有机膦系抑制方解石阶梯面生长的分子动力学研究

doi:10.19964/j.issn.1006-4990.2020-0525

摘要/Abstract

摘要：

有机膦系化合物是工业冷却水系统中常用阻垢剂,对有机膦酸阻垢剂的阻垢性能及机理进行研究,能为新型阻垢剂开发应用提供合理的理论依据。根据周期性键链（PBC）理论模型,运用分子动力学方法（MD）,模拟了工业冷却水循环过程中5种有机膦阻垢剂与方解石4种阶梯面的相互作用机理。结果表明,有机膦酸分子与方解石（104）4个阶梯面的结合能均为负值,相互作用为放热过程,阻垢剂分子对方解石（104）阶梯面的生长具有良好的抑制作用。通过计算结合能,得出阻垢剂分子的吸附能力由强到弱依次为HDTMP、EDTMP、ATMP、NDP、AMP;同时观察到有机膦酸分子主要吸附在晶面的活性生长点,即阶梯面的终端拐角位置与阶梯拐点位置,占据了晶面上结晶的活性位置,抑制了晶面的进一步生长。根据有机膦酸与阶梯面结合能数据,得到4种终端阶梯面的吸附能力由强到弱依次为CO₃-CO₃、CO₃-Ca、Ca-CO₃、Ca-Ca,即稳定性越强则吸附能力越弱。

关键词: 有机膦酸阻垢剂, 方解石, 阶梯面, 分子动力学

Abstract:

Organic phosphonic compounds are commonly used scale inhibitors in industrial cooling water system.Studying on the scale inhibition performance and mechanism of organic phosphonic acid scale inhibitors can provide reasonable theoreti-cal basis for the development and application of new scale inhibitors.The interaction mechanism between five organic phos-phine scale inhibitors and four steps of calcite in the process of industrial cooling water circulation was simulated by using the molecular dynamics （MD）method based on the PBC theoretical model.The results showed that the binding energy of organic phosphonic acid molecule and calcite（104） was minus,the process of interaction was exothermic reaction,and the scale in-hibitor molecule had well repressive effect on the growth of calcite（104）.Through calculating combining capacity,it could be obtained that the adsorption capacity of the scale inhibitor molecule from strong to weak was as fouows HDTMP,EDTMP,ATMP,NDP and AMP.It was observed that the organic phosphonic acid molecules were mainly adsorbed on the active growth point of the crystallo graphic plane that the position of the terminal corner of the stepped plane and the position of the stepped inflection point so that the active position of crystallization plane was occupied and the further growth of the crystal plane was restrained.Based on the binding energy data of organic phosphonic acid and step surface,the adsorption capacity of the four terminal step surfaces from strong to weak was as follows CO₃-CO₃,CO₃-Ca,Ca-CO₃,Ca-Ca,so the stability was stronger,the adsorption capacity was weaker.

Key words: organic phosphonate inhibitor, calcite, stepped surface, molecular dynamic

中图分类号:

TQ132.32

陈春钰,门丽娟,居殿春,郭雷,姚富升,张琪,俞鸿宇. 有机膦系抑制方解石阶梯面生长的分子动力学研究[J]. 无机盐工业, 2021, 53(8): 31-35.

Chen Chunyu,Men Lijuan,Ju Dianchun,Guo Lei,Yao Fusheng,Zhang Qi,Yu Hongyu. Molecular dynamics study on inhibition of calcite stepped surfaces growth by organic phosphonates[J]. Inorganic Chemicals Industry, 2021, 53(8): 31-35.

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晶面	E_att（Total）	E_att（Electrostatic）	E_att（Vdw）
（104）	-1 552.95	-1 546.14	-6.81
（110）	-5 306.38	-5 355.96	49.57
（112）	-11 707.14	-11 755.50	48.36

有机磷化合物	△E
有机磷化合物	Ca-Ca	CO₃-CO₃	Ca-CO₃	CO₃-Ca	E_bind,cor
AMP	-971.8	-785.4	-1 019.5	-1 037.9	-932.6
NDP	-1 026.2	-911.6	-1 053.8	-1 070.1	-1 034.1
ATMP	-1 084.7	-961.8	-1 267.4	-2 375.9	-1 425.4
EDTMP	-1 261.1	-3 384.1	-1 376.1	-3 044.7	-1 723.6
HDTMP	-1 560.8	-3 589.3	-1 580.9	-3 398.8	-2 525.1

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