Experimental and kinetics analysis of ethanol-hydrated calcium-based adsorbents

doi:10.16085/j.issn.1000-6613.2022-2362

Abstract

Abstract:

An efficient HCl removal adsorbent was obtained by hydrating pure calcium oxide with ethanol solution. The adsorption performance on HCl at different reaction temperatures and initial HCl concentrations was investigated in a fixed bed reactor. The experimental data were fitted and analyzed using four reaction kinetic models. The results showed that the adsorbent surface of CA-ET-33 indicated a porous and large specific surface area structure due to the covering and dynamic deposition process of the ethanol organic molecules, while greatly increasing the 2—10nm pore occupancy ratio, which promoted its adsorption of HCl. The apparent reaction kinetic models fit the experimental results in the following order from best to worst: pseudo-second-order kinetic model, Elovich model, pseudo-first-order kinetic model and intra-particle diffusion model. The pseudo-second-order kinetic model can describe the actual adsorption behavior of the adsorbent, showing the adsorption was mainly chemisorption-based. The elevation of temperature provided sufficient activation energy for chemisorption, and the rise of initial HCl concentration enhanced the driving force of the mass transfer from the gas phase to the adsorbent surface. The cumulative adsorption capacity ascended with the addition of temperature, and the increase of HCl initial concentration shortened the period to reach the equilibrium. A general kinetic equation was determined that can predict the adsorption process of HCl of a Ca-based adsorbent.

Key words: ethanol hydration, calcium-based adsorbent, reaction kinetic models, adsorption model prediction

摘要：

利用乙醇溶液对分析纯氧化钙进行消化改性，制备HCl脱氯剂。通过固定床实验，考察不同反应温度和初始HCl浓度下该脱氯剂对HCl的吸附性能，利用四种反应动力学模型对实验数据进行拟合分析。结果表明：乙醇有机物分子的覆盖和动态沉积过程，使脱氯剂CA-ET-33的表面呈现为多孔隙、大比表面积的结构，同时大大增加了2~10nm孔占比，促进了其对HCl的吸附脱除。表观反应动力学模型对实验结果的拟合效果从优到差依次为：准二级吸附动力学模型、Elovich模型、准一级动力学模型、颗粒内扩散模型。准二级动力学模型可准确描述脱氯剂对HCl的吸附机理，吸附以化学吸附为主。温度升高为化学吸附提供了足够的活化能，HCl浓度的升高增大了从气相到固相表面的传质驱动力。脱氯剂的累计吸附量随温度的升高而增大，达到平衡所消耗的时间随HCl浓度的增加而缩短。确定了一个通用的动力学方程，可用于预测钙基脱氯剂对HCl的吸附过程。

关键词: 乙醇消化, 钙基脱氯剂, 反应动力学模型, 吸附模型预测

CLC Number:

X511

WANG Yuqing, DUAN Yufeng, WANG Rui, LIU Xiaoshuo, SHEN Zhen. Experimental and kinetics analysis of ethanol-hydrated calcium-based adsorbents[J]. Chemical Industry and Engineering Progress, 2023, 42(11): 6053-6063.

王雨晴, 段钰锋, 王睿, 刘晓硕, 申镇. 乙醇改性钙基脱氯剂实验及动力学分析[J]. 化工进展, 2023, 42(11): 6053-6063.

Figures/Tables 10

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T/℃	C₀/mg·m^-3	颗粒内扩散模型			准一级动力学模型
T/℃	C₀/mg·m^-3	k_id	c	R²	q_e	k₁	R²
150	163	14062.88	-19751.55	0.96843	407511.62	0.019944	0.89911
150	244	15567.01	-6790.77	0.93919	436455.53	0.028051	0.94356
150	325	15963.22	2641.96	0.9453	286800.56	0.021786	0.90545
200	163	18612.51	-32164.72	0.97111	772876.32	0.009304	0.89555
200	244	22587.93	-33728.60	0.98138	682213.01	0.012068	0.87835
200	325	20680.36	18493.64	0.92433	555430.85	0.011607	0.92905
250	163	28047.48	-105723.07	0.98373	1085500.43	0.0084981	0.87935
250	244	29312.14	-63623.26	0.98361	1003275.02	0.0087053	0.87738
250	325	30364.12	-32319.20	0.97125	1005101.68	0.0079223	0.89946
T/℃	C₀/mg·m^-3	准二级动力学模型			Elovich 模型
T/℃	C₀/mg·m^-3	q_e	k₂	R²	α	β	R²
150	163	344734.86	1.59×10^-8	0.95326	6591.04	1.82×10^-5	0.90259
150	244	315608.75	3.04×10^-8	0.96060	9761.29	1.77×10^-5	0.91557
150	325	296611.80	4.54×10^-8	0.98650	12320.43	1.81×10^-5	0.93628
200	163	637893.42	4.58×10^-9	0.97205	6369.13	9.52×10^-6	0.90726
200	244	636108.04	6.76×10^-9	0.98435	9316.26	9.60×10^-6	0.90927
200	325	546815.62	1.37×10^-8	0.98545	12393.99	9.58×10^-6	0.93486
250	163	1348901.45	9.53×10^-10	0.98306	7005.67	6.63×10^-6	0.90085
250	244	1007604.39	2.70×10^-9	0.97305	9713.18	6.43×10^-6	0.90056
250	325	978129.03	3.74×10^-9	0.99000	11643.79	5.85×10^-6	0.91846

T/℃	C₀/mg·m^-3	颗粒内扩散模型			准一级动力学模型
T/℃	C₀/mg·m^-3	k_id	c	R²	q_e	k₁	R²
150	163	14062.88	-19751.55	0.96843	407511.62	0.019944	0.89911
150	244	15567.01	-6790.77	0.93919	436455.53	0.028051	0.94356
150	325	15963.22	2641.96	0.9453	286800.56	0.021786	0.90545
200	163	18612.51	-32164.72	0.97111	772876.32	0.009304	0.89555
200	244	22587.93	-33728.60	0.98138	682213.01	0.012068	0.87835
200	325	20680.36	18493.64	0.92433	555430.85	0.011607	0.92905
250	163	28047.48	-105723.07	0.98373	1085500.43	0.0084981	0.87935
250	244	29312.14	-63623.26	0.98361	1003275.02	0.0087053	0.87738
250	325	30364.12	-32319.20	0.97125	1005101.68	0.0079223	0.89946
T/℃	C₀/mg·m^-3	准二级动力学模型			Elovich 模型
T/℃	C₀/mg·m^-3	q_e	k₂	R²	α	β	R²
150	163	344734.86	1.59×10^-8	0.95326	6591.04	1.82×10^-5	0.90259
150	244	315608.75	3.04×10^-8	0.96060	9761.29	1.77×10^-5	0.91557
150	325	296611.80	4.54×10^-8	0.98650	12320.43	1.81×10^-5	0.93628
200	163	637893.42	4.58×10^-9	0.97205	6369.13	9.52×10^-6	0.90726
200	244	636108.04	6.76×10^-9	0.98435	9316.26	9.60×10^-6	0.90927
200	325	546815.62	1.37×10^-8	0.98545	12393.99	9.58×10^-6	0.93486
250	163	1348901.45	9.53×10^-10	0.98306	7005.67	6.63×10^-6	0.90085
250	244	1007604.39	2.70×10^-9	0.97305	9713.18	6.43×10^-6	0.90056
250	325	978129.03	3.74×10^-9	0.99000	11643.79	5.85×10^-6	0.91846

序号	T/℃	C₀/mg·m^-3	k₂（实验值）	k₂（计算值）	误差/%
1	105	146	1.898×10^-7	1.817×10^-7	4.433
2	140	439	2.000×10^-9	1.849×10^-9	8.164
3	225	496	2.332×10^-9	2.164×10^-9	7.755

序号	T/℃	C₀/mg·m^-3	k₂（实验值）	k₂（计算值）	误差/%
1	105	146	1.898×10^-7	1.817×10^-7	4.433
2	140	439	2.000×10^-9	1.849×10^-9	8.164
3	225	496	2.332×10^-9	2.164×10^-9	7.755