基于酸度系数（pKa）模型的胺法SO2捕集过程多目标效能分析

doi:10.16085/j.issn.1000-6613.2022-0015

摘要/Abstract

摘要：

筛选高SO₂吸收容量、低解吸能耗的吸收剂是提高胺基烟气SO₂捕集工艺应用潜力的重要途径。本研究采用SMD连续溶剂化模型和密度泛函理论在M05-2X/6-31G*基组水平上预测了5种有机二胺类物质的pK_a，基于预测的pK_a建立起吸收剂对SO₂吸收容量和解吸反应热的数学模型，以探讨有机二胺-酸-水三元体系吸收剂捕集SO₂过程中的效能关系。结果表明，数学模型符合工程精度要求。二胺的SO₂吸收容量和脱质子反应焓都随pK_a增大而增加，筛选有机胺吸收剂展现出对SO₂吸收容量和反应焓的多目标矛盾性特征；量化了5种二胺的SO₂循环吸收容量和解吸反应热的数值关系，在相同SO₂循环容量条件下，5种二胺中羟乙基哌嗪（HEP）的解吸热最小，HEP为有机二胺-酸-水三元体系中的一种潜力二胺类吸收剂。

关键词: 有机胺, SO₂捕集, 分子模拟, 吸收容量, 解吸反应热

Abstract:

The screening of absorbent with high SO₂ absorption capacity and low desorption energy consumption is important to improve the amine-based SO₂ capture process from flue gas. The pK_a values of five diamines were calculated using SMD continuous solvation model and density functional theory at the M05-2X/6-31G* base set level. Two mathematical models of SO₂ absorption capacity and desorption reaction heat of diamines were established based on the predicted pK_a values. The relationship of SO₂ absorption capacity and desorption reaction heat was discussed for the diamine-acid-water ternary absorbent system. The results showed that the mathematical model met the requirement of engineering precision. The SO₂ absorption capacity and deprotonation reaction enthalpy of diamines were increased with the increase of pK_a value. In the screening of organic diamine absorbents, the multi-objective contradictory characteristics of SO₂ absorption capacity and reaction enthalpy were revealed. The numerical relationship between SO₂ cyclic absorption capacity and desorption reaction heat of the five diamines was obtained. The desorption reaction heat of hydroxyethylpiperazine (HEP) was the smallest under the same SO₂ circulating capacity among the five diamines. So, HEP is a promising absorbent in organic diamine-acid-water ternary systems.

Key words: organic amine, SO₂ capture, molecular simulation, absorption capacity, desorption reaction heat

中图分类号:

TQ116.02

王东亮, 谢江鹏, 孟文亮, 李婧玮, 周怀荣. 基于酸度系数（pK_a）模型的胺法SO₂捕集过程多目标效能分析[J]. 化工进展, 2022, 41(10): 5669-5676.

WANG Dongliang, XIE Jiangpeng, MENG Wenliang, LI Jingwei, ZHOU Huairong. Multi-objective capacity and heat analysis of amine-based SO₂ capture process from acidity coefficient (pK_a) model[J]. Chemical Industry and Engineering Progress, 2022, 41(10): 5669-5676.

图/表 11

图1 有机胺捕集烟气SO2工艺流程

表1 lnK-T关系参数

类别	A	B	C	D	温度区间/K	参考
lnK_s1（SO₂）	-10.9670	1972.5	—	—	—	Rabe等^［16］
lnK_s1（HSO $3 -$ ）	-357.5700	5477.1	65.31	-0.1624	—	Millero等^［17］
lnK（H₂SO₄）	>10	—	—	—	—	Sippola等^［18］
lnK（HSO $4 -$ ）	-49.7086	178.1142	10.9523	-0.0598	—	Sippola等^［18］
lnK（EDAH⁺）	-79.7113	-6508.6363	14.4126	-0.0169	298.15~398.15	拟合
lnK（PZH⁺）	-62.6234	-7025.0400	11.8682	-0.0136	298.15~398.15	拟合
lnK（HEPH⁺）	-69.6302	-6496.8100	13.1533	-0.0154	298.15~398.15	拟合
lnK（DIHEPH⁺）	-56.7455	-5761.7300	10.7373	-0.0123	298.15~398.15	拟合
lnK（HEHPPH⁺）	-75.0596	-6708.4600	14.0755	-0.0172	298.15~398.15	拟合
lnK（EDAH $2 2 +$ ）	-66.4837	-5110.9300	12.7213	-0.0140	298.15~398.15	拟合
lnK（PZH $2 2 +$ ）	-92.5319	-3609.9200	17.2128	-0.0208	298.15~398.15	拟合
lnK（HEPH $2 2 +$ ）	-84.1281	-2928.1100	15.6410	-0.0190	298.15~398.15	拟合
lnK（DIHEPH $2 2 +$ ）	-87.4632	-2832.4700	16.4588	-0.0199	298.15~398.15	拟合
lnK（HEHPPH $2 2 +$ ）	-66.4512	-3557.3000	12.5968	-0.0142	298.15~398.15	拟合

表1 lnK-T关系参数

类别	A	B	C	D	温度区间/K	参考
lnK_s1（SO₂）	-10.9670	1972.5	—	—	—	Rabe等^［16］
lnK_s1（HSO $3 -$ ）	-357.5700	5477.1	65.31	-0.1624	—	Millero等^［17］
lnK（H₂SO₄）	>10	—	—	—	—	Sippola等^［18］
lnK（HSO $4 -$ ）	-49.7086	178.1142	10.9523	-0.0598	—	Sippola等^［18］
lnK（EDAH⁺）	-79.7113	-6508.6363	14.4126	-0.0169	298.15~398.15	拟合
lnK（PZH⁺）	-62.6234	-7025.0400	11.8682	-0.0136	298.15~398.15	拟合
lnK（HEPH⁺）	-69.6302	-6496.8100	13.1533	-0.0154	298.15~398.15	拟合
lnK（DIHEPH⁺）	-56.7455	-5761.7300	10.7373	-0.0123	298.15~398.15	拟合
lnK（HEHPPH⁺）	-75.0596	-6708.4600	14.0755	-0.0172	298.15~398.15	拟合
lnK（EDAH $2 2 +$ ）	-66.4837	-5110.9300	12.7213	-0.0140	298.15~398.15	拟合
lnK（PZH $2 2 +$ ）	-92.5319	-3609.9200	17.2128	-0.0208	298.15~398.15	拟合
lnK（HEPH $2 2 +$ ）	-84.1281	-2928.1100	15.6410	-0.0190	298.15~398.15	拟合
lnK（DIHEPH $2 2 +$ ）	-87.4632	-2832.4700	16.4588	-0.0199	298.15~398.15	拟合
lnK（HEHPPH $2 2 +$ ）	-66.4512	-3557.3000	12.5968	-0.0142	298.15~398.15	拟合

图2 计算反应自由能的热力循环

表2 一价质子胺（BN2H+）解离自由能（ΔG1）和二价质子胺（BN2H2+）解离自由能（ΔG2）

温度T/K	解离自由能ΔG₁/kJ·mol^-1					解离自由能∆G₂/kJ·mol^-1
温度T/K	EDAH⁺	PZH⁺	HEPH⁺	DIHEPH⁺	HEHPPH⁺	EDAH $2 2 +$	PZH $2 2 +$	HEPH $2 2 +$	DIHEPH $2 2 +$	HEHPPH $2 2 +$
298.15	55.6187	55.9831	52.2001	45.973	47.1383	37.9241	31.6248	25.9967	22.6101	23.8055
308.15	54.628	54.9944	51.1718	45.0618	46.1351	36.8039	30.5023	24.9643	21.4439	22.7563
318.15	53.3262	53.6688	49.7306	43.657	44.6075	35.9446	29.6664	24.2946	20.7295	22.1856
328.15	52.5966	52.9567	49.0525	43.1891	44.066	34.4923	28.1971	22.8366	19.0488	20.612
338.15	51.5683	51.9323	47.9866	42.2486	43.0294	33.3303	27.0363	21.7666	17.8491	19.5294
348.15	50.5358	50.904	46.9165	41.2998	41.9844	32.1641	25.8701	20.6923	16.6369	18.4426
358.15	49.495	49.8674	45.8381	40.3467	40.931	30.9853	24.6913	19.6097	15.4205	17.3474
368.15	48.4542	48.8224	44.7597	39.3895	39.8819	29.8024	23.5126	18.5187	14.2	16.2439
378.15	47.405	47.7816	43.6729	38.4323	38.8243	28.6152	22.3255	17.4319	12.9711	15.1404
388.15	46.3475	46.7282	42.5777	37.4625	37.7584	27.4156	21.1342	16.3367	11.738	14.0285
398.15	45.2899	45.6707	41.4825	36.4928	36.6967	26.2159	19.9429	15.2332	10.5049	12.9124

表2 一价质子胺（BN2H+）解离自由能（ΔG1）和二价质子胺（BN2H2+）解离自由能（ΔG2）

温度T/K	解离自由能ΔG₁/kJ·mol^-1					解离自由能∆G₂/kJ·mol^-1
温度T/K	EDAH⁺	PZH⁺	HEPH⁺	DIHEPH⁺	HEHPPH⁺	EDAH $2 2 +$	PZH $2 2 +$	HEPH $2 2 +$	DIHEPH $2 2 +$	HEHPPH $2 2 +$
298.15	55.6187	55.9831	52.2001	45.973	47.1383	37.9241	31.6248	25.9967	22.6101	23.8055
308.15	54.628	54.9944	51.1718	45.0618	46.1351	36.8039	30.5023	24.9643	21.4439	22.7563
318.15	53.3262	53.6688	49.7306	43.657	44.6075	35.9446	29.6664	24.2946	20.7295	22.1856
328.15	52.5966	52.9567	49.0525	43.1891	44.066	34.4923	28.1971	22.8366	19.0488	20.612
338.15	51.5683	51.9323	47.9866	42.2486	43.0294	33.3303	27.0363	21.7666	17.8491	19.5294
348.15	50.5358	50.904	46.9165	41.2998	41.9844	32.1641	25.8701	20.6923	16.6369	18.4426
358.15	49.495	49.8674	45.8381	40.3467	40.931	30.9853	24.6913	19.6097	15.4205	17.3474
368.15	48.4542	48.8224	44.7597	39.3895	39.8819	29.8024	23.5126	18.5187	14.2	16.2439
378.15	47.405	47.7816	43.6729	38.4323	38.8243	28.6152	22.3255	17.4319	12.9711	15.1404
388.15	46.3475	46.7282	42.5777	37.4625	37.7584	27.4156	21.1342	16.3367	11.738	14.0285
398.15	45.2899	45.6707	41.4825	36.4928	36.6967	26.2159	19.9429	15.2332	10.5049	12.9124

图3 二胺的酸度系数（pKa）

图4 pKa实验值与计算值的比较

表3 EDA-H3PO3-H2O三元体系吸收剂的SO2溶解度实验值与计算值比较

SO₂分压p(SO₂) /Pa	浓度				相对误差 /%
SO₂分压p(SO₂) /Pa	c(EDA) /mol·L^-1	c(H₃PO₄) /mol·L^-1	c_s(exp) /mol·L^-1	c_s(cal) /mol·L^-1	相对误差 /%
143	0.3	0	0.5610	0.5945	-5.6350
204	0.3	0	0.5630	0.5970	-5.6951
294	0.3	0	0.5820	0.5992	-2.8705
112	0.3	0.13	0.4820	0.4653	3.5891
232	0.3	0.13	0.4660	0.4700	-0.8511
301	0.3	0.13	0.4680	0.4715	-0.7423
108	0.3	0.26	0.3325	0.3380	-1.6272
298	0.3	0.26	0.3450	0.3444	0.1742
373	0.3	0.26	0.3525	0.3462	1.8198
118	0.3	0.39	0.2235	0.2122	5.3252
252	0.3	0.39	0.2288	0.2180	4.9541
337	0.3	0.39	0.2341	0.2211	5.8797

图5 二胺-硫酸-水三元体系吸收剂的SO2吸收容量

图6 二价胺的脱质子反应焓(∆H2)

表4 解吸反应焓ΔHdes与SO2吸收容量α关系的参数

有机胺	a	b	c	d
EDA	-14.2062	21.6396	-10.8574	83.3219
PZ	-8.1086	11.8772	-6.9219	76.1474
HEP	-23.8924	25.9303	-10.7243	67.6164
DIHEP	-91.1772	66.9002	-18.0294	68.1945
HEHPP	-19.6444	24.5696	-11.1515	68.9849

图7 不同SO2循环吸收容量下各二胺对应的解吸反应热

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基于酸度系数（pK_a）模型的胺法SO₂捕集过程多目标效能分析

Multi-objective capacity and heat analysis of amine-based SO₂ capture process from acidity coefficient (pK_a) model

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