CN1119500C - 在石油开采中防止结垢沉积的方法 - Google Patents
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Abstract
含有羧基的果聚糖如羧甲基旋复花粉在石油开采中能成功地用于防止比如由硫酸和碳酸的钙盐、钡盐和锶盐组成的结垢的沉积，其中在处理用水、处理设备或含油地层中引入了0.5-200ppm的每个单糖单元含0.3-3个羧基的含羧基果聚糖。
Description
技术领域
本发明涉及一种在开采石油中防止金属盐沉积的方法。
背景技术
水广泛应用于石油开采中。将水在压力下注入储油层。岩石中的油被水驱替进入近距离的生产井。含有油的岩石也含有水，这种水指的是地层水。这种地层水通常含有潜在的能形成结垢的金属离子，如钡、钙和锶。在一定条件下，这些阳离子产生不溶产物。很多油田坐落在近海处，在那里可利用海水驱替石油。海水含有高浓度的硫酸盐和碳酸盐离子。当海水与地层水混合时，生成不溶盐，如硫酸钡、硫酸钙和碳酸钙。这不仅在多孔岩石中产生沉淀，而且在用于开采石油的管道和其它设备里也产生沉积物。地层水还含有放射性原料，掺杂在生成的沉淀物中。因此，当除去沉淀时，必须采取措施以保护雇佣工人和环境。
结垢的形成可用不同的方法来控制：
(a)对于碳酸钙结垢，加入酸或二氧化碳平衡可能移向(可溶的)碳酸氢盐。然而，加入酸得不到所希望的效果，部分原因是发生了腐蚀和海水的缓冲作用。因为需要大量的酸才能有效地降低PH值，其结果是该方法在经济上缺乏吸引力。
(b)设备可定期进行化学或机械清洗以除掉结垢。化学清洗可用强酸或配合剂如EDTA来进行。其弊端是这种方法不能清洗处理岩石本身中的沉积物，而且这种方法会对环境带来不利因素。
(c)沉积物的形成可通过使用防垢剂得到防止。防垢剂是通过部分抑制晶体生长大大地减少结垢形成的物质。从技术和经济的角度看，这样的防垢剂最具吸引力。
已建议或已使用的用作防垢剂的物质包括聚丙烯酸酯、聚丙烯酰胺、氨基磷酸盐和磷酸盐。比如不同的N-磷酰甲基-聚酰亚胺用作防垢剂在GB-A2248830和WO 97/21905中描述过。这些产品的弊端在于它们是石化产品，因此是不可再生的原料，不能生物降解且对水环境有毒。用于石油开采的化学添加剂的环境状况越来越重要，这专门用于北海的石油开采中。产品主要依据生物降解性和水生生物毒性分类，且更优选最优级产品。因此对具有良好环境状况的防垢剂的需求越来越大。而且许多公知的防垢剂，尤其是磷酸盐，在铁离子存在时性能降低；由于管线和设备的腐蚀可能产生高浓度铁离子，而导致铁结垢如Fe(OH)3和FeCO3。
在US-A 4561982中，氧化多糖如淀粉、纤维素和羧甲基纤维素被建议作为防垢剂。在这些多糖中至少一些葡萄糖环氧化成具有下列分子式的基团：-CH(COOH)-CHA-O-CH(COOH)-O-，其中A是CH2OH，CH2OCH2COOH或COOH。建议用于冷水体系、清淤装置、地热装置等中；没提到石油提和海水。
现在已发现在石油和天然气开采中对结垢抑制用改进剂的需要可通过使用含羧基的旋复花粉和其它含羧基的果聚糖得到满足。这些衍生物具有优良的防垢作用，可生物降解且无毒；另外，它们的性能不受铁离子的存在影响。
发明内容
本发明提供一种在石油开采中使用一种聚羧基化合物防止结垢结垢沉积的方法，其特征在于在处理用水、处理设备或含油地层中引入了每个单糖单元含0.3-3个羧基的含羧基果聚糖。
在本发明中，果聚糖理解为是包括一切含有大量无水果糖单元的低聚糖和多聚糖。果聚糖具有多分散的链长度分布，可以是直链或支化链。果聚糖主要含有β-2，6键，如在左聚糖中。优选地，果聚糖主要含有β-2，1键，如在旋复花粉中。
在本发明中，含羧基的果聚糖理解为是旋复花粉或其它每个无水果糖单元含有0.3-3个羧基的果聚糖的衍生物。具体地说，该衍生物每个无水果糖单元至少含有0.8个羧基。羧基可以是羧烷基如羧甲基、羧乙基、二羧甲基或羧乙氧基羰基。这些基团可以公知的方式通过果聚糖醚化获得。羧基也可以是氧化羟亚甲基或羟甲基。也可用混合的羧基果聚糖。优选地，羧甲基的数量比其它羧基数量要大。最优选羧甲基旋复花粉(CMI)。
取代度(DS)为0.15-2.5的羧甲基旋复花粉(CMI)在WO 95/15984中和Verraest等人在JAOCS，73(1996)pp.55-62发表的一篇文章中报道过。它是通过高温下旋复花粉浓溶液与氯代醋酸钠反应制备。羧乙基旋复花粉(CEI)在WO 96/34017中有报道。旋复花粉氧化在例如WO 91/17189和WO 95/12619(C3-C4氧化，生成二羧基旋复花粉，DCI)和WO 95/07303(C6氧化)中有过报道。在混合羧基衍生物中旋复花粉首先羧甲基化，然后氧化或(优选地)其它相似的反应。
含羧基的果聚糖平均链长(＝聚合度，DP)至少是3到1000。优选地，平均链长是6到60个单元。果聚糖可进行还原处理以除去还原性基团。
根据本发明能转变成羧烷基果聚糖的改性果聚糖衍生物是例如酶催化扩链的果聚糖和果聚糖水解产物，那就是说具有缩短链的果聚糖衍生物和具有改性链长的分馏产物。果聚糖如旋复花粉的分馏可通过如低温结晶(见WO 94/01849)、柱色谱法(见WO 94/12541)、膜过滤(见EP-A 440074和EP-A 627490)或乙醇的选择性沉淀的实现。先前生成的短链果聚糖的水解通过如酶催化(内-旋复花粉酶)、化学(水和酸)或多相催化(酸柱)进行实施。在羧烷基化和(如果可以的话)氧化之后羟烷基化和/或交联化的果聚糖也可用于本发明的方法中。
羧甲基果聚糖可以以纯净物的形式使用，但也可使用直接从羧甲基化得到的技术级产品。具体地讲，已发现任何杂质，如乙二醇酸和二甘醇酸对CMI的作用没有负面影响。既可使用游离酸又可使用盐，如钠盐、钾盐或铵盐。
含羧基果聚糖，特别是CMI在处理用水中的浓度通常在0.5-200ppm(重量份数)之间，特别是在2-50ppm之间。也可使用含羧基果聚糖和其它防垢剂如聚丙烯酸酯或磷酸盐的混合物，比例优选为至少1份含羧基的果聚糖对1份其它试剂。
防垢剂可加入海水并以这种方式用泵入含油地层中。也可在产生大量沉淀处理设备的特定位置引入防垢剂。防垢剂也可连续注入油井底部的液体中。然而，更进一步技术就是“压榨”技术，在此技术中将防垢剂引入岩石中。防垢剂沉淀和/或地层将其吸收。随着时间的推移通过解吸释放出足够多的防垢剂以防止结垢形成。数月后，结垢配制剂储备用完，再重复此过程。此应用不局限于海上石油开采，也可用于在海上和陆地上以水作为驱替剂的提取过程。
具体实施方式
实施例1
确定CMI(DP约等于10)对碳酸钙的防垢作用。将氯化钙溶液和碳酸钠溶液混合制得一种饱和碳酸钙溶液，所形成的碳酸钙的最大量为95毫克/升。将1毫克/升或5毫克/升的防垢剂加入该溶液。溶液PH值调节到10.0，然后在75℃静置，震荡。20小时后用White Band漏斗过滤，确定滤液的钙含量。防垢剂的作用以不加防垢剂(0％防垢剂)实验的钙值和没有沉淀产生(100％防垢剂)的钙值为基准计算。此实验得到如表1所示的结果。
表1
实施例2
| 浓度为1mg/l的防垢作用 | 浓度为5mg/l的防垢作用 | |
| CMI DS＝1.0 | 88 | 100 |
| CMI DS＝2.0 | 21 | 100 |
| 聚丙烯酸酯4500 | 60 | 100 |
确定CMI(DP约等于10)对硫酸钙的防垢作用。将氯化钙溶液和硫酸钠溶液混合制得一种饱和硫酸钙溶液，且所形成的硫酸钙溶液思的最大量为95毫克/升。将1毫克/升、5毫克/升或10毫克/升的防垢剂加入该溶液。溶液PH值调节到7.0，然后在30℃静置。20小时后用RedBand漏斗过滤，确定滤液的钙含量。防垢剂的作用以不加防垢剂(0％防垢剂)实验的钙值和没有沉淀产生(100％防垢剂)的钙值为基准计算。此实验得到如表2所示的结果。
表2
实施例3
| 浓度为1mg/l的防垢作用 | 浓度为5mg/l的防垢作用 | 浓度为10mg/l的防垢作用 | |
| CMI DS＝1.0 | 11.7 | 77.8 | 90.5 |
| CMI DS＝2.0 | 23.1 | 90.0 | 93.0 |
| 磷酸盐 | 35.9 | 87.6 | 89.2 |
| 聚丙烯酸酯4500 | 29.1 | 89.7 | 92.4 |
重复实施例2(硫酸钙结垢抑制)，只是溶液是7天后而不是20小时后过滤。结果如表3所示。
表3
实施例4
| 浓度为1mg/l时的防垢作用(％) | 浓度为5mg/l时的防垢作用(％) | 浓度为10mg/l时的防垢作用(％) | |
| CMI DS＝1.0 | 5.2 | 81.0 | 87.3 |
| CMI DS＝2.0 | 8.0 | 92.4 | 93.9 |
| 磷酸盐 | 2.7 | 56.9 | 86.9 |
| 聚丙烯酸酯4500 | 5.3 | 88.6 | 89.6 |
确定CMI(DP约等于10)对硫酸钡的防垢作用。将氯化钙溶液(380mg/l)和硫酸钠溶液(3350mg/l)以1∶1比例混合制得一种饱和硫酸钡溶液，所形成的硫酸钡溶液的最大量是210毫克/升。将5毫克/升、10毫克/升或15毫克/升的防垢剂加入该溶液。溶液PH值通过加入每100毫升含1毫升醋酸盐的缓冲液(每100毫升含13.6克醋酸钠三水合物和0.5克醋酸)调节到5.5，然后在80℃静置。10小时后真空过滤使其通过0.45um的Milipore过滤器，确定滤液的钡含量。防垢剂的作用以不加防垢剂(0％防垢剂)实验的钡值和没有沉淀产生(100％防垢剂)的钡值为基准计算。结果列于表4中。
表4
实施例5
| 浓度为5mg/l的防垢作用 | 浓度为10mg/l的防垢作用 | 浓度为15mg/l的防垢作用 | |
| CMI DS＝1.0，DP＝10 | 15.0 | 27.5 | 57.5 |
| CMI DS＝2.0，DP＝10 | 78.0 | 96.5 | 100 |
| CMI DS＝2.0，DP＝20 | 82.5 | 98.0 | 100 |
| 五聚磷酸盐(DETPMP) | 18.0 | 38.5 | 55.5 |
重复实施例4，除了硫酸钡溶液含有38毫克/升的Fe2+。结果列于表5中。
表5
| 浓度为5mg/l的防垢作用 | 浓度为10mg/l的防垢作用 | 浓度为15mg/l的防垢作用 | |
| CMI DS＝2.0，DP＝10 | 75.0 | 92.0 | 98.5 |
| CMI DS＝2.0，DP＝20 | 80.5 | 96.0 | 99.0 |
| 五聚磷酸盐(DETPMP) | 12.0 | 21.5 | 34.5 |
Claims (12)
1.一种在石油开采中使用一种聚羧基化合物防止结垢结垢沉积的方法，其特征在于在处理用水、处理设备或含油地层中引入了每个单糖单元含0.3-3个羧基的含羧基果聚糖。
2.如权利要求1所述的方法，其中将含羧基果聚糖以0.5-200ppm的浓度加入到处理用水中。
3.如权利要求2所述的方法，其中将含羧基果聚糖以2-50ppm的浓度加入到处理用水中。
4.如权利要求1或2所述的方法，其中含羧基果聚糖每单糖单元至少含有0.8个羧基。
5.如权利要求1或2所述的方法，其中含羧基果聚糖每单糖单元至少含有0.7-2.5个羧甲基。
6.如权利要求1或2所述的方法，其中含羧基果聚糖是平均聚合度为6-60的一种羧甲基旋复花粉。
7.如权利要求1或2所述的方法，其中结垢结垢包括钙盐、钡盐/或锶盐。
8.如权利要求1或2所述的方法，其中结垢包括碳酸盐/或硫酸盐。
9.如权利要求1或2所述的方法，其中结垢包括铁盐。
10.如权利要求1或2所述的方法，其中使用了一种直接从果聚糖羧烷基化得到的产物。
11.如权利要求1或2所述的方法，其中使用了一种纯净的羧烷基果聚糖；
12.如权利要求1或2所述的方法，其中处理用水是海水。
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| US8758556B2 (en) * | 2009-04-07 | 2014-06-24 | Dequest Ag | Composition for inhibiting calcium salt scale formation |
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| US20130269937A1 (en) * | 2012-04-12 | 2013-10-17 | Halliburton Energy Services, Inc. | Acidizing Fluids Comprising a Salt Block Inhibitor and Methods for Use Thereof |
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| US9963366B2 (en) * | 2013-03-15 | 2018-05-08 | Stephen R. Temple | Methods for treating liquid streams containing quaternary ammonium compounds |
| WO2016014310A1 (en) | 2014-07-23 | 2016-01-28 | Baker Hughes Incorporated | Composite comprising well treatment agent and/or a tracer adhered onto a calcined substrate of a metal oxide coated core and a method of using the same |
| US10641083B2 (en) | 2016-06-02 | 2020-05-05 | Baker Hughes, A Ge Company, Llc | Method of monitoring fluid flow from a reservoir using well treatment agents |
| US10413966B2 (en) | 2016-06-20 | 2019-09-17 | Baker Hughes, A Ge Company, Llc | Nanoparticles having magnetic core encapsulated by carbon shell and composites of the same |
| WO2018156154A1 (en) * | 2017-02-27 | 2018-08-30 | General Electric Company | Sulfate scale inhibition in high pressure and high temperature applications |
| WO2019013799A1 (en) | 2017-07-13 | 2019-01-17 | Baker Hughes, A Ge Company, Llc | SYSTEM FOR DELIVERING OLEO-SOLUBLE WELL PROCESSING AGENTS AND METHODS OF USE THEREOF |
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| CA3079526C (en) | 2017-11-03 | 2022-06-28 | Baker Hughes, A Ge Company, Llc | Treatment methods using aqueous fluids containing oil-soluble treatment agents |
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| NO20006173D0 (no) | 2000-12-05 |
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| TR200003659T2 (tr) | 2001-06-21 |
| EP1093541B2 (en) | 2010-08-25 |
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| DE69908128T2 (de) | 2003-12-18 |
| NZ508679A (en) | 2003-02-28 |
| CA2334782C (en) | 2007-12-18 |
| DK1093541T3 (da) | 2003-06-23 |
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| HUP0102433A3 (en) | 2003-01-28 |
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| NO20006173L (no) | 2001-02-07 |
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| PT1093541E (pt) | 2003-09-30 |
| EP1093541A1 (en) | 2001-04-25 |
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| HUP0102433A2 (hu) | 2001-10-28 |
| EP1093541B1 (en) | 2003-05-21 |
| IL140086A0 (en) | 2002-02-10 |
| DE69908128D1 (de) | 2003-06-26 |
| ES2197691T3 (es) | 2004-01-01 |
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