CN113249110A - 一种有机硼钛复合交联剂-阳离子型刺槐豆胶水基压裂液 - Google Patents
一种有机硼钛复合交联剂-阳离子型刺槐豆胶水基压裂液 Download PDFInfo
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Abstract
本发明涉及一种有机硼钛复合交联剂‑阳离子型刺槐豆胶水基压裂液，该水基压裂液主要通过阳离子型刺槐豆胶与有机硼钛复合交联剂进行交联，其中阳离子型刺槐豆胶通过在结构中引入季铵盐阳离子，减少水不溶物，破胶后残渣少，粘附性好，且有抗菌效果，不易腐败；而有机硼钛复合交联剂，通过与有机醇配位得到；当阳离子型刺槐豆胶与有机硼钛复合交联剂反应时，有机硼钛络合物的有机配位体与阳离子型刺槐豆胶中半乳甘露聚糖链上顺式邻位羟基反应，形成结构稳定的1:1或2:1结构的三维网状冻胶；本发明的压裂液冻胶有良好的交联性能、携砂性，耐高温、抗菌以及较低的破胶残渣。
Description
技术领域
本发明属于石油开采技术领域，具体涉及一种有机硼钛复合交联剂-阳离子型刺槐豆胶水基压裂液。
技术背景
水基压裂液是石油开采过程中使用最广的压裂液体系，目前，多以植物多糖中的纤维素或改性纤维素为主要基液，广泛适用于砂岩、灰岩地层中；而水基压裂液体系存在对水敏性地层损害严重，难以耐超高温，水不溶物多、破胶困难、滤失，改性后粘度下降，破胶残渣腐败等问题，因此，开发一种黏度大，耐高温且破胶残渣少的压裂液具有重要意义。
天然刺槐豆胶(LBG)是一种天然的中性半乳甘露聚糖，分子量约30万道尔顿，水溶液粘度高，本身具有很好的增稠效果，其结构主要以D-甘露聚糖在1,6位上以β-(1,4)糖苷键连接α-D-吡喃半乳糖，其中半乳糖和甘露糖比例为1:4。由于，刺槐豆胶分子支化程度高，几乎不存在结晶区，因此，相比于纤维素线性分子链中具有明显的结晶区，刺槐豆胶的改性过程更简便；另外，天然胶仍存在较多的破胶残渣容易引起腐败，破胶后处理成本高，因此，对刺槐豆胶进行改性可赋予其抗菌性，降低成本。
发明内容
为了解决上述的技术问题，本发明提供了一种有机硼钛复合交联剂-阳离子型刺槐豆胶基液；本发明的另一个目的在于提供一种粘度高、耐高温、抗菌效果好的水基压裂液。
一种有机硼钛复合交联剂-阳离子型刺槐豆胶水基压裂液由基液、助排剂、破胶剂组成；
所述的基液由阳离子型刺槐豆胶和有机硼钛复合物交联得到；
所述的助排剂为助排剂为磺酸盐、磷酸盐、硫酸盐氟碳类表面活性剂；
所述的破胶剂为硫酸铵、双氧水、高锰酸钾中的一种或组合；
所述的有机硼钛复合交联剂-阳离子型刺槐豆胶的水基压裂液结构式如(I)所示：
式中LGD(有机配体)为乙二醇、二乙醇胺、三乙醇胺、葡萄糖、葡萄糖酸中的一种或组合；
所述的阳离子型刺槐豆胶结构式如(II)所示：
式中R为OH或3-氯-2-羟丙基-3-甲基-氯化铵、2，3-环氧丙基三甲基氯化铵、缩水甘油基三烷基铵盐其中的一种；
所述的有机硼钛复合交联剂结构式如(III)所示：
所述的有机硼钛复合交联剂-阳离子型刺槐豆胶水基压裂液的制备步骤为：
1)1.0～5.0g天然刺槐豆胶溶于50～100mL异丙醇溶液中，并加入5～20mL 5％(w/v)的NaOH溶液，然后放入室温的水浴锅中磁力搅拌2h，加入0.1～5.0g季铵盐搅拌均匀，50～80℃下继续搅拌6～10h，反应结束后将得到的溶液倒入含有35％(w/v)HCl的的甲醇100～500mL中，抽滤得到沉淀物，用甲醇水溶液洗涤沉淀物并过滤，减压下干燥，得到阳离子型刺槐豆胶；
2)将50～100g LGD，10～20g钛酸丁酯，依次加入到250mL三口烧瓶中，磁力搅拌，待溶液由乳白色变澄清后，加入3～5g四硼酸钠，用HCl调节pH＝4～5，控制温度缓慢升温至70～80℃，反应2～3h，得到淡黄色透明，具有一定黏度的液体，即有机硼钛复合交联剂；
3)100～250mL的蒸馏水中缓慢加入0.1～1.0g阳离子型刺槐豆胶，磁力搅拌均匀使之充分溶解并形成均匀的溶液，静置后加入0.05～0.5g有机硼钛复合物、0.25～2.5g助排剂、0.01～0.5g破胶剂，磁力搅拌均匀3～10min，即形成无色透明水基压裂液；
所述步骤(1)中的天然刺槐豆胶与季铵盐摩尔比可为1:0.1～2，优选为1:15；
所述步骤(3)中的阳离子型刺槐豆胶与有机硼钛复合物投料比可为99:499～1，优选为124:1。
与现有技术相比，本发明具有如下有益效果：
本发明通过阳离子型刺槐豆胶与有机硼钛复合物交联，增加了压裂液的粘度、稳定性、抗剪切、耐高温等性能；本发明的有机硼钛复合交联剂-阳离子型刺槐豆胶水基压裂液提高天然刺槐豆胶的水溶性，粘附性好且具有抗菌性，破胶后残渣少、不易腐败，节约成本。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚明了，下面结合具体实施方式，对本发明进一步详细说明。应该理解，这些描述只是示例性的，而并非要限制本发明的范围。此外，在以下说明中，省略了对公知结构和技术的描述，以避免不必要地混淆本发明的概念。
实施例1阳离子型刺槐豆胶的制备
1.0～5.0g LBG溶于100mL异丙醇溶液中，并加入5～20mL 5％(w/v)的NaOH溶液，室温下磁力搅拌2h，加入0.1～5.0g 2,3-环氧丙基三甲基氯化铵(Glytac)搅拌均匀，60～80℃下继续搅拌6h，反应结束后将得到的溶液倒入含有35％(w/v)HCl的甲醇200mL中，抽滤得到沉淀物，用甲醇水溶液洗涤沉淀物并过滤，减压下干燥，得到阳离子型刺槐豆胶；
其中LBG与Glytac的摩尔比为1:0.1～2，添加量如表1所示；
表1：LBG与Glytac的添加量
根据(SY/T 5107-2016)测定方法，对实施例1和空白对照LBG进行取代度、数均分子量(Mn)和黏度考察，对上述五组样品以及LBG作为空白对照样品的黏度(7.4.1中常压同轴圆筒黏度计、7.4.2.2公式计算)进行考察，取代度、数均分子量(Mn)和黏度考察方法如下：
1)醚化取代度：用含10％氘代盐酸的氘代水将样品溶解，并用70℃水浴加热，水解0.5h，进行氢谱分析；
计算方法：利用取代基中季铵盐与羟基相连的亚甲基的积分峰面积与刺槐豆胶半乳糖和甘露糖异头质子的峰面积(刺槐豆胶结构单元的数量)之比来计算醚化剂的取代度，即得到平均每个刺槐豆胶链的结构单元上被醚化取代的季铵盐数目；
2)数均分子量(Mn)：采用三重检测凝胶渗透色谱法(GPC/SEC3)，在一个模块化系统进行，该系统包括脱气器、HPLC泵(K-1001)和RI检测器(K-2300)、粘度计(Trisec270型双检测器)和RALLS组成以及两根PL-aquagel-OH凝胶色谱柱(8μm、300×7.5mm)，纯化过程中洗脱液为0.2M NaNO3，0.01M NaH2PO4，0.1％w/vNaN3，pH＝7，流速为1mL/min；
按上述测定方法得到的结果见表2；
表2：LBG与Glytac的添加量对阳离子型刺槐豆胶取代度、数均分子量Mn以及黏度的影响
上述阳离子型刺槐豆胶样品的取代度、Mn和黏度测定结果由表2可知，随着季铵盐添加量的增加，取代度、数均分子量均上升，而黏度随着取代程度的增加而降低，直到实施例1中1-4样品中刺槐豆胶与季铵盐摩尔添加比为1:15时，黏度不再降低；因此，选择该比例下得到的阳离子型刺槐豆胶进一步与有机硼钛复合物进行交联得到实施例3的压裂液样品。
实施例2有机硼钛复合物的制备
将25g乙二醇、25g三乙醇胺，10g钛酸丁酯，依次加入到三口烧瓶中，磁力搅拌，待溶液由乳白色变澄清后，加入3g四硼酸钠，用HCl调节pH＝4～5，控制温度缓慢升温至80℃，反应2h，得到淡黄色透明，具有一定黏度的液体。
实施例3水基压裂液的制备
将0.1～0.5％(w/v)阳离子型刺槐豆胶(实施例1中1-4)缓慢加入蒸馏水中，磁力搅拌均匀，形成均匀的溶液，静置后加入0.001～0.005％(w/v)有机硼钛复合物(实施例2)、1％(w/v)磺酸盐氟碳类表面活性剂、0.3％(w/v)硫酸铵，磁力搅拌均匀10min，即形成无色透明水基压裂液；
其中阳离子型刺槐豆胶与有机硼钛复合物的质量浓度比为99:499～1，添加量如表2所示；
表2：阳离子型刺槐豆胶与有机硼钛复合物的添加量
3)根据(SY/T 5107-2016)测定方法，对上述五组样品进行破胶时间和耐高温性(7.9)、沉降速度(7.12降阻率计算)、残渣量(7.10、7.10.2公式计算)以及抗菌活性测定，抗菌活性测定方法如下：
步骤1：实验所用黄杆菌，在菌种接种前，将菌株(4℃下保存)置于36℃的恒温培养箱中培养1～2d，培养基为牛肉膏蛋白胨培养基；
步骤2：分别将实施例4～6高温破胶后的压裂液加入锥形瓶内，用脱脂棉封口，121℃灭菌0.5h，按107个孢子/100mL培养基的量将黄杆菌孢子液加入到培养基中，振荡(110r/min，37±1℃下进行)培养，每天对菌液浓度(个/mL)测量记录一次；
步骤3：用菌落计数仪(法国Interscience Scan100)测定菌液浓度，观察其生长状况：将黄杆菌原液在37℃下培养：0～20d，再将原液按不同稀释倍数(10、100、1000倍)依次进行稀释，分别测出其在平皿内的菌落数量。
按上述测定方法得到的结果见表4；
表:4：阳离子型刺槐豆胶与有机硼钛复合物的添加量对压裂液性能的影响
从表4结果看出，实施例3中五组样品的交联时间小于5min，交联迅速，耐高温性能可达200℃以上，随着基液中有机硼钛复合物含量的增加，压裂液的交联时间减少，速度加快，压裂液的粘度上升，耐高温性增加，阳离子型刺槐豆胶含量减少也使得破胶残渣减少，破胶黏度可降至2.5mPa·s，表明取代度为0.58的阳离子刺槐豆胶与有机硼钛复合物添加比为100:0.8时得到的压裂液有很好的性能。
表5：抗菌性实验结果
对于实施例3中的五组样品进行抗菌效果测定，20天内计算菌落数，由表5结果可知，随着取代度的增加，压裂液的抗菌效果增加，20天内菌落数为1×105.mL-1，菌落数增长慢，抑菌效果明显，可节约抗菌剂成本。
Claims (5)
1.一种有机硼钛复合交联剂-阳离子型刺槐豆胶水基压裂液，其特征在于，所述的水基压裂液由基液、助排剂、破胶剂组成；
所述的基液由阳离子型刺槐豆胶和有机硼钛复合物交联得到；
所述的助排剂为磺酸盐、磷酸盐、硫酸盐氟碳类表面活性剂；
所述的破胶剂为硫酸铵、双氧水、高锰酸钾中的一种或组合。
所述的基液结构式如(I)所示：
式中LGD(有机配体)为乙二醇、二乙醇胺、三乙醇胺、葡萄糖、葡萄糖酸中的一种或组合。
2.一种有机硼钛复合交联剂-阳离子型刺槐豆胶水基压裂液的制备方法，其特征在于，包括以下步骤：
1)1.0～5.0g天然刺槐豆胶溶于50～100mL异丙醇溶液中，并加入5～20mL 5％(w/v)的NaOH溶液，然后放入室温的水浴锅中磁力搅拌2h，加入0.1～5.0g季铵盐搅拌均匀，50～80℃下继续搅拌6～10h，反应结束后将得到的溶液倒入含有35％(w/v)HCl的甲醇100～500mL中，抽滤得到沉淀物，用甲醇水溶液洗涤沉淀物并过滤，减压下干燥，得到阳离子型刺槐豆胶；
2)将50～100g LGD，10～20g钛酸丁酯，依次加入到250mL三口烧瓶中，磁力搅拌，待溶液由乳白色变澄清后，加入3～5g四硼酸钠，用HCl调节pH＝4～5，控制温度缓慢升温至70～80℃，反应2～3h，得到淡黄色透明，具有一定黏度的液体，即有机硼钛复合交联剂；
3)100mL的蒸馏水中缓慢加入0.1～1.0g阳离子型刺槐豆胶，磁力搅拌均匀使之充分溶解并形成均匀的溶液，静置后加入0.001～0.005g有机硼钛复合物、0.25～2.5g助排剂、0.01～0.5g破胶剂，磁力搅拌均匀3～10min，即形成无色透明水基压裂液。
3.根据权利要求2所述的一种有机硼钛复合交联剂-阳离子型刺槐豆胶的水基压裂液的制备方法，其特征在于，所述季铵盐为3-氯-2-羟丙基-3-甲基-氯化铵、2，3-环氧丙基三甲基氯化铵、缩水甘油基三烷基铵盐其中的一种。
4.根据权利要求2所述的一种有机硼钛复合交联剂-阳离子型刺槐豆胶的水基压裂液的制备方法，其特征在于，所述步骤(1)中的天然刺槐豆胶与季铵盐摩尔比可为1:0.1～2。
5.根据权利要求2所述步骤(3)中的一种有机硼钛复合交联剂-阳离子型刺槐豆胶的水基压裂液的制备方法，其特征在于，所述的阳离子型刺槐豆胶与有机硼钛复合物投料比可为99:499～1。
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