Thermodynamic calculation and analysis of meropenem hydrogenation reaction system

doi:10.11949/0438-1157.20201199

Abstract

Abstract:

Meropenem is an effective and safe antibiotic with high clinical value and is also one of the candidate drugs for treatment of COVID -19. Meropenem hydrogenation can be achieved via two processes:one-pot reaction and two-step process. This paper investigated the involved technical processes. Since most physical properties of the chemicals in meropenem hydrogenation reaction cannot be obtained from handbook, we estimate the properties of these chemicals by the group contribution method (Joback method, Constantinous method, Benson method & Ma Peisheng method), including critical parameters, standard generation heat, standard generation Gibbs free energy, heat capacity, etc. Based on the basic principle of thermodynamics and the estimated properties, the reaction enthalpy change, Gibbs free energy and reaction equilibrium constant in the standard condition and different temperatures (273—323 K) were calculated. The results indicated that meropenem hydrogenation was an exothermic reaction with considerable release of heat, so it is necessary to pay attention to the heat removal during the reaction process, and reducing the operating temperature is conducive to the reaction in the favorable direction of thermodynamics. According to the Gibbs free energy and equilibrium constant of each reaction, hydrogenation is easy to carry out, and condensation reaction is the thermodynamic limiting step of meropenem hydrogenation system. Therefore, it should be emphasized to reduce the operating temperature and remove the reaction products in time to promote the condensation reaction to the thermodynamic direction. The conclusions obtained through the thermodynamic calculation are basically consistent with the industrial practice. The one-pot reaction process is thermodynamicly more favorable than the two-step process. Combining anti-poisoning surrounding catalysts with micro-interface reaction enhancement technology to optimize the one-pot hydrogenation process is a direction worth exploring for upgrading meropenem hydrogenation technology.

Key words: meropenem, hydrogenation, thermodynamic properties, property estimation, group contribution, chemical reactors

摘要：

美罗培南是一种广谱、高效、安全的抗生素，也是治疗新冠肺炎的临床药物之一。研究美罗培南加氢反应的一锅法和两步法工艺过程，利用基团贡献法估算反应体系中各组分的物性，包括临界参数、标准摩尔生成焓、标准摩尔熵、比热容等。利用热力学基本原理，计算美罗培南加氢反应的标准摩尔反应焓、标准摩尔反应熵、标准摩尔反应Gibbs自由能和平衡常数。结果表明，美罗培南加氢反应是放热反应，且放热量较大，降低操作温度有利于反应向热力学有利的方向进行；加氢反应是较容易进行的，缩合反应的平衡常数远小于加氢反应；可着重考虑采用降低操作温度，及时移出反应产物等方式推动缩合反应向正反应方向进行。热力学理论计算与实际情况吻合较好。一锅法在热力学上优于两步法，但需要解决催化剂易中毒问题。将抗中毒的包围型催化剂与微界面反应强化技术结合优化一锅法加氢过程是对美罗培南加氢反应技术升级一个值得探索的方向。

关键词: 美罗培南, 加氢, 热力学性质, 物性估算, 基团贡献, 化学反应器

CLC Number:

TQ 013.1

LIU Zuhu, HU Xingbang, CHEN Shanyong, LI Guoxiang, GUO Xuefeng, ZHANG Zhibing. Thermodynamic calculation and analysis of meropenem hydrogenation reaction system[J]. CIESC Journal, 2021, 72(4): 1863-1873.

刘祖虎, 胡兴邦, 陈善勇, 李国祥, 郭学锋, 张志炳. 美罗培南加氢反应体系的热力学计算和分析[J]. 化工学报, 2021, 72(4): 1863-1873.

Figures/Tables 9

Table 1 Estimated properties of meropenem hydrogenation system

物质	T_m/K	T_b/K	T_c/K	p_c/ MPa	V_c/ (cm³/mol)	Δ_vH_b/ (kJ/mol)	$Δ v H 298 ? ?$ / (kJ/mol)	$Δ f H 298 ?$ (g)/ (kJ/mol)	$Δ f H 298 ?$ (l)/ (kJ/mol)	$S 298 ?$ (g)/ (J/(K?mol))	$S 298 ?$ (l)/ (J/(K?mol))	$c p ?$
物质	T_m/K	T_b/K	T_c/K	p_c/ MPa	V_c/ (cm³/mol)	Δ_vH_b/ (kJ/mol)	$Δ v H 298 ? ?$ / (kJ/mol)	$Δ f H 298 ?$ (g)/ (kJ/mol)	$Δ f H 298 ?$ (l)/ (kJ/mol)	$S 298 ?$ (g)/ (J/(K?mol))	$S 298 ?$ (l)/ (J/(K?mol))	A/(J/(K?mol))	B/(J/ (K^-2?mol))	C/(J/ (K^-3?mol))	D/(J/ (K^-4?mol))
美罗培南	822.13	1004.31	1230.66	2.186	1015.5	79.25	134.77	-649.463	-784.233	413.21	-39.04	48.01	2.16	-1.51×10^-3	4.13×10^-7
保护美罗培南	1241.13	1763.13	2335.41	1.102	1818.5	115.61	186.12	-445.712	-631.832	1750.74	1126.18	37.322	3.46	-2.33×10^-3	5.84×10^-7
母核	898.4	1391.65	1720.42	1.379	1491.5	101.97	176.61	-201.751	-378.361	1203.6	610.95	42.731	2.54	-1.48×10^-3	2.72×10^-7
侧链	674.53	950.34	1199.31	2.405	917.5	79.62	128.99	-86.195	-215.185	976.735	543.88	17.781	1.66	-1.05×10^-3	2.36×10^-7
磷酸二苯酯	368.33	654.54	867.68	3.642	591.5	52.39	75.75	-23.985	-99.735	358.91	104.72	7.69	8.10×10^-1	-2.80×10^-4	-4.36×10^-8
对甲苯胺	290.35	463.75	691.8	4.345	348.5	44.35	54.43	46.767	-7.663	420.7	238.05	-16.59	5.92×10^-1	-3.65×10^-4	8.37×10^-8

Table 1 Estimated properties of meropenem hydrogenation system

物质	T_m/K	T_b/K	T_c/K	p_c/ MPa	V_c/ (cm³/mol)	Δ_vH_b/ (kJ/mol)	$Δ v H 298 ? ?$ / (kJ/mol)	$Δ f H 298 ?$ (g)/ (kJ/mol)	$Δ f H 298 ?$ (l)/ (kJ/mol)	$S 298 ?$ (g)/ (J/(K?mol))	$S 298 ?$ (l)/ (J/(K?mol))	$c p ?$
物质	T_m/K	T_b/K	T_c/K	p_c/ MPa	V_c/ (cm³/mol)	Δ_vH_b/ (kJ/mol)	$Δ v H 298 ? ?$ / (kJ/mol)	$Δ f H 298 ?$ (g)/ (kJ/mol)	$Δ f H 298 ?$ (l)/ (kJ/mol)	$S 298 ?$ (g)/ (J/(K?mol))	$S 298 ?$ (l)/ (J/(K?mol))	A/(J/(K?mol))	B/(J/ (K^-2?mol))	C/(J/ (K^-3?mol))	D/(J/ (K^-4?mol))
美罗培南	822.13	1004.31	1230.66	2.186	1015.5	79.25	134.77	-649.463	-784.233	413.21	-39.04	48.01	2.16	-1.51×10^-3	4.13×10^-7
保护美罗培南	1241.13	1763.13	2335.41	1.102	1818.5	115.61	186.12	-445.712	-631.832	1750.74	1126.18	37.322	3.46	-2.33×10^-3	5.84×10^-7
母核	898.4	1391.65	1720.42	1.379	1491.5	101.97	176.61	-201.751	-378.361	1203.6	610.95	42.731	2.54	-1.48×10^-3	2.72×10^-7
侧链	674.53	950.34	1199.31	2.405	917.5	79.62	128.99	-86.195	-215.185	976.735	543.88	17.781	1.66	-1.05×10^-3	2.36×10^-7
磷酸二苯酯	368.33	654.54	867.68	3.642	591.5	52.39	75.75	-23.985	-99.735	358.91	104.72	7.69	8.10×10^-1	-2.80×10^-4	-4.36×10^-8
对甲苯胺	290.35	463.75	691.8	4.345	348.5	44.35	54.43	46.767	-7.663	420.7	238.05	-16.59	5.92×10^-1	-3.65×10^-4	8.37×10^-8

Table 2 Comparison between SciFinder value and the estimated value in this paper

物质物性	文献实验值/ 文献估算值	本文估算值	偏差
美罗培南,T_b/K	900.4±55(估算值)	1004.31	+5.12%
侧链,T_b/K	828.8±50(估算值)	950.34	+8.14%
磷酸二苯酯,T_m/K	340~341(实验值)	368.33	+8.01%
磷酸二苯酯,T_b/K	650.7±25(估算值)	654.54	一致
对甲苯胺,T_m/K	313±10.0(实验值)	290.35	-7.35%
对甲苯胺,T_b/K	470.4±9.0(实验值)	463.75	一致
对甲苯胺,Δ_vH_b/(kJ/mol)	43.36±3.0(实验值)	44.35	一致

Table 3 Standard molar reaction enthalpy, standard molar entropy change，standard molar reaction Gibbs free energy and standard equilibrium constant of meropenem hydrogenation reaction

公式

$Δ r H 298 ?$ /

(kJ/mol)

$Δ r S 298 ?$ /

(J/(K?mol))

$Δ r G 298 ?$ /

(kJ/mol)

K 298 ?

1.36×10²⁶²

1.47×10²⁸

9.25×10²³³

Table 3 Standard molar reaction enthalpy, standard molar entropy change，standard molar reaction Gibbs free energy and standard equilibrium constant of meropenem hydrogenation reaction

公式

$Δ r H 298 ?$ /

(kJ/mol)

$Δ r S 298 ?$ /

(J/(K?mol))

$Δ r G 298 ?$ /

(kJ/mol)

K 298 ?

式(1)

-1842.568

-1164.91

-1495.425

1.36×10²⁶²

式(2)

-138.021

76.07

-160.69

1.47×10²⁸

式(3)

-1704.547

-1240.98

-1334.735

9.25×10²³³

Table 4 The standard molar Gibbs free energy variation obtained by different group estimation method

基团估算法	$Δ r G 298 ?$ /(kJ/mol)
基团估算法	式(1)	式(2)	式(3)
Joback法	-1021.07	4.44	-1025.51
Benson法	-743.16	300.33	-1043.49
Constantinous法	-1495.425	-160.69	-1334.735

Table 4 The standard molar Gibbs free energy variation obtained by different group estimation method

基团估算法	$Δ r G 298 ?$ /(kJ/mol)
基团估算法	式(1)	式(2)	式(3)
Joback法	-1021.07	4.44	-1025.51
Benson法	-743.16	300.33	-1043.49
Constantinous法	-1495.425	-160.69	-1334.735

Fig.1 Effect of temperature on standard molar enthalpy change of meropenem hydrogenation reaction

Fig.2 Effect of temperature on standard molar entropy change of meropenem hydrogenation reaction

Fig.3 Effect of temperature on standard molar Gibbs free energy change of meropenem hydrogenation reaction

Table 5 Standard equilibrium constant of meropenem hydrogenation reaction at different temperature

反应温度/K	标准平衡常数
反应温度/K	式（1）	式（2）	式（3）
323	1.5×10²³⁷	1.97×10²⁶	7.5×10²¹⁰
318	7×10²⁴¹	4.42×10²⁶	1.6×10²¹⁵
313	4.7×10²⁴⁶	1.02×10²⁷	4.6×10²¹⁹
308	4.5×10²⁵¹	2.41×10²⁷	1.9×10²²⁴
303	6.4×10²⁵⁶	5.86×10²⁷	1.1×10²²⁹
298	1.4×10²⁶²	1.47×10²⁸	9.3×10²³³
293	4.4×10²⁶⁷	3.8×10²⁸	1.2×10²³⁹
288	2.3×10²⁷³	1.02×10²⁹	2.2×10²⁴⁴
283	1.9×10²⁷⁹	2.82×10²⁹	6.6×10²⁴⁹
278	2.5×10²⁸⁵	8.08×10²⁹	3.1×10²⁵⁵
273	5.7×10²⁹¹	2.41×10³⁰	2.4×10²⁶¹

Table A1 Group analysis of meropenem hydrogenation system by Joback method， Constantinous method， Benson method & Ma Peisheng method

名称	化学式	Joback法基团分解		Constantinous法基团分解		Benson法基团分解		马沛生法基团分解
名称	化学式	基团类型	数量	基团类型	数量	基团类型	数量	基团类型	数量
美罗培南	C₁₇H₂₅N₃O₅S	CH₃(1)	4	CH₃(1)(一级)	2	CH₃—(C)	2	CH₃(1)	3
		CH(3)	1	CH₂(2)(一级)	1	CH₃—(N)	2	CH₂(2)R	2
		C(3)	2	CH(3)(一级)	6	CH₂—(2C)	1	CH(3)R	5
		CH₂(ss)(2)	2	CC(4)(一级)	1	CH₂—(C,N)	1	C(3)R	2
		OH(1)	1	COOH(1)(一级)	1	CH—(2C,O)	1	CHOH(2)	1
		CO(2)	1	CH₂NH(2)(一级)	1	CH—(2C,N)	2	CO(2)	1
		CO(ss)(2)	1	CON(CH₃)₂(1)(一级)	1	CH—(2C,S)	1	CO(2)R	1
		COOH(1)	1	CO(2)(一级)缺	1	CH—(3C)	1	COOH(1)	1
		NH(ss)(2)	1	N(3)(一级)缺	1	C—(C,N)	1	N(3)	1
		N(3)	2	S(2)(一级)缺	1	C—(C,S)	1	NH(2)R	1
		S(2)	1	CH_nCH_m—CH_pCH_k[k，n，m，p∈(0,2)]	1	CO—(C,N)	2	N(3)R	1
				四元环(二级)	1	CO—(C,O)	1	S(2)	1
				五元环(二级)	2	OH—(CO)	1
				CHOH(2)(二级)	1	OH—(C)	1
				(CH_m)_R-S-(CH_n)_R[m，n∈(0,2)](二级)	1	N—(2C,CO)	2
				(CH_m)_R-NH_p-(CH_n)_R[m，n，p∈(0,2)](二级)	2	NH—(2C)	1
						S—(2C)	1
保护美罗培南	C₃₂H₃₅N₅O₁₁S	CH₃(1)	4	CH₃(1)(一级)	2	CH₃—(C)	2	CH₃(1)	3
		CH₂(2)	2	CH₂(2)(一级)	1	CH₃—(N)	2	CH₂(2)R	2
		CH(3)	1	CH(3)(一级)	6	CH₂—(2C)	1	CH(3)R	5
		C(3)	2	CC(4)(一级)	1	CH₂—(Cb,O)	2	C(3)R	2
		CH₂(ss)(2)	2	(CH)_A(2)(一级)	8	CH₂—(C,N)	1	CH₃(1)RC	1
		CH(ss)(3)	5	(C)_ACH₂(3)(一级)	2	CH—(2C,CO)	1	CH(2)A	8
		CH(ds)(2)	8	OH(1)(一级)	1	CH—(2C,O)	1	C(3)A	4
		C(ds)(3)	4	COO(2)(一级)	1	CH—(2C,N)	2	CH₂(2)AC	2
		OH(1)	1	CH₂N(2)(一级)	1	CH—(2C,S)	1	CHOH(2)	1
		O(2)	1	(C)_ANO₂(2)(一级)	2	CH—(3C)	1	CO(2)	1
		CO(2)	2	CON(CH₃)₂(1)(一级)	1	Cb—(C)	2	CO(2)R	1
		CO(ss)(2)	1	O(2)(一级)缺	1	CbH	8	COO(2)RC	2
		COO(2)	1	CO(2)(一级)缺	2	Cb(NO₂)	2	N(3)	1
		N(3)	3	N(3)(一级)缺	1	C—(C,N)	1	N(3)R	2
		NO₂(1)	2	S(2)(一级)缺	1	C—(C,S)	1	NO₂(1)	2
		S(2)	1	CH_nCH_m—CH_pCH_k[k，n，m，p∈(0,2)]	1	CO—(C,N)	2	S(2)	1
				四元环(二级)	1	CO—(C,O)	1
				五元环(二级)	2	CO—(O,N)	1
				六元环(二级)	2	O—(C,O)	2
				CHOH(2)(二级)	1	OH—(C)	1
				(CH_m)_R—S—(CH_n)_R[m，n∈(0,2)](二级)	1	O(NO₂)—(C)	4
				(CH_m)_R—NH_p—(CH_n)_R[m，n，p∈(0,2)](二级)	2	N—(2C,CO)	3
						N(NO₂)—(Cb)	2
						S—(2C)	1
母核	C₂₉H₂₇N₂O₁₀P	CH₃(1)	2	CH₃(1)(一级)	2	CH₃—(C)	2	CH₃(1)	1
		CH₂(2)	1	CH(3)(一级)	4	CH₂—(Cb,O)	1	CH(3)R	3
		CH(3)	1	CC(4)(一级)	1	CH— (2C,CO)	1	C(3)R	2
		C(3)	2	(CH)_A(2)(一级)	14	CH—(2C,O )	1	CH₃(1)RC	1
		CH(ss)(3)	3	(C)_A(3)(一级)	2	CH—(2C,N)	1	CH(2)A	14
		CH(ds)(2)	14	(C)_ACH₂(3)(一级)	1	CH—(3C)	1	C(3)A	4
		C(ds)(3)	4	OH(1)(一级)	1	Cb—(C)	1	CH₂(2)AC	1
		OH(1)	1	COO(2)(一级)	1	Cb—(O)	2	CHOH(2)	1
		O(2)	3	(C)_ANO₂(2)(一级)	1	CbH	14	CO(2)R	1
		CO(ss)(2)	1	O(2)(一级)缺	3	Cb(NO₂)	1	COO(2)RC	1
		COO(2)	1	CO(2)(一级)缺	1	C— (C,N)	1	O(2)	1
		O(1)	1	N(3)(一级)缺	1	C—(C,O)	1	O(2)AC	2
		N(3)	1	PO(3)(一级)缺	1	CO—(C,N)	1	N(3)R	1
		NO₂(1)	1	CH_nCH_m—CH_pCH_k[k，n，m，p∈(0,2)]	1	CO—(C,O)	1	NO₂(1)	1
		P(5)缺	1	四元环(二级)	1	O—(C,CO)	1	PO(3)缺	1
				五元环(二级)	1	O—(C,PO)	3
				六元环(二级)	3	OH—(C)	1
				CHOH(2)(二级)	1	O(NO₂)—(C)	2
				(CH_m)_R—NH_p—(CH_n)_R[m，n，p∈(0,2)](二级)	1	N—(2C,CO)	1
						N(NO₂)—(Cb)	1
						PO—(3O)	1
侧链	C₁₅H₁₉N₃O₅S	CH₃(1)	2	CH₂(2)(一级)	1	CH₃—(N)	2	CH₃(1)	2
		CH₂(2)	1	CH(3)(一级)	2	CH₂—(2C)	1	CH₂(2)R	2
		CH₂(ss)(2)	2	(CH)_A(2)(一级)	4	CH₂—(Cb,O)	1	CH(3)R	2
		CH(ss)(3)	2	(C)_ACH₂(3)(一级)	1	CH₂—(C,N)	1	CH(2)A	4
		CH(ds)(2)	4	CH₂N(2)(一级)	1	CH—(2C,N)	1	C(3)A	2
		C(ds)(3)	2	(C)_ANO₂(2)(一级)	1	CH—(2C,S)	1	CH₂(2)AC	1
		O(2)	1	CON(CH₃)₂(1)(一级)	1	Cb—(C)	1	CO(2)	1
		CO(2)	2	O(2)(一级)缺	1	CbH	4	COO(2)RC	1
		N(3)	2	CO(2)(一级)缺	1	Cb(NO₂)	1	N(3)	1
		NO₂(1)	1	SH(1)(一级)缺	1	CO—(C,N)	1	N(3)R	1
		SH(1)	1	五元环(二级)	1	CO—(O,N)	1	NO₂(1)	1
				六元环(二级)	1	O—(C,CO)	1	SH(1)RC	1
				(CH_m)_R—NH_p—(CH_n)_R[m，n，p∈(0,2)](二级)	1	O(NO₂) —(C)	2
						N—(2C,CO)	2
						N(NO₂) —(C_b)	1
						SH—(C)	1
磷酸二苯酯	C₁₂H₁₁O₄P	CH(ds)(2)	10	(CH)_A(2)(一级)	10	Cb—(O)	2	CH(2)A	10
		C(ds)(3)	2	(C)_A(3)(一级)	2	CbH	10	C(3)A	2
		OH(1)	1	OH(1)(一级)	1	O—(C,PO)	2	O(2)AC	2
		O(2)	2	O(2)(一级)缺	2	OH—(P)	1	PO(3)缺	1
		O(1)	1	PO(3)(一级)缺	1	PO—(3O)	1	OH(1)缺	1
		P(5)缺	1	六元环(二级)	2
对甲苯胺	C₇H₉N	CH₃(1)	1	(CH)_A(2)(一级)	4	CH₃—(C_b)	1	CH(2)A	4
		CH(ds)(2)	4	(C)_ACH₃(2)(一级)	1	Cb—(C)	1	C(3)A	2
		C(ds)(3)	2	(C)_ANH₂(2)(一级)	1	Cb—(N)	1	CH₃(1)AC	1
		NH₂(1)	1	六元环(二级)	1	C_bH	4	NH₂(1)AC	1
						NH₂—(Cb)	1

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