植物胶冲洗液交联机理及其防塌改性研究
发布时间：2018-07-31 10:32
【摘要】：随着我国经济建设发展速度的加快,国家对矿产资源需求量逐渐增大,然而我国大部分的老矿山已出现资源枯竭的现象,未来地质找矿无疑将需要向更深、更复杂地层的方向拓展。因此,岩心钻探工程就会经常钻遇松散破碎、易垮塌等复杂地层。植物胶是一种天然植物高分子聚合物,具有很好的亲水性和可溶性,其胶液经过适当的改性处理后具有良好的粘结性、粘滞性、降失水性、流变性、润滑性、防塌性、携岩能力和减震性能,对孔壁和岩心都可起到很好的保护作用。植物胶冲洗液配制简单,性能稳定,可实现自然降解,具有很好的环保性,集中体现了无固相冲洗液的优良性能。工程实践证明,在松散破碎、易垮塌等复杂地层下使用普通冲洗液进行钻探,易出现钻进效率低、钻孔垮塌、取心率低和施工成本高等问题,而采用植物胶冲洗液往往会收到很好的成效。为了更好地降低植物胶冲洗液使用成本,在植物胶冲洗液中加入交联剂增加其粘度是必不可少的措施,因此弄清楚植物胶冲洗液与交联剂的交联过程,对正确掌握交联剂的使用方法至关重要。本文分别选取了种子类植物胶:瓜尔胶、香豆胶、田菁胶和胡里豆胶,根茎类植物胶:魔芋胶,作为研究对象。采用红外光谱法,分析得出这五种植物胶各自所含的主要成分:瓜尔胶、香豆胶、田菁胶和胡里豆胶的主要成分为半乳甘露聚糖,魔芋胶的主要成分为葡甘露聚糖。结合核磁共振,分析得出瓜尔胶、香豆胶、田菁胶和胡里豆胶半乳甘露聚糖中半乳糖和甘露糖的摩尔比。经过对植物胶交联剂的筛选,确定使用有机硼作为植物胶冲洗液的交联剂。在交联实验中发现选取的五种植物胶与有机硼混合后,属于半乳甘露聚糖类的植物胶可与有机硼发生交联反应,而葡甘露聚糖类的魔芋胶与有机硼不会发生交联反应。在此基础上对比分析了五种植物胶交联前后红外光谱图,证实了由交联实验提出的观点,并分析得出半乳甘露聚糖与有机硼交联,实质上是半乳甘露聚糖中半乳糖支链上的羟基与有机硼释放出来的硼酸根离子发生络合反应。并且进一步采用粘度法分析提出瓜尔胶冲洗液交联体系的交联反应机理:在有机硼加量很少时,植物胶与有机硼混合后,由于溶液中只有少量的硼酸根离子存在,这些硼酸根离子会先与半乳甘露聚糖链上靠近链两端的半乳糖发生络合反应,从而使半乳甘露聚糖分子两端的半乳糖支链通过有机硼而彼此链接起来,形成更长的多糖链,即分子间的交联,随着有机硼缓慢的电离出较多的硼酸根离子,这些硼酸根离子就会与其他支链上的半乳糖发生络合反应,使半乳甘露聚糖分子的形态由不规则的线状发生卷曲和收缩的变化形成线团状,即发生分子内的交联。在提出了这一交联反应机理后,使用粒度分析法分析了交联过程中胶体粒度的变化,而这一变化与提出的交联反应机理正好吻合,从而证实了这一观点。通过对硅酸盐防塌机理和不同模数硅酸钠防塌效果的研究,分析得出模数为3.2模的硅酸钠,其粒径分布最均匀,分布范围最集中,因而提出其防塌性最佳。利用不同模数硅酸钠的植物胶冲洗液浸泡标准岩心,通过观察岩心的坍塌程度可以看出,使用3.2模硅酸钠的植物胶冲洗液岩心的完整度最高,说明防塌效果最好。在确定了植物胶冲洗液体系的组成后,通过正交法分析得出了该冲洗液体系的优化配方为:5‰GH+1‰有机硼+2‰S-PHP+2%Na2O·n Si O2(其中有机硼是有机硼和水按1:2比例的混合液、Na2O·n Si O2为3.2模的水玻璃溶液)。对优化配方综合性能进行评价实验得出,GH植物胶冲洗液防塌体系在各项综合性能上可以满足钻探所需综合性能的要求。通过膨胀量实验、页岩回收率实验以及半透膜微观结构分析得出,GH植物胶冲洗液防塌体系的防塌效果较好,能够满足复杂地层的防塌性能要求。
[Abstract]:With the rapid development of China's economic development, the demand for mineral resources is increasing gradually. However, most of the old mines in our country have been exhausted, and the future geological prospecting will undoubtedly need to be deeper and more complex. Therefore, the core drilling engineering will often encounter loosely broken, collapsing and so on. Plant gum is a kind of natural plant polymer, which has good hydrophilic and soluble properties. After proper modification, the glue has good adhesion, viscosity, water loss, rheology, lubrication, collapse resistance, rock carrying capacity and shock absorption ability, and has a good protective effect on the hole wall and core. The adhesive washing liquid is simple in preparation and stable in performance. It can be degraded naturally and has good environmental protection. It embodies the excellent performance of non solid flushing fluid. Engineering practice has proved that it is easy to use ordinary flushing fluid for drilling in complex strata such as loose, broken and collapsing. It is easy to have low drilling efficiency, hole collapse, low heart rate and high construction cost. In order to reduce the use cost of the plant gum washing liquid, it is necessary to add the crosslinker in the wash liquid of plant glue to increase the viscosity of the plant glue washing solution. Therefore, the crosslinking process of the plant gum washing liquid and the crosslinker is clear, and the use method of the crosslinker is correctly grasped. Seed gum: guar gum, gum bean gum, Sesbania Gum and Huli gum, rhizomatous gum, konjac gum, were selected as the research object. The main components of the five kinds of plant gum were analyzed by infrared spectroscopy. The main components of guar gum, gum gum, Sesbania Gum and Huli gum were half milk Gump. Chitosan, the main component of konjac gum is glucomannan. Combined with nuclear magnetic resonance, the mole ratio of guar gum, gum bean gum, sesbania gum, and mannan gum galactoman is analyzed. After screening the crosslinker of plant gum, the use of organo boron as a crosslinker for plant gum washing liquid is determined. After mixing the five kinds of plant gum and organo boron, the plant gum belonging to the galactooligosaccharide can cross link with organo boron, and the gluconan gluconan gum and organo boron can not react with the organic boron. On this basis, the infrared spectra of the five kinds of plant gum before and after crosslinking are compared and analyzed, which proves that the cross-linking experiment was put forward. The cross-linking reaction between galactoman and organic boron is in essence the complexation reaction between the hydroxyl groups on the galactomannan branching chain and borate ions released from organic boron. Furthermore, the mechanism of the crosslinking reaction of the guar gum flushing fluid is further analyzed by the viscosity method: the addition of organic boron is very little. With the presence of only a small amount of borate ions in the solution, the borate ions will first react with the galactose near the chain at both ends of the galactoman chain, so that the galactose branched chains at both ends of the galactoman molecule are linked to each other to form longer and more, because of the presence of only a small amount of borate ions in the solution. The carbohydrate chain, that is, intermolecular crosslinking, with the slow ionization of borate ions, the borate ions will react with the galactose on other branches and make the morphology of the galactomannan molecules formed from the irregular linear form of curl and contraction to form a linear group, that is, intramolecular crosslinking. After the cross linking reaction mechanism was put forward, the particle size of the colloid in the crosslinking process was analyzed by the particle size analysis method, which coincided with the proposed cross linking reaction mechanism, which confirmed this view. Through the study of the mechanism of the anti collapse of silicate and the effect of different modulus of sodium silicate on the anti collapse effect, the 3.2 modulus of silicon was obtained. Sodium silicate has the most uniform particle size distribution and the most concentrated distribution range, thus the best anti collapse property is put forward. Using the plant glue washing liquid with different modulus of sodium silicate to soak the standard core, by observing the collapse degree of the core, it can be seen that the integrity of the rock core with the 3.2 model sodium silicate is the highest, indicating that the anti collapse effect is the best. After the composition of the plant gum washing liquid system, the optimum formula of the system was obtained by orthogonal analysis: 5 per thousand GH+1 per thousand organic boron +2 per 1000 S-PHP+2%Na2O. N Si O2 (organic boron is a mixture of organic boron and water according to 1:2 ratio, Na2O. N Si O2 is 3.2 mould water glass solution). The comprehensive performance of the optimized formula is evaluated. It is concluded that the anti collapse system of GH plant gum washing liquid can meet the requirements of comprehensive performance of drilling. Through the experiment of expansion, the experiment of shale recovery and the microstructural analysis of the semi permeable membrane, it is concluded that the anti collapse effect of the anti collapse system of GH plant glue washing liquid is better, and it can meet the requirements of the anti collapse performance of the complex strata.
【学位授予单位】：成都理工大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：P634.8
本文编号：2155314
[Abstract]:With the rapid development of China's economic development, the demand for mineral resources is increasing gradually. However, most of the old mines in our country have been exhausted, and the future geological prospecting will undoubtedly need to be deeper and more complex. Therefore, the core drilling engineering will often encounter loosely broken, collapsing and so on. Plant gum is a kind of natural plant polymer, which has good hydrophilic and soluble properties. After proper modification, the glue has good adhesion, viscosity, water loss, rheology, lubrication, collapse resistance, rock carrying capacity and shock absorption ability, and has a good protective effect on the hole wall and core. The adhesive washing liquid is simple in preparation and stable in performance. It can be degraded naturally and has good environmental protection. It embodies the excellent performance of non solid flushing fluid. Engineering practice has proved that it is easy to use ordinary flushing fluid for drilling in complex strata such as loose, broken and collapsing. It is easy to have low drilling efficiency, hole collapse, low heart rate and high construction cost. In order to reduce the use cost of the plant gum washing liquid, it is necessary to add the crosslinker in the wash liquid of plant glue to increase the viscosity of the plant glue washing solution. Therefore, the crosslinking process of the plant gum washing liquid and the crosslinker is clear, and the use method of the crosslinker is correctly grasped. Seed gum: guar gum, gum bean gum, Sesbania Gum and Huli gum, rhizomatous gum, konjac gum, were selected as the research object. The main components of the five kinds of plant gum were analyzed by infrared spectroscopy. The main components of guar gum, gum gum, Sesbania Gum and Huli gum were half milk Gump. Chitosan, the main component of konjac gum is glucomannan. Combined with nuclear magnetic resonance, the mole ratio of guar gum, gum bean gum, sesbania gum, and mannan gum galactoman is analyzed. After screening the crosslinker of plant gum, the use of organo boron as a crosslinker for plant gum washing liquid is determined. After mixing the five kinds of plant gum and organo boron, the plant gum belonging to the galactooligosaccharide can cross link with organo boron, and the gluconan gluconan gum and organo boron can not react with the organic boron. On this basis, the infrared spectra of the five kinds of plant gum before and after crosslinking are compared and analyzed, which proves that the cross-linking experiment was put forward. The cross-linking reaction between galactoman and organic boron is in essence the complexation reaction between the hydroxyl groups on the galactomannan branching chain and borate ions released from organic boron. Furthermore, the mechanism of the crosslinking reaction of the guar gum flushing fluid is further analyzed by the viscosity method: the addition of organic boron is very little. With the presence of only a small amount of borate ions in the solution, the borate ions will first react with the galactose near the chain at both ends of the galactoman chain, so that the galactose branched chains at both ends of the galactoman molecule are linked to each other to form longer and more, because of the presence of only a small amount of borate ions in the solution. The carbohydrate chain, that is, intermolecular crosslinking, with the slow ionization of borate ions, the borate ions will react with the galactose on other branches and make the morphology of the galactomannan molecules formed from the irregular linear form of curl and contraction to form a linear group, that is, intramolecular crosslinking. After the cross linking reaction mechanism was put forward, the particle size of the colloid in the crosslinking process was analyzed by the particle size analysis method, which coincided with the proposed cross linking reaction mechanism, which confirmed this view. Through the study of the mechanism of the anti collapse of silicate and the effect of different modulus of sodium silicate on the anti collapse effect, the 3.2 modulus of silicon was obtained. Sodium silicate has the most uniform particle size distribution and the most concentrated distribution range, thus the best anti collapse property is put forward. Using the plant glue washing liquid with different modulus of sodium silicate to soak the standard core, by observing the collapse degree of the core, it can be seen that the integrity of the rock core with the 3.2 model sodium silicate is the highest, indicating that the anti collapse effect is the best. After the composition of the plant gum washing liquid system, the optimum formula of the system was obtained by orthogonal analysis: 5 per thousand GH+1 per thousand organic boron +2 per 1000 S-PHP+2%Na2O. N Si O2 (organic boron is a mixture of organic boron and water according to 1:2 ratio, Na2O. N Si O2 is 3.2 mould water glass solution). The comprehensive performance of the optimized formula is evaluated. It is concluded that the anti collapse system of GH plant gum washing liquid can meet the requirements of comprehensive performance of drilling. Through the experiment of expansion, the experiment of shale recovery and the microstructural analysis of the semi permeable membrane, it is concluded that the anti collapse effect of the anti collapse system of GH plant glue washing liquid is better, and it can meet the requirements of the anti collapse performance of the complex strata.
【学位授予单位】：成都理工大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：P634.8
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