CN107722959A - 一种胍胶压裂液有机钛交联剂及其制备方法 - Google Patents
一种胍胶压裂液有机钛交联剂及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种胍胶压裂液有机钛交联剂,以多元醇和含胺基的有机硅化合物形成的缩聚产物为骨架,表面修饰具有交联性能的Ti4+;还公开了该有机钛交联剂的制备方法,具体为:首先将多元醇分散于反应介质中,然后加入含胺基的有机硅化合物,搅拌反应,得到反应体系A;将钛源分散于分散介质中,得到反应体系B;将反应体系A加入反应体系B中,搅拌反应,即得。本发明合成了具有多活性位点的有机钛交联剂,其空间结构可增加交联剂与胍胶的接触概率,使胍胶分子链更多的形成分子间交联,有效地提高交联效率,使形成的压裂液具有更好的粘弹性和耐温性能,可在使用中减少胍胶的用量,继而减少残渣含量,并且减少对地层和支撑剂充填层的伤害。
Description
技术领域
本发明属于油田化学助剂技术领域,具体涉及一种胍胶压裂液有机钛交联剂及其制备方法。
背景技术
在我国剩余石油储量和探明天然气地质储量中,低渗透油气资源占总油气资源储量的80%以上,而水力压裂是开采低渗透储藏油气资源的一种重要技术手段。常用的水力压裂液是胍胶压裂液,其交联剂主要有硼酸、硼砂、有机硼和过渡金属离子(钛离子、锆离子等)、有机钛、有机锆等。
目前,具有稳定性能的低浓度胍胶压裂液越来越引起人们的关注。H.Sun 等研究了交联剂尺度对交联胍胶流变行为的影响,结果表明增大交联剂的尺度可增加其交联效率和交联流体的粘度,可有效的降低胍胶浓度和残渣含量。Magnus.U.Legemah等成功制备了多活性位点的聚胺基硼酸交联剂,交联活性位点增多可有效提高交联效率,降低胍胶浓度。但硼类交联剂交联的胍胶压裂液体系不耐高温,高温下其粘度会迅速降低,无法用于高温井中。而过渡金属类交联剂由于其与胍胶间形成特殊的共价键,因此,其交联的胍胶压裂液体系在高温下还能保持较高的粘度。但是,目前过渡金属类交联剂交联的胍胶压裂液普遍存在破胶后残渣含量大的问题,对地层和支撑剂充填层造成一定的伤害,限制了其大规模使用。
发明内容
基于以上技术不足,本发明的目的在于提供了一种胍胶压裂液有机钛交联剂,通过以多元醇和含胺基的有机硅化合物形成的缩聚产物为骨架,表面修饰具有交联性能的Ti4+,制备一种高交联效率且耐温性好的交联剂。交联效率的提高可有效降低胍胶浓度和残渣含量,减少对地层和支撑剂充填层的伤害,而耐温性好可使其用于高温深井。
为了实现上述目的,本发明采用的技术方案为:
一种胍胶压裂液有机钛交联剂的制备方法,包括以下步骤:
(1)将多元醇加入反应介质中,升温至50~80℃,搅拌0.5~1小时;然后加入含胺基的有机硅化合物,于50~90℃搅拌1.5~3.5小时,得到反应体系A;
(2)取钛源加入分散介质中,混匀,得到反应体系B;
(3)将反应体系A加入反应体系B中,于70~90℃搅拌2~4小时,即得;
其中,多元醇、含胺基的有机硅化合物及钛源的质量比为(1~7)∶25∶(20~40)。
优选地,步骤(1)中所述多元醇为山梨醇、季戊四醇中的一种。
优选地,步骤(1)中所述含胺基的有机硅化合物为γ-氨丙基三乙氧基硅烷、γ-氨丙基三甲氧基硅烷、N-氨乙基-γ-氨丙基三甲氧基硅烷、N-氨乙基-γ-氨丙基三乙氧基硅烷及苯胺基甲基三甲氧基硅烷中的一种。
优选地,步骤(1)中所述反应介质为C1~C5的烷基醇中的一种或两种以上。
优选地,步骤(2)中所述钛源为四氯化钛、钛酸四丁酯及钛酸四乙酯中的一种。
采用上述方法制备得到的胍胶压裂液有机钛交联剂。
上述原料均为普通市售产品。
本发明是以多元醇和含胺基的有机硅化合物的缩合产物为骨架,表面修饰具有交联性能的Ti4+,制备了有机钛交联剂;如以季戊四醇(多元醇)和γ-氨丙基三乙氧基硅烷(含胺基的有机硅化合物)的缩合产物为骨架,表面修饰Ti4+,首先γ-氨丙基三乙氧基硅烷(KH550)水解,然后与季戊四醇脱水缩合,最后Ti4+与上述缩合产物上的胺基形成稳定的配位络合物,形成及反应机理如下:
本发明制得的有机钛交联剂通过空间结构可增加交联剂和胍胶分子链的接触概率,使胍胶分子链间更易形成分子间交联(有效交联),有效地提高交联效率,可在使用中减少胍胶的用量,继而减少破胶后的残渣含量,降低对地层和支撑剂充填层的伤害。
附图说明
图1是实施例1制得的有机钛交联剂和TiCl4分别作为交联剂时胍胶粘度变化曲线图;
图2为实施例1制得的有机钛交联剂和TiCl4分别交联胍胶的频率扫描图。
具体实施方式
为了使本发明的技术目的、技术方案和有益效果更加清楚,下面结合具体实施例对本发明的技术方案作出进一步的说明,但所述实施例旨在解释本发明,而不能理解为对本发明的限制,实施例中未注明具体技术或条件者,按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。
实施例1
一种胍胶压裂液有机钛交联剂的制备方法,包括以下步骤:
(1)将0.61 g季戊四醇加入80 g无水乙醇中,升温至50 ℃,300 rpm恒温恒速搅拌0.5h,以使季戊四醇完全溶解;然后缓慢滴加5 g γ-氨丙基三乙氧基硅烷,升温至80℃,恒速搅拌3 h,得到反应体系A;
(2)取4 g四氯化钛加入20 g无水乙醇中,混匀,得到反应体系B;
(3)将反应体系A缓慢滴加于反应体系B中,升温至80℃,搅拌3小时,即得淡黄色澄清透明的胍胶压裂液有机钛交联剂。
实施例2
一种胍胶压裂液有机钛交联剂的制备方法,包括以下步骤:
(1)将0.20 g季戊四醇加入80 g 反应介质(由50 g无水乙醇和30g丙三醇混匀而成)中,升温至50 ℃,300 rpm恒温恒速搅拌0.5 h,以使季戊四醇完全溶解;然后缓慢滴加5 gγ-氨丙基三乙氧基硅烷,升温至80℃,恒速搅拌3 h,得到反应体系A;
(2)取4 g四氯化钛加入20 g无水乙醇中,混匀,得到反应体系B;
(3)将反应体系A缓慢滴加于反应体系B中,升温至80℃,搅拌3小时,即得。
实施例3
一种胍胶压裂液有机钛交联剂的制备方法,包括以下步骤:
(1)将0.61 g季戊四醇加入80 g无水乙醇中,升温至50 ℃,300 rpm恒温恒速搅拌0.5h,以使季戊四醇完全溶解;然后缓慢滴加5 g苯氨基甲基三甲氧基硅烷,升温至80℃,恒速搅拌3 h,得到反应体系A;
(2)取8 g四氯化钛加入20 g无水乙醇中,混匀,得到反应体系B;
(3)将反应体系A缓慢滴加于反应体系B中,升温至80℃,搅拌3小时,即得。
实施例4
一种胍胶压裂液有机钛交联剂的制备方法,包括以下步骤:
(1)将1.4 g山梨醇加入50g无水乙醇和30 g丙三醇中,升温至80 ℃,300 rpm恒温恒速搅拌1 h;然后缓慢滴加5 g γ-氨丙基三甲氧基硅烷,升温至90℃,恒速搅拌2 h,得到反应体系A;
(2)取8 g钛酸四丁酯加入20 g无水乙醇中,混匀,得到反应体系B;
(3)将反应体系A缓慢滴加于反应体系B中,升温至80℃,搅拌3小时,即得。
实施例5
一种胍胶压裂液有机钛交联剂的制备方法,包括以下步骤:
(1)将1 g季戊四醇加入80 g无水乙醇中,升温至50 ℃,300 rpm恒温恒速搅拌0.5 h,以使季戊四醇完全溶解;然后缓慢滴加5 g苯氨基甲基三甲氧基硅烷,于50℃,恒速搅拌3.5h,得到反应体系A;
(2)取4 g四氯化钛加入20 g无水乙醇中,混匀,得到反应体系B;
(3)将反应体系A缓慢滴加于反应体系B中,于90℃搅拌2小时,即得。
性能检测
1. 挑挂性能测试
取3份50 mL质量分数为0.3%的胍胶溶液,用氢氧化钠调pH为9,再分别加入1.5 mL实施例1、2、3制备的有机钛交联剂,搅拌至液面微微凸起,停止搅拌, 3~5 min后,均能完全挑挂,可见交联效果明显。
2. 悬砂性能测试
取3份100 mL质量分数为0.3%的胍胶溶液,用氢氧化钠调pH为9,加入20~40目的标准陶粒,搅拌均匀,分别加入1.5 mL实施例1、2、3制得的有机钛交联剂,搅拌至不可流动,倒入100 mL量筒中,3 h后陶粒微量沉降,可见交联效果较好,悬砂性能优良。
3. 破胶性能测试
取3份100 mL质量分数为0.3%的胍胶溶液,用氢氧化钠调pH为9,分别加入1.5 mL实施例1、2、3制备的交联剂,同时加入过硫酸铵,100℃下恒温破胶3 h。经测试,实施例1、2、3制备的交联剂的破胶液粘度分别约为3.0 mPa.s、4.0 mPa.s 、4.0 mPa.s,低于SY/T 6376-2008 《压裂液通用技术条件》对破胶液粘度的要求(≤ 5mPa.s),可见最终破胶状态比较理想。
4. 对比试验
以TiCl4作为对比交联剂,分别取不同量实施例1制得的有机钛交联剂和TiCl4分别加入到50mL质量分数为0.3%的胍胶溶液中,胍胶粘度变化如图1所示,当用量为1.5 mL时,实施例1制得的有机钛交联剂交联的胍胶粘度大于TiCl4交联的胍胶粘度,这可能是因为实施例1制备的有机钛交联剂的交联位点更多和其空间结构,易于使胍胶分子形成分子间交联(有效交联),形成的网状结构更紧密,具有更优的耐温性。对于实施例1制得的有机钛交联剂,用量为2 mL时交联的胍胶粘度小于用量为1.5 mL时交联的胍胶粘度,说明发生了过度交联。而对于TiCl4,用量为2 mL时交联的胍胶粘度大于用量为1.5 mL时交联的胍胶粘度,说明还未发生过度交联。从而说明了交联剂同样用量情况下,实施例1制备的有机钛交联剂的交联效率更高。
图2为实施例1制得的有机钛交联剂和TiCl4交联胍胶的频率扫描图。从图2中可见,随着频率的增大,交联形成的网状结构不稳定,分子链部分解缠结变为局部有序,破坏速率大于重建速率,使网状结构受到破坏,故G′逐渐的降低。对于实施例1制备的有机钛交联剂的G′,用量为2 mL时小于用量为1.5 mL时,说明发生了过度交联;而对于TiCl4,用量为2 mL时大于用量为1.5 mL时,说明还未发生过度交联,且实施例1制备的有机钛交联剂的G′大于TiCl4的G′,从而也说明了交联剂同样用量情况下,实施例1制备的交联剂的交联效率更高,具有较好的粘弹性。实施例1制备的交联剂交联的胍胶的G′大于TiCl4交联的胍胶的G′,这可能是因为实施例1制备的交联剂具有空间结构且交联位点多,可与胍胶分子形成更庞大且紧密的网状结构,因此表现出更好的耐温性和粘弹性。
分别取硼酸、TiCl4以及实施例1制得的有机钛交联剂交联胍胶并对其进行性能测试,结果如表1所示。
表1 交联剂性能测试结果
从表1中我们可以看出实施例1制备的有机钛交联剂交联低浓度的胍胶就能形成性能好的冻胶,由于胍胶浓度低,所以残渣含量少。这是因为实施例1 制备的有机钛交联剂的交联效率高,故其交联低浓度的胍胶就能形成性能好的冻胶。
经检测,实施例4、5也具有良好的交联效果,且悬砂性能优良,最终破胶状态也比较理想。
最后应说明的是:以上各实施例仅用以说明本发明的技术方案,而非对其限制;尽管参照前述各实施例对本发明进行了详细的说明,本领域的普通技术人员应当理解:其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分或者全部技术特征进行等同替换;而这些修改或者替换,并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。
Claims (7)
1.一种胍胶压裂液有机钛交联剂的制备方法,其特征在于,包括以下步骤:
(1)将多元醇加入反应介质中,升温至50~80℃,搅拌0.5~1小时;然后加入含胺基的有机硅化合物,于50~90℃搅拌1.5~3.5小时,得到反应体系A;
(2)取钛源加入分散介质中,混匀,得到反应体系B;
(3)将反应体系A加入反应体系B中,于70~90℃搅拌2~4小时,即得;
其中,多元醇、含胺基的有机硅化合物及钛源的质量比为(1~7)∶25∶(20~40)。
2.根据权利要求1所述的胍胶压裂液有机钛交联剂的制备方法,其特征在于:步骤(1)中所述多元醇为山梨醇、季戊四醇中的一种。
3.根据权利要求1所述的胍胶压裂液有机钛交联剂的制备方法,其特征在于:步骤(1)中所述含胺基的有机硅化合物为γ-氨丙基三乙氧基硅烷、γ-氨丙基三甲氧基硅烷、N-氨乙基-γ-氨丙基三甲氧基硅烷、N-氨乙基-γ-氨丙基三乙氧基硅烷及苯胺基甲基三甲氧基硅烷中的一种。
4.根据权利要求1所述的胍胶压裂液有机钛交联剂的制备方法,其特征在于:步骤(1)中所述反应介质为C1~C5的烷基醇中的一种或两种以上。
5.根据权利要求1所述的胍胶压裂液有机钛交联剂的制备方法,其特征在于:步骤(2)中所述钛源为四氯化钛、钛酸四丁酯及钛酸四乙酯中的一种。
6.根据权利要求1所述的胍胶压裂液有机钛交联剂的制备方法,其特征在于:步骤(2)中所述分散介质为C1~C5的烷基醇中的一种或两种以上。
7.采用权利要求1至6任一所述方法制备得到的胍胶压裂液有机钛交联剂。
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