摘要: |
目前所用的胍胶交联剂在耐温抗剪切性能上较以前有了一定程度提高,但仍不能满足深井、超深井的开采工艺需求。研究以四硼酸钠和氧氯化锆为主要原料,甘露醇和甘露醇/柠檬酸/乳酸混合分别作为配位体,通过合成工艺条件考察,研发出一种与胍胶稠化剂配伍良好的具超高耐温性能的有机硼锆交联剂。采用红外光谱与核磁氢谱对交联剂进行结构表征,表明所制交联剂中存在锆与配体酸上羧基的络合键和硼与有机物的络合键。同时通过实验测定得到压裂液配方:0.35%(w)超级胍胶+2%(w)硫代硫酸钠+0.6%(w)NaOH+0.02%(w)过硫酸铵+0.6%(w)CF-5A助排剂+0.4%(w)有机硼锆交联剂,在170 s-1、180 ℃下剪切2 h,能保持黏度在100 mPa·s左右,该体系耐温性能优异。破胶剂用量0.02%(w)时,7 h完全破胶,破胶液黏度低,残渣量少,表面张力小,破胶性能良好。 |
关键词: 高温胍胶 有机硼锆交联剂 延迟交联 耐温抗剪切性 破胶性能 |
DOI:10.3969/j.issn.1007-3426.2017.02.016 |
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Synthesis and properties of ultra high temperature resistant guanidine cross-linking agent |
Shen Li1, Huang Wenzhang1,2,3, Xiang Lin2, Li Lin2, Deng Lei2, Zhu Limin2, Liu Yangyang3
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1. College of Chemistry and Chemical Engineering, Chongqing University, Chongqing, China;2. College of Chemistry and Chemical Engineering, Chongqing University of Science and Technology, Chongqing, China;3. College of Chemistry and Chemical Engineering, Southwest Petroleum University,Chengdu, Sichuan, China
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Abstract: |
At present, the temperature resistance and shear resistance of guanidine crosslinking agent are improved, but still can not meet the require of deep wells and ultra-deep wells’ development. In this paper, using borax and zirconium oxychloride as main raw material, with mannitol and mannitol/citric acid/lactic acid as ligands respectively, the synthetic process conditions were studied, then a compound-type organic boron-zirconium cross-linking agent with high temperature resistance was developed. The structure of the crosslinker was characterized by IR and 1H NMR. The results showed that the complex bond of zirconium with the carboxylic acid on the ligand acid and the complex bond formed by boron and the organic substance were obtained. At the same time, the formula of fracturing fluid was obtained through experiment:0.35% GHPG+2% Na2S2O3+0.6% NaOH+0.02%(NH4)2S2O8+0.6% CF-5A + 0.4% BZC. And the viscosity was maintained at 100 mPa·s for 2 h at 170 s-1,180 ℃, the crosslink agent system has excellent temperature resistance. The system has good breaking gel performance, the breaker dosage is 0.02%, and complete breaking gel can be achieved in 7 h. The broken glue liquid has low viscosity, less residue, and small surface tension. |
Key words: high temperature guanidine gum organic boron zirconium cross-linking agent delayed cross-linking temperature and shear resistance breaking performance |