\Theta}$/ (kJ·mol⁻¹)	323	−687.19	−720.51	−753.83	−199.68	−232.99
	338	−685.13	−718.07	−751.02	−199.00	−231.94
	353	−683.02	−715.57	−748.13	−198.31	−230.86
	368	−680.85	−713.00	−745.15	−197.59	−229.74
${\Delta _f}H_{{\rm{l}},T}^{\Theta}$/ (kJ·mol⁻¹)	323	−734.79	−770.40	−810.10	−236.06	−273.54
	338	−731.57	−766.73	−805.82	−234.26	−271.20
	353	−728.66	−763.38	−801.91	−232.39	−268.77
	368	−725.26	−759.92	−797.36	−230.41	−266.21
$S_{{\rm{g}},T}^{\Theta}$ / (J·mol⁻¹·K⁻¹)	323	351.47	400.16	437.33	243.30	286.23
	338	357.70	407.53	445.83	245.34	289.40
	353	363.83	414.77	454.20	247.36	292.54
	368	369.84	421.90	462.45	249.34	295.65
$S_{{\rm{l}},T}^{\Theta}$ / (J·mol⁻¹·K⁻¹)	323	204.10	245.70	263.12	130.67	160.69
	338	220.30	263.57	283.70	141.02	173.25
	353	234.54	279.33	301.85	150.82	185.15
	368	249.16	294.40	320.58	160.16	196.54

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表 6 酯交换反应（1）−（4）在不同温度下的Δ_rH^Θ（kJ/mol）和Δ_rS^ΘJ/（mol·K）

Table 6 Calculated enthalpy Δ_rH^Θ（kJ/mol）and entropy Δ_rS^ΘJ/（mol·K）values of transesterifications（1）−（4）at different temperatures

T/K	Reaction（1）		Reaction（2）		Reaction（3）		Reaction（4）
T/K	Δ_rH^Θ	Δ_rS^Θ	Δ_rH^Θ	Δ_rS^Θ	Δ_rH^Θ	Δ_rS^Θ	Δ_rH^Θ	Δ_rS^Θ
323	−0.35	−1.02	1.87	11.58	−2.22	−12.60	−4.09	−24.18
338	−0.37	−1.06	1.78	11.04	−2.15	−12.10	−3.93	−23.14
353	−0.49	−1.35	1.66	10.46	−2.15	−11.81	−3.81	−22.27
368	−0.50	−1.34	1.14	8.86	−1.64	−10.20	−2.78	−19.06

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表 7 酯交换反应（1）−（4）在不同温度下的Δ_rG^Θ（kJ/mol）和K^Θ

Table 7 Calculated Gibbs free energy Δ_rG^Θ（kJ/mol）and equilibrium constant K^Θ of reactions（1）−（4）at different temperatures

T/K	Reaction（1）		Reaction（2）		Reaction（3）		Reaction（4）
T/K	Δ_rG^Θ	K^Θ	Δ_rG^Θ	K^Θ	Δ_rG^Θ	K^Θ	Δ_rG^Θ	K^Θ
323	−2.054 × 10⁻²	1.007	−1.870	2.006	1.849	0.502	3.720	0.250
338	−1.172 × 10⁻²	1.004	−1.952	2.003	1.939	0.502	3.891	0.250
353	−1.345 × 10⁻²	1.004	−2.032	1.998	2.018	0.503	4.051	0.251
368	−6.880 × 10⁻³	1.002	−2.120	2.000	2.114	0.501	4.234	0.251

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表 8 实验测定的n_(DMO)/n_(EtOH) = 1/4时各温度下的平衡常数及组成

Table 8 Measured equilibrium constant and composition (initial ratio of n_(DMO)/n_(EtOH)=1/4)

T/K	t/min	x_DMO /%	s_MEO /%	s_DEO /%	w_MEO /%	w_DEO /%	K^Θ
323	120	56.79	75.35	24.65	42.79	14.00
	180	77.38	63.43	36.57	49.08	28.30
	300	82.69	51.63	48.37	42.69	40.00
	360	86.35	49.49	50.51	42.73	43.62
	480	87.89	47.82	52.18	42.03	45.86	0.96
338	30	55.03	79.93	20.07	43.98	11.04
	60	77.67	60.63	39.37	47.09	30.58
	120	84.51	51.39	48.61	43.42	41.08
	180	86.52	48.92	50.08	42.33	43.33
	360	88.15	46.62	52.38	41.10	46.17	1.00
353	30	60.02	77.10	22.90	46.27	13.74
	60	80.61	59.80	40.20	48.20	32.04
	120	85.46	50.56	49.44	43.21	42.25
	180	87.48	49.35	50.65	43.17	44.31
	360	88.16	47.65	52.35	42.01	46.15	1.00

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表 9 计算的n_(DMO)/n_(EtOH) = 1/4时各温度下的组成

Table 9 Calculated composition (initial ratio of n_(DMO)/n_(EtOH) = 1/4) at different temperatures

n_(DMO)/ n_(EtOH)	T/K	x_DMO /%	s_MEO /%	s_DEO /%	w_MEO /%	w_DEO /%
1/4	323	88.95	49.58	50.42	44.10	44.84
	338	88.93	49.57	50.43	44.08	44.85
	353	88.92	49.52	50.48	44.03	44.89
	368	88.92	49.59	50.41	44.10	44.82

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表 10 不同物质的量比原料DMO转化率及DEO选择性和产率计算值与实验值比较

Table 10 Comparison between calculated and experimental values of DMO conversion, DEO selectivity and yield of raw materials with different initial molar ratios of reactants

n_(DMO)/ n_(EtOH)	Calculation			Experiment
n_(DMO)/ n_(EtOH)	x_DMO /%	s_DEO /%	w_DEO /%	x_DMO /%	s_DEO /%	w_DEO /%	K^Θ
1/6	93.75	60.00	56.25	93.50	61.75	57.74	1.00
1/12	97.95	75.00	73.46	97.92	75.81	74.23	1.00
1/24	99.40	85.71	85.20	99.38	88.32	87.78	1.01

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