植物膠沖洗液交聯(lián)機(jī)理及其防塌改性研究
發(fā)布時(shí)間：2018-07-31 10:32
【摘要】：隨著我國經(jīng)濟(jì)建設(shè)發(fā)展速度的加快,國家對礦產(chǎn)資源需求量逐漸增大,然而我國大部分的老礦山已出現(xiàn)資源枯竭的現(xiàn)象,未來地質(zhì)找礦無疑將需要向更深、更復(fù)雜地層的方向拓展。因此,巖心鉆探工程就會經(jīng)常鉆遇松散破碎、易垮塌等復(fù)雜地層。植物膠是一種天然植物高分子聚合物,具有很好的親水性和可溶性,其膠液經(jīng)過適當(dāng)?shù)母男蕴幚砗缶哂辛己玫恼辰Y(jié)性、粘滯性、降失水性、流變性、潤滑性、防塌性、攜巖能力和減震性能,對孔壁和巖心都可起到很好的保護(hù)作用。植物膠沖洗液配制簡單,性能穩(wěn)定,可實(shí)現(xiàn)自然降解,具有很好的環(huán)保性,集中體現(xiàn)了無固相沖洗液的優(yōu)良性能。工程實(shí)踐證明,在松散破碎、易垮塌等復(fù)雜地層下使用普通沖洗液進(jìn)行鉆探,易出現(xiàn)鉆進(jìn)效率低、鉆孔垮塌、取心率低和施工成本高等問題,而采用植物膠沖洗液往往會收到很好的成效。為了更好地降低植物膠沖洗液使用成本,在植物膠沖洗液中加入交聯(lián)劑增加其粘度是必不可少的措施,因此弄清楚植物膠沖洗液與交聯(lián)劑的交聯(lián)過程,對正確掌握交聯(lián)劑的使用方法至關(guān)重要。本文分別選取了種子類植物膠:瓜爾膠、香豆膠、田菁膠和胡里豆膠,根莖類植物膠:魔芋膠,作為研究對象。采用紅外光譜法,分析得出這五種植物膠各自所含的主要成分:瓜爾膠、香豆膠、田菁膠和胡里豆膠的主要成分為半乳甘露聚糖,魔芋膠的主要成分為葡甘露聚糖。結(jié)合核磁共振,分析得出瓜爾膠、香豆膠、田菁膠和胡里豆膠半乳甘露聚糖中半乳糖和甘露糖的摩爾比。經(jīng)過對植物膠交聯(lián)劑的篩選,確定使用有機(jī)硼作為植物膠沖洗液的交聯(lián)劑。在交聯(lián)實(shí)驗(yàn)中發(fā)現(xiàn)選取的五種植物膠與有機(jī)硼混合后,屬于半乳甘露聚糖類的植物膠可與有機(jī)硼發(fā)生交聯(lián)反應(yīng),而葡甘露聚糖類的魔芋膠與有機(jī)硼不會發(fā)生交聯(lián)反應(yīng)。在此基礎(chǔ)上對比分析了五種植物膠交聯(lián)前后紅外光譜圖,證實(shí)了由交聯(lián)實(shí)驗(yàn)提出的觀點(diǎn),并分析得出半乳甘露聚糖與有機(jī)硼交聯(lián),實(shí)質(zhì)上是半乳甘露聚糖中半乳糖支鏈上的羥基與有機(jī)硼釋放出來的硼酸根離子發(fā)生絡(luò)合反應(yīng)。并且進(jìn)一步采用粘度法分析提出瓜爾膠沖洗液交聯(lián)體系的交聯(lián)反應(yīng)機(jī)理:在有機(jī)硼加量很少時(shí),植物膠與有機(jī)硼混合后,由于溶液中只有少量的硼酸根離子存在,這些硼酸根離子會先與半乳甘露聚糖鏈上靠近鏈兩端的半乳糖發(fā)生絡(luò)合反應(yīng),從而使半乳甘露聚糖分子兩端的半乳糖支鏈通過有機(jī)硼而彼此鏈接起來,形成更長的多糖鏈,即分子間的交聯(lián),隨著有機(jī)硼緩慢的電離出較多的硼酸根離子,這些硼酸根離子就會與其他支鏈上的半乳糖發(fā)生絡(luò)合反應(yīng),使半乳甘露聚糖分子的形態(tài)由不規(guī)則的線狀發(fā)生卷曲和收縮的變化形成線團(tuán)狀,即發(fā)生分子內(nèi)的交聯(lián)。在提出了這一交聯(lián)反應(yīng)機(jī)理后,使用粒度分析法分析了交聯(lián)過程中膠體粒度的變化,而這一變化與提出的交聯(lián)反應(yīng)機(jī)理正好吻合,從而證實(shí)了這一觀點(diǎn)。通過對硅酸鹽防塌機(jī)理和不同模數(shù)硅酸鈉防塌效果的研究,分析得出模數(shù)為3.2模的硅酸鈉,其粒徑分布最均勻,分布范圍最集中,因而提出其防塌性最佳。利用不同模數(shù)硅酸鈉的植物膠沖洗液浸泡標(biāo)準(zhǔn)巖心,通過觀察巖心的坍塌程度可以看出,使用3.2模硅酸鈉的植物膠沖洗液巖心的完整度最高,說明防塌效果最好。在確定了植物膠沖洗液體系的組成后,通過正交法分析得出了該沖洗液體系的優(yōu)化配方為:5‰GH+1‰有機(jī)硼+2‰S-PHP+2%Na2O·n Si O2(其中有機(jī)硼是有機(jī)硼和水按1:2比例的混合液、Na2O·n Si O2為3.2模的水玻璃溶液)。對優(yōu)化配方綜合性能進(jìn)行評價(jià)實(shí)驗(yàn)得出,GH植物膠沖洗液防塌體系在各項(xiàng)綜合性能上可以滿足鉆探所需綜合性能的要求。通過膨脹量實(shí)驗(yàn)、頁巖回收率實(shí)驗(yàn)以及半透膜微觀結(jié)構(gòu)分析得出,GH植物膠沖洗液防塌體系的防塌效果較好,能夠滿足復(fù)雜地層的防塌性能要求。
[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.
【學(xué)位授予單位】：成都理工大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2015
【分類號】：P634.8
本文編號：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.
【學(xué)位授予單位】：成都理工大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2015
【分類號】：P634.8
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2 顏鵬;陳禮儀;張川;張濤;;植物膠沖洗液防塌改性的研究[J];西部探礦工程;2015年01期
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，本文編號：2155314
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