Page 200 - 《精细化工》2020年第4期

第 37 卷第 4 期 精 细 化 工 Vol.37, No.4
202 0 年 4 月 FINE CHEMICALS Apr. 2020

油田化学品与油品添加剂
环境友好型交联酸的性能及其反应动力学

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罗明良 1,2 ，巩锦程 ，战永平 1,2 ，司晓冬 ，罗 帅 ，李钦朋
〔1. 非常规油气开发教育部重点实验室 中国石油大学（华东），山东 青岛 266580；2. 中国石油大学（华
东） 石油工程学院，山东 青岛 266580〕
摘要：以乳酸、葡萄糖酸、聚乙烯亚胺（PEI）及聚丙烯酰胺类稠化剂为主要原料，采用溶液共混法制备了一种
环境友好型耐高温交联酸 EAC-1。结合 FTIR、流变测试、SEM 等分析了乳酸与葡萄糖酸混合形成的复合酸溶
蚀 CaCO 3 的协同作用机理以及交联酸 EAC-1 的流变性、微观结构以及破胶性能，明确了交联酸的反应速率常数
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及其反应动力学方程。结果表明，当乳酸及葡萄糖酸物质的量比为 1∶1 时，乳酸和葡萄糖酸可与 Ca 通过共价
–1
键作用形成一种具有高溶解度的螯合物，使残酸中无二次沉淀生成；当 PEI 质量分数为 0.12%时, 170 s 、110 ℃
下交联酸黏度保持在 50 mPa·s 以上；交联剂 PEI 与稠化剂形成的立体网状结构保证体系具有良好的耐温耐剪切
能力，且交联酸破胶均匀，无残渣，破胶液黏度仅为 4.2 mPa·s；EAC-1 的反应速率常数比以盐酸为主体酸的交
联酸 HC-1 小 1 个数量级，表明 EAC-1 交联酸具有良好的缓速性能，有利于延长酸液有效作用距离。
关键词：交联酸；酸岩反应动力学；缓速性能；油田化学品与油品添加剂
中图分类号：TE357.2; TE39 文献标识码：A 文章编号：1003-5214 (2020) 04-0834-07

Performance and reaction kinetics of environmental-friendly crosslinked acid

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LUO Mingliang , GONG Jincheng , ZHAN Yongping , SI Xiaodong , LUO Shuai , LI Qinpeng
〔1. Key Laboratory of Unconventional Oil & Gas Development , Ministry of Education, China University of Petroleum (East
China)，Qingdao 266580, Shandong, China; 2. School of Petroleum Engineering, China University of Petroleum (East China),
Qingdao 266580, Shandong, China〕
Abstract: An environmental-friendly crosslinked acid (EAC-1) with high-temperature resistance was
prepared by solution blending method using lactic acid, gluconic acid, polyethyleneimine (PEI) and
polyacrylamide thickener as main raw materials. The synergistic mechanism of CaCO 3 dissolution by
complex acid composed of lactic acid and gluconic acid, the rheology, microstructures and gel breaking
properties of EAC-1 were analyzed by FTIR, rheological test, SEM and so on. The reaction rate constant
and reaction kinetic equation of crosslinked acid were also determined. The results showed that when the
molar ratio of lactic acid to gluconic acid was 1∶1, lactic acid and gluconic acid could form a chelate with
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high-solubility with Ca through covalent bond, and no secondary precipitation happened in the residual
–1
acid. The viscosity of crosslinked acid maintained above 50 mPa·s at 170 s and 110 ℃ when the mass
fraction of PEI was 0.12%. The three- dimensional network structure formed by crosslinking agent PEI and
thickener made the system have good high-temperature resistance and shearing resistance. The crosslinked
acid exhibited uniform gel breaking without residues, and the viscosity was 4.2 mPa·s after gel breaking.
The reaction rate constant of EAC-1 was one order of magnitude smaller than that of HC-1 using
hydrochloric acid as main acid, showing that crosslinked acid EAC-1 had good retarding effect for
prolonging the effective action distance of acid fluid in acidizing fracturing.
Key words: crosslinked acid; acid-rock reaction kinetics; retarding property; oil field chemicals and
petroleum additives

收稿日期：2019-08-26; 定用日期：2019-10-23; DOI: 10.13550/j.jxhg.20190816
基金项目：国家自然科学基金（51874334,51674278）；山东省自然科学基金（ZR2018MEE010）；“十三五”国家科技重大专项
（2017ZX005030005）
作者简介：罗明良（1974—），男，教授，E-mail：yfsailing_wxg@163.com。