CN107090284B - 一种超分子自组装稠油驱油剂的制备方法 - Google Patents
一种超分子自组装稠油驱油剂的制备方法 Download PDFInfo
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Abstract
本发明首先以γ‑CD(γ‑环糊精)为原料，制备6‑单对甲苯磺酰基‑γ‑CD，将6位羟基活化，然后使其与丙烯酰胺反应，制备出N‑γ‑CD‑丙烯酰胺，再与丙烯酰胺共聚，制备出丙烯酰胺‑N‑γ‑CD‑丙烯酰胺共聚物(Ⅰ)；以脑磷脂为原料，将其先后分别与2倍的碘甲烷和稍过量的苄基氯反应，生成N,N‑二甲基‑N‑苄基脑磷脂(II)；将Ⅰ与II按比1：1混合，制备出分子自组装稠油驱油剂。制备出的驱油剂性能优异，驱油效率高。
Description
技术领域
本发明属油田采油助剂领域，特别是涉及一种由分子自组装原理制备稠油驱油剂的方法。
背景技术
近年来，我国多数油田已经进入中后期开发阶段，伴随着稠油开采量的不断增加，高密度、高粘度、流动性差的特性给原油开采和输送带来了极大困难，而稠油开发的关键在于如何降低原油粘度、改善其流动性等方面。化学法是较为成功的稠油开采技术，特别是稠油乳化降粘技术研究已深入到微观技术领域。该技术应用在井筒举升方面取得了较好的效果，但应用在油藏处理方面，该类技术存在严重的局限性，无法进行大规模推广。比如，化学降粘剂的普适性较差、应用范围较窄、化学吞吐的处理范围小、经济效益相对较差。另外，基于化学剂对环境造成的污染，美国一些大的油田化学公司正着手寻找活性寡聚物来代替小分子原油乳化降粘剂，比如利用生物酶的增效作用，降低小分子原油乳化剂的使用浓度等
本发明是基于超分子自组装的相关理论以及稠油自主分散的实际需要，设计适宜的主、客体分子(均为两亲分子)，通过主体分子通过油水界面对稠油中沥青、胶质分子聚集体的嵌合，再借助客体分子与主体分子的自组装，将稠油自发分散至水相，达到提高稠油采收率的目的。
发明内容
本发明首先以γ-CD(γ-环糊精)为原料，制备6-单对甲苯磺酰基-γ-CD，将6位羟基活化，然后使其与丙烯酰胺反应，制备出N-γ-CD-丙烯酰胺，再与丙烯酰胺共聚，制备出丙烯酰胺-N-γ-CD-丙烯酰胺共聚物(Ⅰ)；以脑磷脂为原料，将其先后分别与2倍的碘甲烷和稍过量的苄基氯反应，生成N,N-二甲基-N-苄基脑磷脂(Ⅱ)；将Ⅰ与Ⅱ按比1：1混合，制备出分子自组装稠油驱油剂。制备出的驱油剂性能优异，驱油效率高。
具体实施方式
实施例1
(1)取0.05molγ-环糊精和0.055mol氢氧化钠置于研钵中，滴入少许乙醇和蒸馏水，研磨均匀，25℃碱化1h，加入0.05mol对甲苯磺酰氯，继续研磨0.5h后，置于40℃烘箱内，反应0.5h，取出，继续研磨0.5h，置于40℃烘箱内，反应0.5h，反复进行6次，冷却，乙醇洗涤3次，得白色固体粉末，将0.05mol丙烯酰胺溶解于100ml蒸馏水中，保持温度在10℃，搅拌下逐渐加入上述白色固体粉末，直至所有固体溶解，再加入0.01g过硫酸钾，通入氮气10min，驱尽反应器内空气，升温至50℃，保温反应3h，生成无色粘稠液体；
(2)将0.05mol的脑磷脂和100ml水加入带有搅拌装置的反应容器中，加热搅拌分散后，通入氮气驱尽反应器内空气，大约15分钟，升温至80℃，搅拌下用滴液漏斗缓慢滴入0.055mol碘甲烷，反应3.0h，然后再缓慢滴入0.055mol苄基氯，反应4.0h，生成浅黄色粘稠状液体产物；
(3)将(1)和(2)生成的产物分别用100ml水稀释后，混合，搅拌，生成浅黄色透明粘稠液体。
实施例2
准确称取实施例1(3)中制备的浅黄色粘稠液体，分散溶解于清水中，搅拌1-2h，配置出药剂浓度分别为0.01％、0.03％、0.05％、0.07％和0.1％的驱油剂溶液。用BROOKFILDDV-III+型流变仪测定各种浓度溶液在40℃至80℃下的粘度。结果见表1。
表1驱油剂溶液不同浓度和温度下的粘度(mPa.s)
实施例3
准确称取100.0g粒径为0.1-0.3mm的石英砂若干，分别称取粘度(25℃)为700mPa.s、1500mPa.s、56500mPa.s、125860mPa.s四种脱水原油各20.0g，加热至80℃后(使原油可以流动)与石英砂充分搅拌混合，制备出四种含油石英砂，编号分别为1#～4#，冷却至室温备用；准确称取实施例2中配置的不同浓度的驱油剂溶液各50.0g，分别倒入上述四种油砂中，然后将容器(准确称量)密封后置于60℃恒温箱中保温24h。倒出容器中的液体，收取油砂，于105℃干燥箱中烘去水分，冷却至室温，称量，按式(1)计算洗油率。按照上述同样方法测定40℃和80℃温度下驱油剂溶液的洗油率。见表2至表4。从可以看出，在洗油效果上，药剂对原油粘度小的油砂好于对原油粘度大的油砂，并且随着温度的升高，洗油率均增大；在三种温度下，对于原油粘度小的1#油砂，0.01％的药剂浓度洗油率都超过了25％，最大达到了82.5％。对于原油粘度大的4#油砂，0.01％的药剂浓度洗油率都超过了10％，最大达到65.3％。结果表明，无论是低粘度原油还是高粘度原油，通过调节实施例1中制备的药剂的使用浓度，可以有效清洗油砂上的原油。
洗油率(％)＝(处理后油砂总重－100.0－空白量)÷20.0×100 式(1)
其中，空白量(g)＝清水处理后的油砂总重－100.0
表2 40℃温度下不同浓度驱油剂溶液的洗油率(％)
表3 60℃温度下不同浓度驱油剂溶液的洗油率(％)
表4 80℃温度下不同浓度驱油剂溶液的洗油率(％)
实施例4
选择胜利油田玉皇庙夏8区块油井原油，按下列方法制备人造岩心并进行驱替实验：准确称取1800g石英砂(粒径：0.3-0.6mm)和200g原油(胜利油田玉皇庙夏8区块油井脱水原油，见表5)于60℃干燥箱内保温24h，然后将原油和石英砂充分搅拌混合均匀，备用；将上述2000g油砂从岩心管(直径×长度：2.5cm×10cm)上端装入，填入时边装边用有机玻璃棒压实。然后将模拟岩心加盖密封固定，放入恒温箱中，60℃保温过夜。
将上述模拟岩心介入驱替装置，首先在60℃恒温水浴中用60℃热水驱替(驱替速度：3ml/min)，直到没有原油流出时，收集驱出的原油，脱水后称重；然后改用0.01％的驱油剂水溶液15g按同样的驱替速度驱替，并收集驱出的原油，脱水后称重。计算0.01％的本驱油剂水溶液15g在60℃热水驱后采收率提高率。结果见表6。
表5 60℃温度下胜利油田玉皇庙夏8区块油井原油
| 油井号 | 夏8-1 | 夏8-11 | 夏19-1 | 夏19-8 |
| 原油粘度，mPa.s | 20750 | 19500 | 21380 | 21000 |
表6 60℃温度下0.01％驱油剂驱替采收率提高值
Claims (1)
1.一种由超分子自组装稠油驱油剂的制备方法。包括下列步骤：
(1)取0.05molγ-环糊精和0.055mol氢氧化钠置于研钵中，滴入少许乙醇和蒸馏水，研磨均匀，25℃碱化1h，加入0.05mol对甲苯磺酰氯，继续研磨0.5h后，置于40℃烘箱内，反应0.5h，取出，继续研磨0.5h，置于40℃烘箱内，反应0.5h，反复进行6次，冷却，乙醇洗涤3次，得白色固体粉末，将0.05mol丙烯酰胺溶解于100ml蒸馏水中，保持温度在10℃，搅拌下逐渐加入上述白色固体粉末，直至所有固体溶解，再加入0.01g过硫酸钾，通入氮气10min，驱尽反应器内空气，升温至50℃，保温反应3h，生成无色粘稠液体；
(2)将0.05mol的脑磷脂和100ml水加入带有搅拌装置的反应容器中，加热搅拌分散后，通入氮气驱尽反应器内空气，大约15分钟，升温至80℃，搅拌下用滴液漏斗缓慢滴入0.055mol碘甲烷，反应3.0h，然后再缓慢滴入0.055mol苄基氯，反应4.0h，生成浅黄色粘稠状液体产物；
(3)将(1)和(2)生成的产物分别用100ml水稀释后，混合，搅拌，生成浅黄色透明粘稠液体。
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| CN110410047B (zh) * | 2019-06-17 | 2021-09-28 | 中国石油天然气股份有限公司 | 一种针对高含气油田的驱油方法及其气体能量释放驱油剂 |
| CN116892387B (zh) * | 2023-07-10 | 2024-05-24 | 河南省科学院同位素研究所有限责任公司 | 一种油田气驱监测用放射性同位素示踪剂的制备方法 |
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| CN104164226A (zh) * | 2013-05-20 | 2014-11-26 | 北京德美高科科技有限责任公司 | 一种高温洗油剂 |
| CN104861950A (zh) * | 2015-05-19 | 2015-08-26 | 重庆科技学院 | 一种超分子线性聚丙烯酰胺驱油剂及其制备方法 |
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| CN104164226A (zh) * | 2013-05-20 | 2014-11-26 | 北京德美高科科技有限责任公司 | 一种高温洗油剂 |
| CN104140493A (zh) * | 2014-07-24 | 2014-11-12 | 西南石油大学 | 一种水溶性离子型疏水缔合聚合物驱油剂及其制备方法和应用 |
| CN104861950A (zh) * | 2015-05-19 | 2015-08-26 | 重庆科技学院 | 一种超分子线性聚丙烯酰胺驱油剂及其制备方法 |
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