CN110669212B - 利用溶胶-凝胶法制备金属-螯合物型缓凝剂的工艺 - Google Patents
利用溶胶-凝胶法制备金属-螯合物型缓凝剂的工艺 Download PDFInfo
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Abstract
本发明涉及利用溶胶‑凝胶法制备金属‑螯合物型缓凝剂的工艺，过程如下：按一定的质量比称取四水硝酸钙、九水硝酸铝、九水硝酸铁加入去离子水中，将混合液置于磁力搅拌机上搅拌使其混合均匀，加入一水合柠檬酸或葡萄糖酸、乙二醇或丙三醇后，置于水浴锅中反应，得到金属‑螯合物型缓凝剂。本发明原理可靠，克服了已有缓凝剂生产周期长、制备复杂等缺陷，工艺操作简单，原料廉价易得，生产周期短，制备的缓凝剂温度适应范围广，稠化时间可调，适用于大规模工业化生产，具有广阔的市场应用前景。
Description
技术领域
本发明涉及油气田勘探开发领域固井过程中一种新型缓凝剂的制备方法，特别是涉及一种利用溶胶-凝胶法制备金属-螯合物型缓凝剂的工艺，属于固井水泥浆外加剂的制备方法。
背景技术
石油工业是经济发展的血液，固井质量的好坏直接影响石油的开采及油气井的生产寿命。随着钻井技术的提高，石油勘探开发不断向高温井、深井及超深井方向发展,注水泥井段上下地层温差和压差越来越大，在高温高压下，为保证施工的安全性与固井的质量，通常在水泥浆中加入缓凝剂，以增加水泥浆的稠化时间，防止泵送水泥浆在整个泵送过程中快速稠化和凝结，以此来控制水泥浆的可泵时间。
常规G级油井水泥的水化过程主要包括：初始活泼期、诱导期、加速期和硬化期。在初始反应的快速活泼期，当水泥与水接触时，立即开始一个很短但是异常激烈的放热反应，而后其水化速率迅速下降进入诱导期。缓凝剂的加入，主要影响该反应阶段，其作用机理一般为缓凝剂分子与游离的Ca2+或水分子结合形成复盐，吸附在水泥颗粒表面，毒化晶体的核晶过程，从而阻止了晶体的生长，抑制水泥的水化(王振军,何廷树.缓凝剂作用机理及对水泥混凝土性能影响[J].公路,2006(07):149-154)。
目前国内外常用的缓凝剂为木质素硫磺盐类、糖类化合物、羟基羧酸及其盐类。木质素类缓凝剂的原料属于天然产物，受地区和温度影响较大，在生产地的选择上有很大的局限性。羟基羧酸类缓凝剂的合成所需的原料较多，合成过程也相对复杂，时间较长，易产生副产物，造成环境污染。鉴于此，本发明提供一种新型缓凝剂的制备方法，克服了已有缓凝剂原料不易获取、制备复杂、时间周期长、有副产物等缺陷，通过该方法制备的缓凝剂温度适应范围广，稠化时间可调，同时由于其为铁铝酸四钙前驱体，在长期高温养护作用下会转变为铁铝酸四钙，铁铝酸四钙属于水泥的组成矿物之一，这种转变将对水泥石的后期强度的发展起到积极的作用。
发明内容
本发明的目的在于提供利用溶胶-凝胶法制备金属-螯合物型缓凝剂的工艺，原理可靠，克服了已有缓凝剂生产周期长、制备复杂等缺陷，工艺操作简单，原料廉价易得，生产周期短。通过该方法制备的缓凝剂温度适应范围广，稠化时间可调，适用于大规模工业化生产，具有广阔的市场应用前景。
为达到以上技术目的，本发明采用以下技术方案。
利用溶胶-凝胶法制备金属-螯合物型缓凝剂的工艺，过程如下：按一定的质量比称取四水硝酸钙、九水硝酸铝、九水硝酸铁加入去离子水中，将混合液置于磁力搅拌机上搅拌使其混合均匀，加入一水合柠檬酸或葡萄糖酸、乙二醇或丙三醇后，置于水浴锅中反应，得到金属-螯合物型缓凝剂。
所述利用溶胶-凝胶法制备金属-螯合物型缓凝剂的工艺，依次包括以下步骤：
(1)将四水硝酸钙80-120g、九水硝酸铝20-40g、九水硝酸铁10-15g加入到50-70ml去离子水中，置于磁力搅拌机上搅拌50-60min，使其混合均匀，得到溶液A；
(2)将螯合剂30-50g加入溶液A中，置于60-80℃水浴锅中搅拌得到淡黄色溶液B，所述螯合剂为一水合柠檬酸或葡萄糖酸；
(3)向溶液B中搅拌加入酯化剂5-20g发生酯化反应，所述酯化剂为乙二醇或丙三醇，持续12-24小时，得到金属-螯合物型缓凝剂。
所述步骤(2)中，将螯合剂加入溶液A中，置于60℃水浴锅中搅拌1-2小时后，再将水浴锅温度调至80℃。
利用溶胶-凝胶法制备金属-螯合物型缓凝剂的反应机理如下(以一水合柠檬酸为例)：
四水硝酸钙、九水硝酸铝、九水硝酸铁与一水合柠檬酸在水溶液中发生反应，由于硝酸盐易溶于水，金属硝酸盐在水中水解为金属阳离子(M+)和硝酸根离子(NO3 -)，柠檬酸作为螯合剂加入到溶液中，可以提供三个羧基氧原子和一个羟基氧原子与金属阳离子配位，两分子的柠檬酸与金属阳离子形成六配位的八面体结构，同时柠檬酸的螯合反应的进行使得溶液中产生大量游离的H+，为反应提供一个酸性的环境。
乙二醇的加入，将与螯合物上未发生反应的两个羧基发生酯化反应，使得螯合物相互联结形成低聚物，即缓凝剂的主要成分。
与现有技术相比，本发明具有以下有益效果：
(1)采用胶体化学法—溶胶凝胶法，通过化学合成，避免合成过程中引入新的杂质，制备的金属-螯合物缓凝剂不仅不影响水泥石的抗压强度，而且还能有效延缓水泥稠化时间；
(2)各种原料来源广、价格低，具有低成本的优势；
(3)制备的缓凝剂温度适应范围更广，且稠化时间可调；
(4)该方法操作简单，产率高，生产周期短，对原料的品质要求较低，适合大规模工业化应用。
具体实施方式
下面根据实施例进一步说明本发明，以便于本领域的技术人员理解本发明。但应该清楚，本发明不限于具体实施方式的范围，只要各种变化在所附的权利要求限定和本发明技术方案的精神和内容，均属本发明的保护范围之列。
一、耐高温油井水泥缓凝剂的制备
实施例1
一种利用溶胶-凝胶法制备金属-螯合物型缓凝剂的工艺，具体包括以下步骤：
用天平依次称量四水硝酸钙(Ca(NO3)2·4H2O)80g，九水硝酸铝(Al(NO3)3·9H2O)20g，九水硝酸铁(Fe(NO3)3·9H2O)10g，然后加入50ml去离子水中，置于磁力搅拌机上搅拌50min，使其混合均匀，得到混合液A；称量一水合柠檬酸(C6H8O7·H2O)40g加入混合液A中，置于80℃水浴锅中搅拌得到淡黄色溶液B；向淡黄色溶液B中依次加入乙二醇5g发生酯化反应，持续12小时，得到金属-螯合物型缓凝剂。
实施例2
一种利用溶胶-凝胶法制备金属-螯合物型缓凝剂的工艺，具体包括以下步骤：
用天平依次称量四水硝酸钙(Ca(NO3)2·4H2O)90g，九水硝酸铝(Al(NO3)3·9H2O)30g，九水硝酸铁(Fe(NO3)3·9H2O)10g，然后加入60ml去离子水中，置于磁力搅拌机上搅拌50min，使其混合均匀，得到混合液A；称量葡萄糖酸30g加入混合液A中，置于80℃水浴锅中搅拌得到淡黄色溶液B；向淡黄色溶液B中依次加入丙三醇10g发生酯化反应，持续12小时，得到金属-螯合物型缓凝剂。
实施例3
一种利用溶胶-凝胶法制备金属-螯合物型缓凝剂的工艺，具体包括以下步骤：
用天平依次称量四水硝酸钙(Ca(NO3)2·4H2O)120g，九水硝酸铝(Al(NO3)3·9H2O)40g，九水硝酸铁(Fe(NO3)3·9H2O)15g，然后加入70ml去离子水中，置于磁力搅拌机上搅拌60min，使其混合均匀，得到混合液A；称量一水合柠檬酸(C6H8O7·H2O)50g加入混合液A中，置于60℃水浴锅中搅拌得到淡黄色溶液B；向淡黄色溶液B中加入丙三醇20g发生酯化反应，一小时后将水浴锅温度调至80℃，持续15小时，得到金属-螯合物型缓凝剂。
实施例4
一种利用溶胶-凝胶法制备金属-螯合物型缓凝剂的工艺，具体包括以下步骤：
用天平依次称量四水硝酸钙(Ca(NO3)2·4H2O)100g，九水硝酸铝(Al(NO3)3·9H2O)20g，九水硝酸铁(Fe(NO3)3·9H2O)15g，然后加入70ml去离子水中，置于磁力搅拌机上搅拌60min，使其混合均匀，得到混合液A；称量葡萄糖酸40g加入混合液A中，置于60℃水浴锅中搅拌得到淡黄色溶液B；向淡黄色溶液B中加入乙二醇15g发生酯化反应，两小时后将水浴锅温度调至80℃，持续20小时，得到金属-螯合物型缓凝剂。
二、耐高温油井水泥缓凝剂的缓凝性能测试
将实施例1中合成的缓凝剂加入水泥浆配方中(表一所示)，在温度90℃，压力45MPa的稠化条件进行试验，以验证该螯合物的缓凝性能。
表一实验配方
表二同一温度(90℃)不同加量下固井用水泥浆工程性能测试结果(实施例1)
表三不同温度下同一加量固井用水泥浆工程性能测试结果(实施例2)
三、耐高温油井水泥缓凝剂的强度性能测试
将实施例1中合成的缓凝剂加入水泥浆配方中(见表一)，在温度90℃下进行养护，分别测试其1，3，7天的强度。
表四抗压强度
由表四可以看出，本发明制备的缓凝剂在有效改善水泥稠化时间的同时，并不影响水泥石高温养护后的强度。
Claims (2)
1.利用溶胶-凝胶法制备金属-螯合物型缓凝剂的方法，依次包括以下步骤：
（1）将四水硝酸钙80-120g、九水硝酸铝20-40g、九水硝酸铁10-15g加入到50-70ml去离子水中，置于磁力搅拌机上搅拌50-60min，使其混合均匀，得到溶液A；
（2）将螯合剂30-50g加入溶液A中，置于60-80℃水浴锅中搅拌得到淡黄色溶液B，所述螯合剂为一水合柠檬酸或葡萄糖酸；
（3）向溶液B中搅拌加入酯化剂5-20g发生酯化反应，所述酯化剂为乙二醇或丙三醇，持续12-24小时，得到金属-螯合物型缓凝剂。
2.如权利要求1所述的利用溶胶-凝胶法制备金属-螯合物型缓凝剂的工艺，其特征在于，所述步骤（2）中，将螯合剂加入溶液A中，置于60℃水浴锅中搅拌1-2小时后，再将水浴锅温度调至80℃。
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