郑怡杰，龚 鹏，邓卓然，何 鑫，张春梅，梅开元，程小伟

（西南石油大学 新能源与材料学院，油气藏地质及开发工程全国重点实验室，四川 成都 610500）

引用格式：

郑怡杰，龚鹏，邓卓然，等. 镁橄榄石对油井水泥抗CO₂腐蚀性能的影响［J］. 中国粉体技术，2024，30（2）：151-163.

ZHENG Y J， GONG P， DENG Z R， et al. Effect of magnesium olivine on CO₂ corrosion resistance of oil well cement［J］. China Powder Science and Technology，2024，30（2）：151−163.

DOI：10.13732/j.issn.1008-5548.2024.02.013

收稿日期：2023-10-02，修回日期：2023-11-29，上线日期：2024-02-20。

基金项目：国家自然科学基金项目，编号：42207206。

第一作者简介：郑怡杰（1999—），男，硕士生，研究方向为超临界CO₂环境下油井水泥石抗腐蚀性能。E-mail:2817950245@qq.com。

通信作者简介：程小伟（1977—），男，教授，博士，四川省学术和技术带头人，博士生导师，研究方向为先进胶凝材料与其在固井中应用。 E-mail：chengxw@swpu.edu.cn。

摘要：【目的】 研究减轻超临界CO₂环境对油井水泥石腐蚀渗透的影响。【方法】 以镁橄榄石为外掺料配制不同的油井水泥，分析温度为150 ℃，CO₂总压为50 MPa条件下镁橄榄石水泥石的抗压强度，优选出镁橄榄石的最佳掺量；利用渗透率、热重分析（thermo gravimetric analysis，TGA）、X 射线衍射（X-Ray diffraction，XRD）和扫描式电子显微镜（scanning electron microscope，SEM）进行测试，评价镁橄榄石对油井水泥石抗CO₂腐蚀性能的影响，分析镁橄榄石对油井水泥石抗CO₂腐蚀的影响机理。【结果】 镁橄榄石的掺入不会影响油井水泥的流动度，当镁橄榄石质量分数为2%时，对比腐蚀前油井水泥石的，抗压强度提高 35. 47%，渗透率降低 0. 010 4 mD；腐蚀 28 d 后，镁橄榄石水泥石的抗压强度为空白水泥石的193. 71%，且仍高于腐蚀前。【结论】 镁橄榄石是一种抗CO₂腐蚀外加剂，能提升油井水泥的抗CO₂腐蚀性能。

关键词：镁橄榄石；高温高压；超临界二氧化碳；腐蚀；油井水泥石

Abstract

Objective Using CO₂ injection to enhance oil and gas recovery is crucial in the carbon neutralization process. However，the presence of supercritical CO₂ in CCUS wells poses higher demands on the corrosion resistance of wellbore cement. Magnesia olivine，characterized by abundant sources and low cost， has been extensively studied in the field of construction cement. Yet， research on enhancing the resistance of wellbore cement to CO₂ corrosion using magnesia olivine is relatively limited.In this study，con⁃ducted in the unique environment of CCUS wells，corrosion experiments will be carried out using supercritical CO₂ saturated solutions. Various testing methods，including compressive strength， permeability，X-ray diffraction（XRD），thermogravimetric analysis（TGA），and scanning electron microscopy（SEM），will be employed to investigate the optimal dosage of magnesia oliv⁃ine and its role in the micro-mechanism of corrosion resistance. This research aims to provide new theoretical and practical support for enhancing the resistance of wellbore cement to CO₂ corrosion，contributing technological solutions towards achieving the“carbon neutrality and peak carbon”goals.

Methods Utilizing layered olivine magnesium with an average particle size of 23 μm as an additive and cement slurry with a density of 1. 92 g/cm³， oil well cements with varying additive concentrations（0，0. 5，1，1. 5，2，2. 5，3 wt.%）were formulated and cured following GB/T 19139—2012. Under conditions of 150 °C and 50 MPa CO₂ pressure，compressive strength and per⁃meability were tested for both blank samples and samples with magnesium olivine，aiming to identify the optimal dosage of mag⁃nesium olivine. Thermal Gravimetric Analysis（TGA），X-ray Diffraction（XRD），and Scanning Electron Microscopy （SEM）were employed to analyze the impact and mechanisms of magnesium olivine on the CO₂ corrosion resistance performance of the cement slurry.

Results and Discussion Formulated cement slurries with different concentrations （0，0. 5，1，1. 5，2，2. 5，3%） of magnesium olivine. No significant impact on the density of oil well cement slurries was observed with the addition of magnesium olivine.Maintained good fluidity of the slurry，indicating favorable rheological properties. Conducted testing under conditions of 150 °C and 50 MPa CO₂ pressure. Magnesium olivine addition enhanced the compressive strength of cement both before and after corrosion， showing a 35. 47% increase at 2% olivine concentration. The compressive strength initially increased and then decreased with higher olivine concentrations. Improved compressive strength attributed to the filling of micro-pores by magnesium olivine，enhancing cement density. Super-critical CO₂ corrosion resulted in the formation of calcium carbonate（CaCO₃）on the cement surface.The presence of magnesium olivine contributed to the reduction of Ca（OH）₂ and the formation of dense CaCO_3,enhancing the cement's resistance to CO₂ corrosion. The addition of 2% magnesium olivine demonstrated the highest compressive strength before and after corrosion. Extended corrosion testing up to 28 days revealed a gradual decrease in compressive strength for both control and magnesium olivine-added cement. Magnesium olivine-added cement showed better longterm performance，with slower deterioration in compressive strength compared to the blank cement stone，which improved by 193. 71%. The permeability of the cement was effectively reduced by magnesium olivine，indicating improved resistance to CO₂ corrosion. XRD and TGA analysis confirmed the presence of magnesium olivine and the formation of carbonates（CaCO₃）in the corroded cement.The addition of magnesium olivine reduced Ca（OH）₂ content and influenced the types of carbonate phases formed during corrosion. SEM images illustrated the microstructural changes in cement，showing the impact of magnesium olivine on the formation of corrosion products. Magnesium olivine addition resulted in a denser microstructure， reduced pore formation，and better overall cement integrity. The observed improvements in cement performance were attributed to the role of magnesium olivine in hindering the penetration of CO₂，optimizing microstructure， and promoting the formation of stable carbonate phases. The optimal addition of 2% magnesium olivine was identified as providing the best balance between enhancing compressive strength and resisting CO₂ corrosion in oil well cement. The study demonstrates the potential of magnesium olivine as an effective additive for improving the durability and performance of oil well cement in the context of super-critical CO₂ corrosion.

Conclusion The optimal addition of 2% magnesium olivine was identified as providing the best balance between enhancing compressive strength and resisting CO₂ corrosion in oil well cement. The study demonstrates the potential of magnesium olivine as an effective additive for improving the durability and performance of oil well cement in the context of super-critical CO₂ corrosion.

Keywords：magnesium olivine； high temperature and high pressure； supercritical CO₂； corrosion； oil-well cement

参考文献（References）

［1］宋新民，杨思玉. 国内外CCS技术现状与中国主动应对策略［J］. 油气藏评价与开发，2011，1（1）：25-30.

SONG X M， YANG S Y. Current situation of CCS technology at home and abroad and the positive strategy that China should adopt toward it［J］. Reservoir Evaluation and Development，2011（1）：25-30.

［2］TURGUT M G. Carbon dioxide emissions， capture， storage and utilization： review of materials， processes and technologies［J］. Progress in Energy & Combustion Science，2022，89：100965.

［3］ZENG H， XIAO C， CHEN X， et al. State of China's climate in 2018［J］. Atmospheric and Oceanic Science Letters，2019，12（5）：349-354.

［4］FRANKLIN M O. Carbon capture， utilization， and storage： an update［J］. SPE Journal，2018，23（6）：2444-2455.

［5］VIJETA A， RISHABH K S， KUMAR R， et al. Separation and sequestration of CO₂ in geological formations［J］. Materials Science for Energy Technologies，2019，2（3）：647-656.

［6］FREIRE A L， JOSÉ H J， MOREIRA. Potential applications for geopolymers in carbon capture and storage［J］. International Journal of Greenhouse Gas Control，2022，118：103687.

［7］CHEN X H， WU X. The roles of carbon capture， utilization and storage in the transition to a low-carbon energy system using a stochastic optimal scheduling approach［J］. Journal of Cleaner Production，2022，366：132860.

［8］ALFARGE D， WEI M， BAI B J. Data analysis for CO₂-EOR in shale-oil reservoirs based on a laboratory database ［J］.Journal of Petroleum Science and Engineering，2018，162：697-711.

［9］胡永乐，郝明强，陈国利，等. 中国CO₂驱油与埋存技术及实践［J］. 石油勘探与开发，2019，46（4）：716-727.HU Y L， HAO M Q， CHEN G L， et al. Technologies and practice of CO₂ flooding and sequestration in China［J］. Petroleum Exploration and Development，2019，46（4）：716-727.

［10］WANG Y Y， WANG X G， DONG R C， et al. Reservoir heterogeneity controls of CO₂-EOR and storage potentials in residual oil zones： Insights from numerical simulations［J］. Petroleum Science，2023，3：023.

［11］MOHAMED R G， IBRAHIM A F， ADEBAYO A. Uncertainty quantification for CO₂ storage during intermittent CO₂-EOR in oil reservoirs［J］. International Journal of Coal Geology，2023，266：104177.

［12］STEFAN B. Sequestration of CO₂ in geological media： criteria and approach for site selection in response to climate change［J］. Energy Conversion and Management，2000，41（9）：953-970.

［13］姚晓， 唐明述. 油井水泥石CO₂腐蚀的热力学条件［J］. 油气藏地质及开发工程国家重点实验室西南石油大学；中国石化西南石油工程有限公司固井分公司，1999，16（1）：10-14.

YAO X， TANG M S. Study on the structure and properties of two microcrosslinked carboxymethyl celluloses［J］. Oilfield Chemistry，1999，16（1）：10-14.

［14］刘思楠，张力为，甘满光，等 . 地质封存环境 CO₂压力影响水泥碳化程度的试验研究［J］. 中国电机工程学报，2022，42（9）：3126-3135.

LIU S N， ZHANG L W， GAN M G， et al. Experimental study of the effect of CO₂ pressure on the degree of cement carbon⁃ation under geologic CO₂ storage environment［J］. Proceedings of the CSEE，2022，42（9）：3126-3135.

［15］WOOYONG UM， KENTON R A， JUNG， et al. Geochemical alteration of wellbore cement by CO₂ or CO₂ + H₂S reaction during long-term carbon storage［J］. Greenhouse Gases： Science and Technology，2017，7（5）：852-865.

［16］MIAO X X， ZHANG L W， WANG Y， et al. Characterisation of wellbore cement microstructure alteration under geologic carbon storage using X-ray computed micro-tomography： a framework for fast CT image registration and carbonate shell morphology quantification［J］. Cement and Concrete Composites，2020，108：103524.

［17］KUTCHKO B G， STRAZISAR B R， DZOMBAK D A， et al. Degradation of well cement by CO₂ under geologic sequestra⁃tion conditions［J］. Environmental Science and Technology，2007，41（13）：4787-4792.

［18］谢超，王起才，于本田，等 . 纳米 SiO₂-矿渣-水泥复合胶凝材料的抗硫酸盐侵蚀试验［J］. 材料科学与工程学报，2020，38（1）：88-93.

XIE C， WANG Q C， YU B T， et al. Experimental study on sulfate attack resistance of nano SiO₂-slag-cemnet composite cementitious［J］. Materials. Journal of Materials Science and Engineering，2020，38（1）：88-93.

［19］LEDESMA R B， LOPES N F， BACCA K G， et al. Zeolite and fly ash in the composition of oil well cement： evaluation of degradation by CO₂ under geological storage condition［J］. Journal of Petroleum Science and Engineering，2020，185：106656.

［20］BARBARA G K， BRIAN R S， NICOLAS H， et al. CO₂ reaction with hydrated Class H well cement under geologic sequestration conditions： effects of flyash admixtures［J］. Environmental Science and Technology，2009，43（10）：3947-3952.

［21］佟钰，闫海敏，王昭宁，等 . 纳米二氧化硅粒径对水泥砂浆抗压强度及抗氯离子渗透性能的影响［J］. 中国粉体技术，2022，28（5）：11-16.

TONG Y， YAN H， WANG Z N， et al. Influence of particle size of nano-silica on compressive strength and chloride ion penetration resistance of cement mortar［J］. China Powder Science and Technology，2022，28（5）：11-16.

［22］CAO M L， MING X， YIN H， et al. Influence of high temperature on strength， ultrasonic velocity and mass loss of calcium carbonate whisker reinforced cement paste［J］. Composites： Part B， Engineering，2019，163：438-446.

［23］PAUL， CHANDRA S， ROOYEN V， et al. Properties of cement-based composites using nanoparticles： a comprehensive review［J］. Construction and Building Materials，2018，189：1019-1034.

［24］YEON J J， KWANG S Y， TAE S Y. Effect of nano-silica and curing conditions on the reaction rate of class G well cement exposed to geological CO₂-sequestration conditions［J］. Cement and Concrete Research，2018，109：208-216.

［25］PALILU J M A， SOEGIJONO B A， MARBUN B T H C. The role of MgO as swelling cements admixtures under CO₂ attack on API Class-G cement［J］. Journal of Physics： Conference Series，2019，1245（1）：012036.

［26］FASIHNIKOUTALAB M H， POURAKBAR S， BALL R J. The effect of olivine content and curing time on the strength of treated soil in presence of potassium hydroxide［J］. International Journal of Geo-synthetics and Ground Engineering，2017，3（2）：12.

［27］PAUL W， RICHARD J， PAINE K. Olivine as a reactive aggregate in lime mortars［J］. Construction and Building Materials，2019，195：115-126.

［28］ACHANG M， RADONJIC M. Adding olivine micro particles to Portland cement based wellbore cement slurry as a sacrificial material： a quest for the solution in mitigating corrosion of wellbore cement［J］. Cement and Concrete Composites，2021，121：104078.

［29］尹玉明，赵伶玲 . 基于分子动力学的镁橄榄石表面分子吸附与溶解研究［J］. 东南大学学报（自然科学版），2021，51（1）：121-128.

YIN Y M， ZHAO L L. Study on molecules adsorption and dissolution on the surface of forsterite based on molecular dynamics［J］. Journal of Southeast University，2021，51（1）：121-128.

［30］POWER I M， KENWARD P A， DIPPLE G M， et al. Room temperature magnesite precipitation［J］. Crystal Growth and Design，2017，17（11）：5652-5659.

［31］陈凡斌，张浩. 玄武岩纤维对油井水泥石韧性改善的室内研究［J］. 科技视界（学术刊），2015，1：2095-2457.

CHEN F B， ZHANG H. The Development and research status of thermal recovery cement slurry technology［J］. Science and Technology Vision，2015，1：2095-2457.

［32］程小伟，张明亮，杨永胜，等. 玄武岩纤维对铝酸盐水泥石性能的影响［J］. 石油钻采工艺，2016，38（1）：42-47. 

CHENG X W， ZHANG M L， YANG Y S， et al. Effects of basalt fiber on the performance of aluminate cement stone［J］. Oil Drilling and Production Technology，2016，38（1）：42-47.

［33］田辉，郭辛阳，宋雨媛，等 . 基于化学热力学的耐二氧化碳腐蚀水泥水化产物控制［J］. 钻采工艺，2021，44（2）： 86-89. 

TIAN H， GUO X Y， SONG Y Y， et al. Control of hydration products of CO₂ resistant cements based on chemical thermo⁃ dynamics［J］. Drilling and Production Technology，2021，44（2）：86-89.

［34］陆沛青，刘仍光，杨广国，等 . 增强油井水泥石抗二氧化碳腐蚀方法［J］. 材料科学与工程学报，2020，38（4）： 566-570. 

LU P Q， LIU R G， YANG G G， et al. Methods of strengthening anti-CO₂ corrosion of oil well cement stone［J］. Journal of Materials Science and Engineering，2020，38（4）：566-570.

［35］王春迎，杜志明，丛晓民，等. 碱式碳酸镁的热分解研究［J］. 应用化工，2008（6）：657-660. 

WANG C Y， DU Z M， CONG X M， et al. Investigation in thermal decomposition of basic magnesium carbonate［J］. Applied Chemical Industry，2008（6）：657-660.

［36］BREMEN A M， PLOCH T， MHAMDI A， et al. A mechanistic model of direct forsterite carbonation［J］. Chemical Engineering Journal，2021，404：126480