乙二胺盐酸盐与氢氧化钙反应动力学

doi:10.19964/j.issn.1006-4990.2023-0364

Abstract

Abstract:

The industrial production process of diamino silane coupling agent results in the generation of a significant quantity of ethylenediamine hydrochloride by-product.This by-product can be repurposed via neutralization reaction with calcium hydroxide to acquire anhydrous ethylenediamine.The conductivity method was utilized to establish the interdependence of ethylenediamine hydrochloride conversion rate and conductivity.The impact of various factors including liquid-solid ratio，salt concentration，and temperature on the conversion rate of ethylenediamine hydrochloride was explored and the optimal process conditions were determined.The experimental results indicated that the conversion rate of ethylenediamine hydrochloride was declined with the increase of liquid-solid ratio and ethylenediamine hydrochloride concentration.The kinetic equations for ethylenediamine hydrochloride and calcium hydroxide were established based on the shrinking core model.The experimental data was analyzed to determine the activation energy of the reaction process，revealing that internal diffusion primarily controlled the neutralization reaction between ethylenediamine hydrochloride and calcium hydroxide.The kinetic model Kt=1-3（1-x）^2/3+2（1-x） was applied，giving an activation energy of 30.89 kJ/mol.This study established a valuable empirical foundation for extracting anhydrous ethylenediamine from the by-product of ethylenediamine hydrochloride.

Key words: ethylenediamine hydrochloride, shrinking core model, kinetics, calcium chloride

CLC Number:

TQ115

ZHANG Yu, ZHAO Guiyan, TIAN Yongchang, QIU Xiaokui, SUN Jiali, XU Lixin. Reaction kinetics of ethylenediamine hydrochloride with calcium hydroxide[J]. Inorganic Chemicals Industry, 2024, 56(5): 64-69.

Figures/Tables 10

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References 20

1	李超，王继琼.乙撑胺生产技术及市场现状［J］.天津化工，2017，31（4）：10-11.
	LI Chao， WANG Jiqiong.乙撑胺生产技术及市场现状［J］.Tianjin Chemical Industry，2017，31（4）：10-11.
2	周晶，邱俊.乙二胺合成工艺及催化剂的研究进展［J］.化学世界，2016，57（9）：583-589.
	ZHOU Jing， QIU Jun.Research progress of the synthetic process of ethylenediamine and its catalysts［J］.Chemical World，2016，57（9）：583-589.
3	杨溢，兰昭洪，田保亮，等.乙二胺合成工艺进展［J］.石油化工，2012，41（5）：603-608.
	YANG Yi， LAN Zhaohong， TIAN Baoliang，et al.Progress in research of ethylenediamine synthesis［J］.Petrochemical Technology，2012，41（5）：603-608.
4	刘玉普，邸友莹，何东华，等.乙二胺盐酸盐的低温热容和热化学性质［J］.高等学校化学学报，2010，31（6）：1227-1230.
	LIU Yupu， DI Youying， HE Donghua，et al.Low-temperature heat capacities and thermochemistry properties of ethylene diamine dihydrochloride［J］.Chemical Journal of Chinese Universities，2010，31（6）：1227-1230.
5	罗娟，胡忠于，仇明华.脱除乙二胺盐酸盐中HCl的新方法［J］.吉首大学学报（自然科学版），2004，25（1）：92-93.
	LUO Juan， HU Zhongyu， QIU Minghua.Research about how to extract hydrochloride existing in ethylenediamine［J］.Journal of Jishou University（Natural Science Edition），2004，25（1）：92-93.
6	BUDDE F J.Process for the recovery of ethylene amines：US，5072048［P］.1991-12-10.
7	王伟，毛伟，吕婧，等.萃取精馏法分离乙二胺和H₂O的共沸物［J］.化学工程，2014，42（10）：25-28.
	WANG Wei， MAO Wei， Jing LÜ，et al.Separation of EDA and H₂O azeotrope by extractive distillation［J］.Chemical Engineering （China），2014，42（10）：25-28.
8	JAYARAMAN K， VELAYUTHAM D， SRINIVASAN R K，et al.Isolation of ethylenediamine from industrial solution of ethylenediamine hydrochloride by electrodialysis［J］.Journal of Chemical Technology & Biotechnology，2003，78（6）：626-631.
9	CESAS R， ZAJACK T.Neutralization of Ethylenediamine Hydrochloride and recovery of Ethylenediamine：US，20100069673［P］. 2010-03-18.
10	胡江华，罗晗晗，甘俊，等.一种从双胺基硅烷副产物乙二胺盐酸盐中制取无水乙二胺的方法：中国，110172024B［P］.2022-03-04.
11	赵锋伟，惠丰，袁俊，等.乙醇胺缩合胺化反应合成乙二胺研究进展［J］.化工进展，2020，39（S2）：212-220.
	ZHAO Fengwei， HUI Feng， YUAN Jun，et al.Progress in selective synthesis of ethylenediamine via condensation amination of monoethanolamine［J］.Chemical Industry and Engineering Progress，2020，39（S2）：212-220.
12	张海江.管道化反应器合成乙二胺的工艺研究［D］.杭州：浙江大学，2008.
	ZHANG Haijiang.Study on the synthesis of ethylenediamine with a tubular reactor［D］.Hangzhou：Zhejiang University，2008.
13	彭嘉伟，邓德华，刘赞群.电导率法测定氯氧镁水泥中醇可抽提氯离子含量［J］.建筑材料学报，2022，25（8）：877-884.
	PENG Jiawei， DENG Dehua， LIU Zanqun.Determination of alcohol leachable chloride ion content of magnesium oxychloride cement by conductivity method［J］.Journal of Building Materials，2022，25（8）：877-884.
14	王浩森，任柄臣，许德华，等.硝酸分解磷钾矿的浸出工艺及动力学［J］.无机盐工业，2023，55（5）：45-51.
	WANG Haosen， REN Bingchen， XU Dehua，et al.Leaching process and kinetics of phosphorus-potassium ore decomposition by nitric acid［J］.Inorganic Chemicals Industry，2023，55（5）：45- 51.
15	王智玉，廖玮婷，谢雷，等.超临界乙醇中木质素解聚的宏观动力学模型［J］.林产工业，2021，58（6）：55-60.
	WANG Zhiyu，LIAO Weiting，XIE Lei，et alMacro［P］.kinetics model of lignin depolymerization in supercritical ethanol［J］.China Forest Products Industry，2021，58（6）：55-60.
16	孟留洋，李解，苏文柔，等.白云鄂博钾长石微波碱浸反应等温动力学分析［J］.稀有金属，2020，44（10）：1113-1120.
	MENG Liuyang， LI Jie， SU Wenrou，et al.Isothermal kinetics of alkaline leaching of potassium feldspar from Bayan obo under microwave irradiation［J］.Chinese Journal of Rare Metals，2020，44（10）：1113-1120.
17	高新愿.磷石膏制硫酸钾第一阶段反应动力学研究［D］.南昌：南昌大学，2018.
	GAO Xinyuan.Study on the First Stage Reaction Kinetics of Potassium Sulfate from Phosphogypsum［D］.Nanchang：Nanchang University，2018.
18	周海，杨三可，解田.磷酸分解磷矿的动力学及影响因素研究［J］.应用化工，2021，50（6）：1472-1477.
	ZHOU Hai， YANG Sanke， XIE Tian.Study on the dissolution kinetics of phosphate ore in phosphoric acid and its influencing factors［J］.Applied Chemical Industry，2021，50（6）：1472-1477.
19	HOMMA S， OGATA S， KOGA J，et al.Gas-solid reaction model for a shrinking spherical particle with unreacted shrinking core［J］.Chemical Engineering Science，2005，60（18）：4971-4980.
20	KAVCı E， ÇALBAN T， ÇOLAK S，et al.Leaching kinetics of ulexite in sodium hydrogen sulphate solutions［J］.Journal of Industrial and Engineering Chemistry，2014，20（5）：2625-2631.

反应温度/K	斜率	T^-1/K^-1	ln K
303	6.3×10^-4	3.30×10^-3	-7.37
318	9.8×10^-4	3.14×10^-3	-6.92
333	1.43×10^-3	3.00×10^-3	-6.54
348	1.95×10^-3	2.87×10^-3	-6.24
363	2.35×10^-3	2.75×10^-3	-6.05

反应温度/K	斜率	T^-1/K^-1	ln K
303	4.0×10^-4	3.30×10^-3	-7.81
318	8.8×10^-4	3.14×10^-3	-7.04
333	1.62×10^-3	3.00×10^-3	-6.42
348	2.43×10^-3	2.87×10^-3	-6.02
363	2.98×10^-3	2.75×10^-3	-5.81

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Reaction kinetics of ethylenediamine hydrochloride with calcium hydroxide

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