CN112239658B - A kind of fluid loss reducer for drilling fluid based on nanofiber-chitosan composite and preparation method thereof - Google Patents
A kind of fluid loss reducer for drilling fluid based on nanofiber-chitosan composite and preparation method thereofDownload PDFInfo
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Abstract
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Description
Translated fromChinese技术领域technical field
本发明涉及一种石油勘探钻井过程中用到的钻井液产品，特别是涉及到为了减少钻井液绿叶进入地层从引发井壁失稳和储层污染的降滤失剂。The invention relates to a drilling fluid product used in the drilling process of petroleum exploration, in particular to a fluid loss control agent for reducing the green leaves of the drilling fluid entering the stratum and causing wellbore instability and reservoir pollution.
背景技术Background technique
钻井过程中，会钻遇复杂地层，在该过程中，钻井液会和地层接触，在接触瞬间，钻井液滤液就会自发进入地层，如果进入的滤液过多，就有可能引发地层失稳，从而导致扩径或缩径等事故发生，严重时有可能导致井壁失稳和卡钻等复杂事故。因此，在钻井行业，对钻井液在地层中的失水是有严格要求的。为了减少钻井液滤液进入地层孔隙，一般需要在钻井液中加入降滤失剂，目前，常用的降滤失剂有共矿物类(以黏土及其改性物为主)、天然有机物及其衍生物(如磺化褐煤、改性淀粉、羧甲基纤维素等)、多元共聚物(以丙烯酰胺共聚物为主)等，随着环保的日益严格，目前，主要降滤失剂以天然聚合物及其衍生物为主，目前，最为成熟的是改性淀粉，包括AM-AA-淀粉接枝共聚物、AM-AMPS-淀粉共聚物、AMPS-DMDAAC-AM-淀粉共聚物、阳离子化改性淀粉、醚化淀粉、苯基阳离子淀粉等等。但上述淀粉改性物的抗温性都有一定的提高，但都在150℃以内，目前没有关于壳聚糖及其衍生物在钻井液降滤失剂中应用的报道。During the drilling process, complex formations will be encountered. During this process, the drilling fluid will contact the formation. At the moment of contact, the drilling fluid filtrate will spontaneously enter the formation. If too much filtrate enters, it may cause formation instability. As a result, accidents such as diameter expansion or diameter reduction occur, and in severe cases, it may lead to complex accidents such as wellbore instability and pipe sticking. Therefore, in the drilling industry, there are strict requirements for the water loss of the drilling fluid in the formation. In order to reduce the penetration of drilling fluid filtrate into the formation pores, it is generally necessary to add fluid loss control agents to the drilling fluid. At present, commonly used fluid loss control agents include co-minerals (mainly clay and its modifications), natural organic compounds and their derivatives (such as sulfonated lignite, modified starch, carboxymethyl cellulose, etc.), multi-copolymers (mainly acrylamide copolymers), etc., with the increasingly strict environmental protection, at present, the main fluid loss reducer is natural polymer At present, the most mature is modified starch, including AM-AA-starch graft copolymer, AM-AMPS-starch copolymer, AMPS-DMDAAC-AM-starch copolymer, cationic modified starch Sexual starch, etherified starch, phenyl cationic starch, etc. However, the temperature resistance of the above-mentioned starch modified products has been improved to a certain extent, but they are all within 150 ° C. There is no report on the application of chitosan and its derivatives in drilling fluid fluid loss control agents.
壳聚糖又称脱乙酰甲壳素，其主要化学成分为聚葡萄糖胺(1-4)-2-氨基-B-D葡萄糖((C6H11NO4)N)，可用于增稠剂及被膜剂，被广泛用于医药、化工、化妆品、食品等领域。壳聚糖带分子中含有羟基和氨基，具有较强的化学活性，可与氯乙酸反应生成羧甲基衍生物。通过羧甲基化后，其在水中的溶解度及抗温能力得到进一步提高，但这种提高比较有限，在120℃条件下就可能发生降解。Chitosan, also known as chitosan, its main chemical composition is polyglucosamine (1-4)-2-amino-BD glucose ((C6 H11 NO4 )N), which can be used as a thickener and coating agent , are widely used in medicine, chemical industry, cosmetics, food and other fields. The chitosan tape molecule contains hydroxyl and amino groups, which have strong chemical activity and can react with chloroacetic acid to form carboxymethyl derivatives. After carboxymethylation, its solubility in water and temperature resistance are further improved, but this improvement is relatively limited, and degradation may occur at 120 °C.
纳米纤维是一种新型的纤维材料，一般采用熔喷、静电纺丝与双组份纺丝工艺来制备纳米纤维。网络状纳米纤维素具有纤细纤维，具有一定的剪切稀释性和触变性，能提高其他材料的抗温能力。纳米纤维在石油行业还没有开展正式应用。最近，人们开始研究纤维素纳米晶在钻井液中的应用，王建全等人(CN201610274343.6)采用纳米纤维素晶须和其他纤维素组合，形成了一种钻井液降滤失剂。但这种降滤失剂只涉及到纳米纤维和其他纤维素产品的相互作用，及其在降滤失方面的作用，没有涉及到甘蔗方法制备纳米纤维的方法，没有涉及到纳米纤维和羧甲基壳聚糖之间的协同作用。本发明通过采用甘蔗残渣的烘干、粉碎、提纯、透析、阳离子化，在此基础上与羧甲基壳聚糖相结合，形成纳米纤维-壳聚糖复合物，而纳米二氧化硅的存在可以增强其抗温和充填纳米孔隙能力，低分子醇的存在可以促进纳米复合物在水溶液分散及其在泥饼微纳米孔隙中充填作用，从而提高其降滤失作用。三者具有一定的协同作用，纳米纤维可以提高羧甲基壳聚糖在溶液中的伸展性和切力；纳米颗粒的布朗运动和大比表面，可以提高聚合物及纳米纤维的抗温作用；而纳米纤维和羧甲基壳聚糖形成的网络结构，又能使纳米颗粒得到有效保护，使其不至于在高温条件下与其他处理剂及黏土相结合，从而最大程度发挥其作用。在常温条件下，2.0wt％纳米纤维-壳聚糖复合物加入基浆后，滤失量可从16.5mL降低至5mL，经过150℃/16h老化后，其滤失量仍能保持在6.2mL。因此，该处理剂具有较强的降滤失和抗温作用，该处理剂无毒，可完全生物降解。Nanofiber is a new type of fiber material, which is generally prepared by melt blowing, electrospinning and bicomponent spinning processes. The networked nanocellulose has fine fibers, has certain shear thinning and thixotropy, and can improve the temperature resistance of other materials. Nanofibers have not yet been formally used in the petroleum industry. Recently, people have begun to study the application of cellulose nanocrystals in drilling fluids. Wang Jianquan et al. (CN201610274343.6) used nanocellulose whiskers in combination with other cellulose to form a fluid loss control agent for drilling fluids. However, this fluid loss control agent only involves the interaction of nanofibers and other cellulose products, and its effect on fluid loss reduction. It does not involve the method of preparing nanofibers by the sugarcane method, nor does it involve nanofibers and carboxymethyl. synergy between chitosan-based chitosan. The present invention adopts the drying, pulverizing, purifying, dialysis and cationization of sugarcane residue, and on this basis, combines with carboxymethyl chitosan to form nanofiber-chitosan composite, and the existence of nano-silica It can enhance its temperature resistance and ability to fill nanopores, and the presence of low molecular alcohol can promote the dispersion of nanocomposites in aqueous solution and their filling in the micro-nanopores of mud cakes, thereby improving their filtration reduction effect. The three have a certain synergistic effect. Nanofibers can improve the extensibility and shear force of carboxymethyl chitosan in solution; the Brownian motion and large specific surface of nanoparticles can improve the temperature resistance of polymers and nanofibers; The network structure formed by nanofibers and carboxymethyl chitosan can effectively protect the nanoparticles from combining with other treatment agents and clay under high temperature conditions, so as to maximize their effects. Under normal temperature conditions, after adding 2.0wt% nanofiber-chitosan composite into the base slurry, the filtration loss can be reduced from 16.5mL to 5mL, and after aging at 150℃/16h, the filtration loss can still be maintained at 6.2mL . Therefore, the treatment agent has a strong effect of reducing fluid loss and temperature resistance, and the treatment agent is non-toxic and can be completely biodegraded.
发明内容SUMMARY OF THE INVENTION
本发明的目的是为了解决当前水基钻井液用多元共聚物抗高温降滤失剂存在的环境兼容性差的特点，提出了可降解的纳米纤维-壳聚糖复合物方法，同时辅以纳米二氧化硅和低分子醇，通过协同作用，可提高钻井液降滤失作用和抗温能力。该方法简单、可靠，所制得的纳米纤维-壳聚糖复合物在常温条件下，2.0wt％纳米纤维-壳聚糖复合物加入基浆后从16.5mL降低至5mL，经过150℃/16h老化后，其滤失量仍能保持在6.2mL。该处理剂对环境无任何不良影响，急性毒性EC50＞60000。The purpose of the present invention is to solve the characteristics of poor environmental compatibility of the current multi-copolymer anti-high temperature fluid loss control agent for water-based drilling fluids, and proposes a degradable nanofiber-chitosan composite method, supplemented by nanometer two Silica and low-molecular-weight alcohol, through synergistic action, can improve the fluid loss reduction effect and temperature resistance of drilling fluid. The method is simple and reliable, and the prepared nanofiber-chitosan composite is reduced from 16.5 mL to 5 mL after adding 2.0wt% nanofiber-chitosan composite to the base slurry under normal temperature conditions, and after 150°C/16h After aging, its filtration loss can still be maintained at 6.2mL. The treatment agent has no adverse effect on the environment, and the acute toxicity EC50 is >60000.
本发明采用技术方案如下：The present invention adopts the technical scheme as follows:
一种基于纳米纤维-壳聚糖复合物，按质量百分比计算如下组分含量：阳离子纳米纤维素42～46.5％、分散剂5.0～7.0％、羧甲基壳聚糖26～31％、纳米二氧化硅12.5～14％、5～11％低分子醇。A composite based on nanofiber-chitosan, the following components are calculated by mass percentage: cationic nanocellulose 42-46.5%, dispersant 5.0-7.0%, carboxymethyl chitosan 26-31%, nano-di Silica 12.5-14%, 5-11% low molecular alcohol.
本发明技术方案所述的分散剂为二辛基磺化琥珀酸钠、三辛基磺化琥珀酸钠、二辛基磺化丁二酸钠中的一种或任意两种组合。The dispersant described in the technical solution of the present invention is one or any combination of two of sodium dioctyl sulfosuccinate, sodium trioctyl sulfosuccinate, and sodium dioctyl sulfosuccinate.
本发明技术方案所述的纳米二氧化硅粒径优选为10～50nm，进一步优选的纳米二氧化硅为SJ-801、SJ-1500、SJ-2500、SJ-3500中的一种或任意两种组合，该产品为潍坊三佳化工有限公司生产。The particle size of nano-silica described in the technical solution of the present invention is preferably 10-50 nm, and further preferred nano-silica is one or any two of SJ-801, SJ-1500, SJ-2500 and SJ-3500 Combination, this product is produced by Weifang Sanjia Chemical Co., Ltd.
本发明技术方案所述的低分子醇为乙二醇、丙醇、丙三醇的一种或任意两种组合。The low-molecular-weight alcohol described in the technical solution of the present invention is one or any combination of two of ethylene glycol, propanol and glycerol.
本发明具体的制备方法，包括下面的步骤：The concrete preparation method of the present invention comprises the following steps:
1、甘蔗渣的预处理1. Pretreatment of bagasse
(1)将甘蔗渣用去离子水清洗干净，晾干，用压榨机压制，连续数次，将其中所有糖分榨出后，用去离子水清洗干净，放入到烘箱中，在80℃±5℃条件下干燥5h，取出；(1) Wash the bagasse with deionized water, dry it, press it with a press for several times, squeeze out all the sugar in it, wash it with deionized water, and put it in an oven at 80°C ± Dry at 5°C for 5h, take out;
(2)用粉碎机将干燥好的甘蔗渣粉碎，用标准检验筛检验，粉碎至800目～1000目，待用。(2) Pulverize the dried bagasse with a pulverizer, check with a standard inspection sieve, pulverize to 800-1000 mesh, and set aside.
其中，所用的甘蔗渣是属于糖蔗榨汁之后的残渣，糖蔗主要产于广西、广东等亚热带地区，主要成分为维生素、脂肪、蛋白质有机酸、钙、铁等物质。Among them, the used bagasse is the residue after the sugar cane is squeezed. The sugar cane is mainly produced in subtropical regions such as Guangxi and Guangdong, and the main components are vitamins, fats, protein organic acids, calcium, iron and other substances.
2、阳离子纳米纤维悬浮液的制备2. Preparation of Cationic Nanofiber Suspension
(1)将200～300g的冰醋酸(浓度98％)和100～200g次氯酸加入到2000mL三口圆底烧瓶中，缓慢加入去离子水900mL，边滴加边搅拌(转速300rpm)，温度调至30℃，直至完全溶解；(1) Add 200-300g of glacial acetic acid (98% concentration) and 100-200g of hypochlorous acid into a 2000mL three-necked round-bottomed flask, slowly add 900mL of deionized water, add dropwise while stirring (rotation speed 300rpm), adjust the temperature to 30°C until completely dissolved;
(2)在上述的三口烧瓶中分批加入400～600g预处理好的甘蔗渣，以300rpm低速搅拌1h，加完后，温度升高至50℃，将搅拌速度提至2000rpm，搅拌2h，得到乳白色悬浮液；(2) Add 400～600g of pretreated bagasse in the above-mentioned three-necked flask in batches, stir at a low speed of 300rpm for 1h, after adding, the temperature is raised to 50°C, the stirring speed is increased to 2000rpm, and stirred for 2h to obtain milky white suspension;
(3)将前面的乳白色悬浮液的pH调节至4.0～5.0，加入20～30g季铵盐阳离子表面活性剂，继续反应1～2h。将体系转入到5000mL大塑料杯中，加入过量的去离子水，终止反应；(3) The pH of the preceding milky white suspension is adjusted to 4.0-5.0, 20-30 g of quaternary ammonium salt cationic surfactant is added, and the reaction is continued for 1-2 hours. Transfer the system to a 5000mL large plastic cup, add excess deionized water to terminate the reaction;
(4)将上述分散体系分批转至离心机中，在20000rpm下离心20min，沉淀，将上层清液倒出，加入去离子水，再次高速离心，直至上层清液澄清为止，经多次离心，直至体系pH5.0～6.0为止；(4) transfer the above-mentioned dispersion system to a centrifuge in batches, centrifuge at 20000rpm for 20min, precipitate, pour out the supernatant, add deionized water, and centrifuge again at high speed until the supernatant is clarified, after repeated centrifugation , until the pH of the system is 5.0 to 6.0;
(5)将上述的分散体系分批通过再生纤维素透析袋(孔径20nm)在去离子水中透析，透析时间6～9天，直至体系pH6.0～8.0为止，将透析袋中分散体系低温旋转蒸发浓缩至浓度为30％为止，转入到密封瓶中密封待用，即可得到阳离子纳米纤维悬浮液。(5) Dialyze the above dispersion system in batches through regenerated cellulose dialysis bags (pore size 20nm) in deionized water, the dialysis time is 6 to 9 days, until the pH of the system is 6.0 to 8.0, and the dispersion system in the dialysis bag is rotated at low temperature Evaporate and concentrate until the concentration is 30%, transfer it into a sealed bottle and seal it for use, and then the cationic nanofiber suspension can be obtained.
其中，所用的季铵盐阳离子表面活性剂为十六烷基三甲基溴化铵、十六烷基三甲基氯化铵、十二烷基三甲基溴化铵、十二烷基三甲基氯化铵中的一种或任意两种组合。Wherein, the used quaternary ammonium salt cationic surfactant is cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, dodecyl trimethyl ammonium bromide, dodecyl trimethyl ammonium bromide, One or any combination of Methyl Ammonium Chloride.
3、羧甲基壳聚糖的制备3. Preparation of carboxymethyl chitosan
(1)在2000mL三口圆底烧瓶中加入1000mL的去离子水，分批加入50～80g壳聚糖粉末，缓慢依次滴加60～90g冰醋酸(浓度98％)和100～120g，边加入边搅拌(转速500rpm)，温度控制在70～80℃，反应6～8h，反应结束，用HC1溶液将体系调节pH调节至6.0～7.0；(1) Add 1000mL of deionized water to a 2000mL three-necked round-bottomed flask, add 50-80g chitosan powder in batches, slowly dropwise add 60-90g glacial acetic acid (98% concentration) and 100-120g, while adding Stir (rotation speed 500rpm), control the temperature at 70～80°C, react for 6～8h, when the reaction ends, adjust the pH of the system to 6.0～7.0 with HCl solution;
(2)静置6-7天，取下层沉淀，用去离子水重新溶解、过滤，分批通过再生纤维素透析袋(孔径20nm)在去离子水中透析5天，将透析袋中分散体系取出，冷却至室温后干燥、粉碎、过筛，即可得到羧甲基壳聚糖。(2) Let stand for 6-7 days, remove the lower layer of precipitate, redissolve and filter with deionized water, dialyze in deionized water in batches through a regenerated cellulose dialysis bag (pore size 20nm) for 5 days, and take out the dispersion system in the dialysis bag , cooled to room temperature, dried, crushed and sieved to obtain carboxymethyl chitosan.
其中，所用壳聚糖粉末属于甲壳素脱N-乙酰基的产物，N-脱乙酰度＞90％，相对分子质量约为3×105～7×105，运动粘度0.25～0.65Pa·s。Among them, the chitosan powder used is the product of de-N-acetylation of chitin, the degree of N-deacetylation is more than 90%, the relative molecular mass is about 3×105 ～7×105 , and the kinematic viscosity is 0.25～0.65Pa·s .
4、基于纳米纤维-壳聚糖粉复合物的钻井液用降滤失剂的制备4. Preparation of fluid loss control agent for drilling fluid based on nanofiber-chitosan powder composite
(1)在高压均质器中加入去离子水2000mL，分批加入阳离子纳米纤维悬浮液600～800g，在20000rpm条件下均质化1～2h，加入20～40g分散剂，在500rpm条件下均质化20min；(1) Add 2000 mL of deionized water to the high-pressure homogenizer, add 600-800 g of cationic nanofiber suspension in batches, homogenize for 1-2 hours at 20,000 rpm, add 20-40 g of dispersant, and homogenize at 500 rpm. Qualitative 20min;
(2)在上述的均质器中缓慢加入120～150g羧甲基壳聚糖，在800rpm条件下均质化2h；(2) Slowly add 120-150g carboxymethyl chitosan into the above-mentioned homogenizer, and homogenize for 2h under the condition of 800rpm;
(3)将转速提高至15000rpm，依次缓慢加入50～80g纳米二氧化硅和20～60g低分子醇，均质化4h；(3) increase the rotational speed to 15000rpm, slowly add 50-80g nano-silica and 20-60g low molecular alcohol in turn, and homogenize for 4h;
(4)将上述产物置于烘箱中，在80±5℃烘干，并用粉碎机将干燥好的产物粉碎，用标准检验筛筛分，粉碎至800～1000目，即可得到基于纳米纤维-壳聚糖复合物的钻井液用降滤失剂。(4) placing the above product in an oven, drying at 80±5°C, and pulverizing the dried product with a pulverizer, sieving it with a standard inspection sieve, and pulverizing to 800-1000 mesh, to obtain a nanofiber-based nanofiber- Fluid loss control agent for drilling fluid of chitosan complex.
与现有技术相比，本发明效果更为突出：(1)本发明的纳米纤维-壳聚糖复合物，通过氨基和羟基的氢键相互作用，制备出纳米复合物，通过季铵盐表面活性剂反应，生成阳离子纳米纤维，提高其降滤失和快速封堵微小孔隙的能力；(2)球状纳米颗粒和低分子醇的存在，促进聚合物在水中分散及快速进入泥饼纳微孔隙中，从而提高了其抗温作用和降滤失作用；(3)2.0wt％纳米纤维-壳聚糖复合物加入基浆后从16.5mL降低至5mL，经过150℃/16h老化后，其滤失量仍能保持在6.2mL。Compared with the prior art, the effect of the present invention is more prominent: (1) the nanofiber-chitosan composite of the present invention prepares the nanocomposite through the hydrogen bond interaction between the amino group and the hydroxyl group, and passes the surface of the quaternary ammonium salt. The active agent reacts to form cationic nanofibers, which improve their ability to reduce filtration loss and quickly block tiny pores; (2) the presence of spherical nanoparticles and low-molecular-weight alcohols promotes polymer dispersion in water and rapid entry into the nano-pores of mud cakes (3) After adding 2.0wt% nanofiber-chitosan composite into the base slurry, it was reduced from 16.5mL to 5mL, and after aging at 150℃/16h, its filtration Loss can still be maintained at 6.2mL.
下面结合实施例进一步阐述本发明。The present invention is further described below in conjunction with the examples.
附图说明Description of drawings
图1是加入纳米纤维-壳聚糖复合物降滤失剂后基浆的滤失量变化情况Fig. 1 is the change of the filtrate of the base slurry after adding the nanofiber-chitosan composite filtrate reducer
具体实施例specific embodiment
实施例1：Example 1:
(1)将200g的冰醋酸(浓度98％)和100～200g次氯酸加入到2000mL三口圆底烧瓶中，缓慢加入去离子水900mL，边滴加边搅拌(转速300rpm)，温度调至30℃，直至完全溶解；在上述的三口烧瓶中分批加入400g预处理好的甘蔗渣，以300rpm低速搅拌1h，加完后，温度升高至50℃，将搅拌速度提至2000rpm，搅拌2h，得到乳白色悬浮液；将前面的乳白色悬浮液的pH调节至4.0～5.0，加入20g十六烷基三甲基溴化铵，继续反应1h。将体系转入到5000mL大塑料杯中，加入过量的去离子水，终止反应；将上述分散体系分批转至离心机中，在20000rpm下离心20min，沉淀，将上层清液倒出，加入去离子水，再次高速离心，直至上层清液澄清为止，经多次离心，直至体系pH5.0～6.0为止；将上述的分散体系分批通过再生纤维素透析袋(孔径20nm)在去离子水中透析，透析时间6天，直至体系pH6.0～8.0为止，将透析袋中分散体系低温旋转蒸发浓缩至浓度为30％为止，转入到密封瓶中密封待用，即可得到阳离子纳米纤维悬浮液；(2)在2000mL三口圆底烧瓶中加入1000mL的去离子水，分批加入50g壳聚糖粉末，缓慢依次滴加60g冰醋酸(浓度98％)和100g，边加入边搅拌(转速500rpm)，温度控制在70℃，反应6h，反应结束，用HC1溶液将体系调节pH调节至6.0～7.0；静置6天，取下层沉淀，用去离子水重新溶解、过滤，分批通过再生纤维素透析袋(孔径20nm)在去离子水中透析5天，将透析袋中分散体系取出，冷却至室温后干燥、粉碎、过筛，即可得到羧甲基壳聚糖；(3)在高压均质器中加入去离子水2000mL，分批加入阳离子纳米纤维悬浮液600g，在20000rpm条件下均质化1h，加入20g二辛基磺化琥珀酸钠，在500rpm条件下均质化20min；在上述的均质器中缓慢加入120g羧甲基壳聚糖，在800rpm条件下均质化2h；将转速提高至15000rpm，依次缓慢加入50g纳米二氧化硅SJ-801和20g乙二醇，均质化4h；将上述产物置于烘箱中，在80±5℃烘干，并用粉碎机将干燥好的产物粉碎，用标准检验筛筛分，粉碎至800～1000目，即可得到基于纳米纤维-壳聚糖复合物的钻井液用降滤失剂。(1) Add 200g of glacial acetic acid (concentration 98%) and 100～200g of hypochlorous acid into a 2000mL three-necked round-bottomed flask, slowly add 900mL of deionized water, add dropwise while stirring (rotating speed 300rpm), and adjust the temperature to 30 ℃ until completely dissolved; add 400 g of pretreated bagasse in batches to the above three-necked flask, stir at a low speed of 300 rpm for 1 h, after adding, the temperature is raised to 50 ° C, the stirring speed is increased to 2000 rpm, and stirred for 2 h, A milky white suspension was obtained; the pH of the preceding milky white suspension was adjusted to 4.0-5.0, 20 g of cetyltrimethylammonium bromide was added, and the reaction was continued for 1 h. Transfer the system to a 5000mL large plastic cup, add excess deionized water to terminate the reaction; transfer the above dispersion system to a centrifuge in batches, centrifuge at 20000rpm for 20min, precipitate, pour out the supernatant, add Ionized water, centrifuged at high speed again until the supernatant was clear, and centrifuged for several times until the pH of the system was 5.0 to 6.0; the above dispersion system was dialyzed in deionized water through regenerated cellulose dialysis bags (pore size 20nm) in batches , the dialysis time is 6 days, until the pH of the system is 6.0 ~ 8.0, the dispersion system in the dialysis bag is concentrated to a concentration of 30% by low-temperature rotary evaporation, transferred to a sealed bottle and sealed for use, and the cationic nanofiber suspension can be obtained. (2) Add 1000mL of deionized water in a 2000mL three-necked round-bottomed flask, add 50g of chitosan powder in batches, slowly dropwise add 60g of glacial acetic acid (98% concentration) and 100g, and stir while adding (rotating speed 500rpm) , the temperature was controlled at 70°C, the reaction was completed for 6 hours, and the pH of the system was adjusted to 6.0-7.0 with HCl solution; after standing for 6 days, the lower layer of precipitate was removed, redissolved with deionized water, filtered, and passed through regenerated cellulose in batches The dialysis bag (pore size 20nm) was dialyzed in deionized water for 5 days, the dispersion system in the dialysis bag was taken out, cooled to room temperature, dried, pulverized and sieved to obtain carboxymethyl chitosan; (3) Homogenized under high pressure Add 2000 mL of deionized water to the vessel, add 600 g of cationic nanofiber suspension in batches, homogenize for 1 h at 20,000 rpm, add 20 g of sodium dioctyl sulfosuccinate, and homogenize for 20 min at 500 rpm; Slowly add 120g of carboxymethyl chitosan to the homogenizer, and homogenize at 800rpm for 2h; increase the speed to 15000rpm, slowly add 50g of nano-silica SJ-801 and 20g of ethylene glycol in sequence, and homogenize for 4h The above product is placed in an oven, dried at 80±5°C, and pulverized with a pulverizer, sieved with a standard inspection sieve, and pulverized to 800-1000 mesh, to obtain a nanofiber-chitosan based Fluid loss reducer for drilling fluids of sugar complexes.
实施例2：Example 2:
(1)将250g的冰醋酸(浓度98％)和150g次氯酸加入到2000mL三口圆底烧瓶中，缓慢加入去离子水900mL，边滴加边搅拌(转速300rpm)，温度调至30℃，直至完全溶解；在上述的三口烧瓶中分批加入500g预处理好的甘蔗渣，以300rpm低速搅拌1h，加完后，温度升高至50℃，将搅拌速度提至2000rpm，搅拌2h，得到乳白色悬浮液；将前面的乳白色悬浮液的pH调节至4.0～5.0，加入25g十二烷基三甲基溴化铵，继续反应1.5h。将体系转入到5000mL大塑料杯中，加入过量的去离子水，终止反应；将上述分散体系分批转至离心机中，在20000rpm下离心20min，沉淀，将上层清液倒出，加入去离子水，再次高速离心，直至上层清液澄清为止，经多次离心，直至体系pH5.0～6.0为止；将上述的分散体系分批通过再生纤维素透析袋(孔径20nm)在去离子水中透析，透析时间8天，直至体系pH6.0～8.0为止，将透析袋中分散体系低温旋转蒸发浓缩至浓度为30％为止，转入到密封瓶中密封待用，即可得到阳离子纳米纤维悬浮液；(2)在2000mL三口圆底烧瓶中加入1000mL的去离子水，分批加入70g壳聚糖粉末，缓慢依次滴加80g冰醋酸(浓度98％)和110g，边加入边搅拌(转速500rpm)，温度控制在75℃，反应7h，反应结束，用HC1溶液将体系调节pH调节至6.0～7.0；静置7天，取下层沉淀，用去离子水重新溶解、过滤，分批通过再生纤维素透析袋(孔径20nm)在去离子水中透析5天，将透析袋中分散体系取出，冷却至室温后干燥、粉碎、过筛，即可得到羧甲基壳聚糖；(3)在高压均质器中加入去离子水2000mL，分批加入阳离子纳米纤维悬浮液700g，在20000rpm条件下均质化1.5h，加入30g三辛基磺化琥珀酸钠，在500rpm条件下均质化20min；在上述的均质器中缓慢加入130g羧甲基壳聚糖，在800rpm条件下均质化2h；将转速提高至15000rpm，依次缓慢加入70g纳米二氧化硅SJ-2500和50g丙醇，均质化4h；将上述产物置于烘箱中，在80±5℃烘干，并用粉碎机将干燥好的产物粉碎，用标准检验筛筛分，粉碎至800～1000目，即可得到基于纳米纤维-壳聚糖复合物的钻井液用降滤失剂。(1) 250g of glacial acetic acid (concentration 98%) and 150g of hypochlorous acid were added to a 2000mL three-necked round-bottomed flask, and 900mL of deionized water was slowly added, while stirring (rotating speed 300rpm) while dropping, and the temperature was adjusted to 30°C, until completely dissolved; add 500 g of pretreated bagasse in batches to the above-mentioned three-necked flask, stir at a low speed of 300 rpm for 1 h, after adding, the temperature is raised to 50 ° C, the stirring speed is increased to 2000 rpm, and stirred for 2 h to obtain a milky white Suspension; adjust the pH of the preceding milky white suspension to 4.0-5.0, add 25 g of dodecyl trimethyl ammonium bromide, and continue the reaction for 1.5 h. Transfer the system to a 5000mL large plastic cup, add excess deionized water to terminate the reaction; transfer the above dispersion system to a centrifuge in batches, centrifuge at 20000rpm for 20min, precipitate, pour out the supernatant, add Ionized water, centrifuged at high speed again until the supernatant was clear, and centrifuged for several times until the pH of the system was 5.0 to 6.0; the above dispersion system was dialyzed in deionized water through regenerated cellulose dialysis bags (pore size 20nm) in batches , the dialysis time is 8 days, until the pH of the system is 6.0 ~ 8.0, the dispersion system in the dialysis bag is concentrated to a concentration of 30% by low-temperature rotary evaporation, transferred to a sealed bottle and sealed for use, and the cationic nanofiber suspension can be obtained. (2) Add 1000mL of deionized water in a 2000mL three-necked round-bottomed flask, add 70g of chitosan powder in batches, slowly dropwise add 80g of glacial acetic acid (98% concentration) and 110g, and stir while adding (rotating speed 500rpm) , the temperature was controlled at 75°C, and the reaction was completed for 7 hours. After the reaction was completed, the pH of the system was adjusted to 6.0-7.0 with HCl solution; after standing for 7 days, the lower layer of precipitate was removed, redissolved with deionized water, filtered, and passed through regenerated cellulose in batches. The dialysis bag (pore size 20nm) was dialyzed in deionized water for 5 days, the dispersion system in the dialysis bag was taken out, cooled to room temperature, dried, pulverized and sieved to obtain carboxymethyl chitosan; (3) Homogenized under high pressure Add 2000 mL of deionized water to the vessel, add 700 g of cationic nanofiber suspension in batches, homogenize for 1.5 h at 20,000 rpm, add 30 g of sodium trioctyl sulfosuccinate, and homogenize for 20 min at 500 rpm; Slowly add 130g of carboxymethyl chitosan to the homogenizer of 1, and homogenize at 800rpm for 2h; increase the rotation speed to 15000rpm, slowly add 70g of nano-silica SJ-2500 and 50g of propanol in turn, and homogenize for 4h The above product is placed in an oven, dried at 80±5°C, and pulverized with a pulverizer, sieved with a standard inspection sieve, and pulverized to 800-1000 mesh, to obtain a nanofiber-chitosan based Fluid loss reducer for drilling fluids of sugar complexes.
实施例3：Example 3:
(1)将300g的冰醋酸(浓度98％)和200g次氯酸加入到2000mL三口圆底烧瓶中，缓慢加入去离子水900mL，边滴加边搅拌(转速300rpm)，温度调至30℃，直至完全溶解；在上述的三口烧瓶中分批加入600g预处理好的甘蔗渣，以300rpm低速搅拌1h，加完后，温度升高至50℃，将搅拌速度提至2000rpm，搅拌2h，得到乳白色悬浮液；将前面的乳白色悬浮液的pH调节至4.0～5.0，加入30g十二烷基三甲基氯化铵，继续反应2h。将体系转入到5000mL大塑料杯中，加入过量的去离子水，终止反应；将上述分散体系分批转至离心机中，在20000rpm下离心20min，沉淀，将上层清液倒出，加入去离子水，再次高速离心，直至上层清液澄清为止，经多次离心，直至体系pH5.0～6.0为止；将上述的分散体系分批通过再生纤维素透析袋(孔径20nm)在去离子水中透析，透析时间9天，直至体系pH6.0～8.0为止，将透析袋中分散体系低温旋转蒸发浓缩至浓度为30％为止，转入到密封瓶中密封待用，即可得到阳离子纳米纤维悬浮液；(2)在2000mL三口圆底烧瓶中加入1000mL的去离子水，分批加入80g壳聚糖粉末，缓慢依次滴加90g冰醋酸(浓度98％)和120g，边加入边搅拌(转速500rpm)，温度控制在80℃，反应8h，反应结束，用HC1溶液将体系调节pH调节至6.0～7.0；静置7天，取下层沉淀，用去离子水重新溶解、过滤，分批通过再生纤维素透析袋(孔径20nm)在去离子水中透析5天，将透析袋中分散体系取出，冷却至室温后干燥、粉碎、过筛，即可得到羧甲基壳聚糖；(3)在高压均质器中加入去离子水2000mL，分批加入阳离子纳米纤维悬浮液800g，在20000rpm条件下均质化2h，加入40g二辛基磺化丁二酸钠，在500rpm条件下均质化20min；在上述的均质器中缓慢加入150g羧甲基壳聚糖，在800rpm条件下均质化2h；将转速提高至15000rpm，依次缓慢加入80g纳米二氧化硅SJ-3500和60g丙三醇，均质化4h；将上述产物置于烘箱中，在80±5℃烘干，并用粉碎机将干燥好的产物粉碎，用标准检验筛筛分，粉碎至800～1000目，即可得到基于纳米纤维-壳聚糖复合物的钻井液用降滤失剂。(1) 300g of glacial acetic acid (concentration 98%) and 200g of hypochlorous acid were added to a 2000mL three-necked round-bottomed flask, 900mL of deionized water was slowly added, and the stirring was performed dropwise (rotation speed 300rpm), and the temperature was adjusted to 30°C, until completely dissolved; add 600g of pretreated bagasse in batches to the above-mentioned three-necked flask, stir at a low speed of 300rpm for 1h, after adding, the temperature is raised to 50°C, the stirring speed is increased to 2000rpm, and stirred for 2h to obtain a milky white Suspension; adjust the pH of the preceding milky white suspension to 4.0-5.0, add 30 g of dodecyl trimethyl ammonium chloride, and continue the reaction for 2 h. Transfer the system to a 5000mL large plastic cup, add excess deionized water to terminate the reaction; transfer the above dispersion system to a centrifuge in batches, centrifuge at 20000rpm for 20min, precipitate, pour out the supernatant, add Ionized water, centrifuged at high speed again until the supernatant was clear, and centrifuged for several times until the pH of the system was 5.0 to 6.0; the above dispersion system was dialyzed in deionized water through regenerated cellulose dialysis bags (pore size 20nm) in batches , the dialysis time is 9 days, until the pH of the system is 6.0 ~ 8.0, the dispersion system in the dialysis bag is concentrated to a concentration of 30% by low-temperature rotary evaporation, transferred to a sealed bottle and sealed for use, and the cationic nanofiber suspension can be obtained. (2) Add 1000mL of deionized water in a 2000mL three-necked round-bottomed flask, add 80g of chitosan powder in batches, slowly dropwise add 90g of glacial acetic acid (98% concentration) and 120g, and stir while adding (rotating speed 500rpm) , the temperature was controlled at 80 °C, and the reaction was completed for 8 h. After the reaction was completed, the pH of the system was adjusted to 6.0-7.0 with HCl solution; after standing for 7 days, the lower layer of precipitate was removed, redissolved with deionized water, filtered, and passed through regenerated cellulose in batches. The dialysis bag (pore size 20nm) was dialyzed in deionized water for 5 days, the dispersion system in the dialysis bag was taken out, cooled to room temperature, dried, pulverized and sieved to obtain carboxymethyl chitosan; (3) Homogenized under high pressure Add 2000 mL of deionized water to the vessel, add 800 g of cationic nanofiber suspension in batches, homogenize at 20,000 rpm for 2 h, add 40 g of sodium dioctyl sulfosuccinate, and homogenize at 500 rpm for 20 min; Slowly add 150g of carboxymethyl chitosan to the homogenizer of 1, and homogenize at 800rpm for 2h; increase the rotation speed to 15000rpm, slowly add 80g of nano-silica SJ-3500 and 60g of glycerol in sequence, and homogenize 4h; put the above product in an oven, dry it at 80±5°C, and pulverize the dried product with a pulverizer, sieve it with a standard inspection sieve, and pulverize to 800-1000 mesh, to obtain a nanofiber-shell based nanofiber-shell Fluid loss control agent for drilling fluids of polysaccharide complexes.
性能测试Performance Testing
(1)滤失量测定：采用钻井液常用API滤失仪测定钻井液的滤失量，配置好钻井液之后，将钻井液老化24h后，检测其初始滤失量，记为FL1；加入2.0wt％纳米纤维-壳聚糖复合物降滤失剂，充分搅拌后，检测其滤失量，记为FL2；150℃/16h老化后，再测定其滤失量，记为FL3。(1) Determination of fluid loss: The fluid loss of the drilling fluid is measured by using the commonly used API fluid loss meter for drilling fluids. After the drilling fluid is configured, after the drilling fluid is aged for 24 hours, the initial fluid loss is detected and recorded as FL1 ; 2.0 wt% nanofiber-chitosan composite filtrate reducer, after fully stirring, the filtration loss was measured and recorded as FL2 ; after aging at 150°C/16h, the filtration loss was measured again and recorded as FL3 .
(2)急性毒性检测：根据《GB/T15441-1995水质急性毒性的测定发光细菌法》检测体系毒性，记为EC50。(2) Acute toxicity test: According to "GB/T15441-1995 Determination of Acute Toxicity of Water Quality Luminescent Bacteria Method", the toxicity of the system is detected and recorded as EC50 .
测试样品为上述实施例纳米纤维-壳聚糖复合物降滤失剂，在4.0wt％膨润土基浆中加入2.0wt％的纳米纤维-壳聚糖复合物降滤失剂，并与4.0％膨润土基浆进行对比，测试了老化前后的滤失量，结果请参阅图1。The test sample is the nanofiber-chitosan composite fluid loss reducer of the above-mentioned embodiment, adding 2.0wt% nanofiber-chitosan composite fluid loss reducer to 4.0wt% bentonite base slurry, and mixing with 4.0wt% bentonite The base slurry was compared, and the fluid loss before and after aging was tested, and the results are shown in Figure 1.
从图1看出，老化前后，实施例的降滤失效果相差不大。本发明的实施例加量为2.0wt％时，API滤失量大幅度降低，2.0wt％纳米纤维-壳聚糖复合物加入基浆后从16.5mL降低至5mL，经过150℃/16h老化后，其滤失量仍能保持在6.2mL。It can be seen from FIG. 1 that before and after aging, the filter loss reduction effect of the embodiment is not much different. When the dosage of the example of the present invention is 2.0wt%, the API filtration loss is greatly reduced, and the 2.0wt% nanofiber-chitosan composite is added to the base slurry from 16.5mL to 5mL. After aging at 150°C/16h , the filtration loss can still be maintained at 6.2mL.
随后考察了三个实例的急性毒性，从结果的可知，三个实例的EC50值分别为68000ppm、65000ppm和63000ppm，均为无毒。Subsequently, the acute toxicity of the three examples was investigated. From the results, the EC50 values of the three examples were respectively 68000 ppm, 65000 ppm and 63000 ppm, all of which were non-toxic.
Claims (4)
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| CN113150755B (en)* | 2021-04-29 | 2022-04-08 | 西南石油大学 | Preparation method of filtrate reducer, drilling fluid and preparation method of drilling fluid |
| CN116589988A (en)* | 2023-03-30 | 2023-08-15 | 成都西油华巍科技有限公司 | Weak gel tackifier for drilling fluid and preparation method and use method thereof |
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| US6080277A (en)* | 1995-02-21 | 2000-06-27 | Tfm Handels-Aktiengesellschaft | Cellulose particles, method for producing them and their use |
| CN107955589A (en)* | 2017-11-08 | 2018-04-24 | 中石化石油工程技术服务有限公司 | Free clay phase water-base drilling fluid a kind of cellulose nano-fibrous and containing the component |
| CN108384520A (en)* | 2018-04-02 | 2018-08-10 | 中国石油天然气集团有限公司 | A kind of degradable fiber sealing agent and preparation method thereof of drilling fluid |
| CN109810678A (en)* | 2017-11-20 | 2019-05-28 | 中石化石油工程技术服务有限公司 | Mud shale formation plugging agent based on nanofiber composite for drilling fluid and preparation method |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US6080277A (en)* | 1995-02-21 | 2000-06-27 | Tfm Handels-Aktiengesellschaft | Cellulose particles, method for producing them and their use |
| CN107955589A (en)* | 2017-11-08 | 2018-04-24 | 中石化石油工程技术服务有限公司 | Free clay phase water-base drilling fluid a kind of cellulose nano-fibrous and containing the component |
| CN109810678A (en)* | 2017-11-20 | 2019-05-28 | 中石化石油工程技术服务有限公司 | Mud shale formation plugging agent based on nanofiber composite for drilling fluid and preparation method |
| CN108384520A (en)* | 2018-04-02 | 2018-08-10 | 中国石油天然气集团有限公司 | A kind of degradable fiber sealing agent and preparation method thereof of drilling fluid |
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