CN1443780A - 配体改性的纤维素产物 - Google Patents
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- C08B11/00—Preparation of cellulose ethers
- C08B11/20—Post-etherification treatments of chemical or physical type, e.g. mixed etherification in two steps, including purification
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Abstract
本发明涉及一种配体改性的纤维素产物，它包含纤维素醚、钙盐和至少一种作为螯合剂的配体。本产物可以用于如钻井流体。
Description
发明领域
本发明涉及包含纤维素醚和配体的改性的纤维素产物。本发明也涉及一种制备改性的纤维素产物的方法，以及含这些产物的钻井流体。
发明背景
当钻孔开采油、天然气、水或其它下层土目标时，钻孔过程最通常是用装备了称作钻头的设备的旋转管进行的。该系统依赖于底部连接了多个狭长钻头的钻管柱的旋转。钻头钻入土壤，当钻孔不断进行时导致碎屑聚集。因此，必需使用一种流体将这些碎屑带到表面清除，从而允许钻头继续工作并且使洞底总是保持清洁而没有碎屑。
当钻孔过程进行时，钻井流体必需保护洞壁，使其不会由于沉积物或形成物与流体和该流体的其它含有元素的反应而导致变形和/或变质。这些化学和物理反应是由于反渗透和/或结晶作用导致的。这一方面的一个特定问题叫做页岩水合。
页岩是一类主要为粘土的矿物质，能与在钻孔过程中出现或在地下的水和盐起反应。该反应可能会阻碍钻孔过程，最坏的情况下此过程必须完全停止。
页岩是属于近晶组的矿石。最有名的是蒙脱石。通常这是粘土形成中最活跃的成分，当暴露于水环境时导致被称作溶胀的流体力学体积的增加并且在钻孔时带来问题。
伊利石、高岭石和绿泥石是是许多因离子和水与这些粘土反应而造成问题的活性粘土类的其它成员。这些粘土可以是高度分散的。在自然界中，这些粘土以混合的组合物形式存在，当钻孔时造成严重程度或轻或重的潜在问题。
页岩稳定化被认为至少部分依赖于通过流体抑制页岩的溶胀和分散过程。
页岩和页岩反应广泛描述于文献中，如：Van Olphen，H.，″AnIntroduction to Clay Colloid Chemistry″，second edition，JohnWiley & Sons，New York，19977，p.30-；以及Darley，H.C.H.andGray，George R.，″Compositions and Properties of Drilling andCompletion Fluids″5th edition，Gulf Publishing Company，Houston，p.140-。
一些纤维素衍生物是已知的钻井流体添加剂。它们可以具有页岩抑制、增稠、减少流体损失和热稳定特性。特别是羧甲基纤维素(CMC)已被用作这种添加剂。
发明概述
本发明的改性纤维素产物包含纤维素醚，如羧甲基纤维素、羧甲基羟乙基纤维素或羧甲基化淀粉，至少一种选自次氮基三乙酸、乙二胺四乙酸、1，2-环己烷二胺-N，N，N’，N’-四乙酸、二亚乙基三胺五乙酸、亚乙二氧基二(亚乙次氮基)四乙酸、N-(2-羟乙基)-乙二胺-N，N’，N”-三乙酸、三亚乙基四胺六乙酸、N-(羟乙基)乙二胺三乙酸的配体，以及至少一种钙盐。
于是，本产物包含钙源[如CaCl2.2H2O或Ca(OH)2]。本产物可以特别作为钻井流体的添加剂。本产物的应用导致了没有水合有害作用的更稳定的页岩形成。钙离子在产物制备或使用中对环境无害。使用中的另一优点是钙不是两性的。
本发明的产物也可以用于钻井流体以外的应用。这种应用的例子为造纸、涂料、采矿、药品、水净化、陶器、清洁剂和油漆。
本发明的另一目的是制备改性的纤维素产物的方法，此方法的特征在于纤维素化合物与至少一种钙盐和至少一种上述配体反应。
本发明的第三个目的是含新产物的钻井流体。
本发明的第四个目的是通过在钻孔过程中使用新产物来抑制钻孔过程中页岩水合。
本发明的第五个独立目的是由纤维素醚和上述配体组成的产物。此配体可以以单价盐，如钠盐的形式存在。当没有二价阳离子存在时，配体形成与纤维素醚分子的直接连接。发明详述
用于本发明的纤维素醚可以是例如羧甲基纤维素、羧甲基羟乙基纤维素或羧甲基化淀粉。特别是可以使用羧甲基纤维素。
认为，在新产物中钙离子与纤维素分子的醚基团和配体连接。
纤维素醚的聚合程度影响产物的粘度。聚合程度越高，得到的产物粘度越高。适当的聚合程度为如200-4000。
醚取代度为如0.5-1.7，特别是0.9-1.5。
使用的盐量特别是在0.1-20wt-％，优选0.1-15wt-％，最优选0.1-5wt-％的范围，以干纤维素计算。使用的配体量特别是在0.1-20wt-％，优选0.1-5wt-％的范围，以干纤维素计算。
根据本发明的一种优选实施方案，配体为次氮基三乙酸。
本发明的产物可以以工业形式(technical form)或以纯化形式获得。以工业形式存在时，它可以含如1-45％wt-％的氯化钠和/或甘醇酸钠。以纯化形式存在时它可以含有含量为95-100wt-％，如大于98wt-％的活性成分。
本产物也可以包含至少一种Mg2+，Cr3+，Fe2+，Fe3+，Al3+，Ti4+，Zn2+，Sn2+，Be2+，Sr2+，Ba2+或Ra2+盐。
此化合物可以作为所谓的“一袋产物”使用，因此它在应用过程中非常灵活多用。
本产物可以通过将纤维素或其衍生物与钙盐和配体反应而制备。这可以通过如纤维素与钙盐和配体在40-80℃的高温下反应而完成。
本发明的钻井流体通过产物与其它必要的添加剂混合而容易地制备。改性的纤维素产物的浓度为如0.1-15kg/m3。钻井流体的补充水可以是淡水或蒸馏水，海水或盐饱和水或其混合物。
本发明的改性CMC产物在所谓分散试验中的页岩抑制行为证明此产物比常规CMC更有效。
本发明的钻井流体也可以包含1，2-乙二醇和/或氯化钾(KCL)或其它盐，如Mg2+，Cr3+，Fe2+，Fe3+，Al3+，Ti4+，Zn2+，Sn2+，Be2+，Sr2+，Ba2+或Ra2+盐。
生产
关于纤维素醚的生产有许多文献。纤维素醚一般是这样制备的：将基于木或基于棉纤维的原材料与反应介质如醇(如异丙醇或乙醇)或丙酮混合，并用碱物质如氢氧化钠将其碱化从而激活纤维素。然后加入醚化的化合物如液态一氯代乙酸(MCA)或它的钠盐(NaMCA)并令其反应。如果需要可以中和产生的产物并减小其粘性。当生产纯化的纤维素醚后，用醇洗掉反应产生的副产物如盐。副产物也可以留在产物中(工业纤维素醚)或仅去除一部分(半纯化纤维素醚)。分离掉使用的溶剂并干燥产物。视预期最终用途而定，将产物研磨、造粒或筛分。
产物中如羧甲基纤维素部分的替代度取决于此过程的反应动力学和一氯代乙酸或其钠盐的浓度以及使用的纤维素类型。
可以在干燥产物之前反应的任何点加入本发明的钙化合物和络合剂，但优选在送入醚化化合物后反应开始时加入。
实施例
下列实施例1和3表示含Ca和配体的产物的制备，实施例5表示仅含配体的产物的制备，实施例2和4表示不合Ca和配体的产物的制备。
实施例1
将5kg木浆(Mestsa Botnia)、2.111kg NaMCA和9.089kg醇溶剂加入反应器并混合。可以选择给反应器提供氮气氛。加入用2.980kg水稀释的2.980kg氢氧化钠，将纤维素在45℃碱化25分钟。加入用0.587kg水稀释的2.346kg MCA。将温度升高到65℃。当温度升高后，加入用320ml水稀释的124g CaCl2.2H2O和222ml次氮基三乙酸的三钠盐(40wt％的水溶液)。反应在65℃进行总共60分钟。在反应之后，回收溶剂并将产物干燥至含湿量小于8wt％。
实施例2
将105g木浆(Mestsa Botnia)、1234g醇溶剂和18g水在备有混合器和任选氮气氛的密闭玻璃烧瓶中混合。将烧瓶置于水浴中。加入用63g水稀释的63g氢氧化钠将纤维素在20℃碱化30分钟。加入用18g水稀释的72g一氯代乙酸。将温度升高到70℃，反应在70℃进行90分钟。用乙醇将产物洗涤三次。在洗涤步骤之间通过过滤将滤液与产物分开。在洗涤之后，回收溶剂并将产物干燥至含湿量小于8wt％。
实施例3
将105g木浆(Mestsa Botnia)、1234g醇溶剂和18g水在备有混合器和任选氮气氛的密闭玻璃烧瓶中混合。将烧瓶置于水浴中。加入用63g水稀释的63g氢氧化钠将纤维素在20℃碱化30分钟。加入用18g水稀释的72g一氯代乙酸。将温度升高到70℃。当温度升高后，加入1.5g CaCl2.2H2O和3ml次氮基三乙酸的三钠盐(40wt％的水溶液)。此后反应在70℃进行90分钟。用乙醇将产物洗涤三次。在洗涤步骤之间通过过滤将滤液与产物分开。在洗涤之后，回收溶剂并将产物干燥至含湿量小于8wt％。
实施例4
将5kg木浆(Mestsa Botnia)、2.111kg NaMCA和9.089kg醇溶剂加入反应器并混合。可以选择给反应器提供氮气氛。加入用2.980kg水稀释的2.980kg氢氧化钠，将纤维素在45℃碱化25分钟。加入用0.587kg水稀释的2.346kg MCA。将温度升高到65℃。反应在65℃总共进行60分钟。在反应之后，回收溶剂并将产物干燥至含湿量小于8wt％。
实施例5
将5kg木浆(Mestsa Botnia)、2.111kg NaMCA和9.089kg醇溶剂加入反应器并混合。可以选择给反应器提供氮气氛。加入用2.980kg水稀释的2.980kg氢氧化钠将纤维素在45℃碱化25分钟。加入用0.587kg水稀释的2.346kg MCA。将温度升高到65℃。当温度升高后，加入222ml次氮基三乙酸的三钠盐(40wt％的水溶液)。反应在65℃总共进行60分钟。在反应之后，回收溶剂并将产物干燥至含湿量小于8wt％。
表1.实施例产物的典型参数
试验室结果分散试验(热滚动试验)
| 实施例 | 取代度 | 以mPas表示的2wt-％水溶液的粘度 | pH |
| 1 | 1.16 | 110 | 11.4 |
| 2 | 1.09 | 29 | 10.6 |
| 3 | 1.08 | 25 | 10.5 |
| 4 | 1.16 | 41 | 11.5 |
| 5 | 1.23 | 42 | 11.4 |
作为页岩抑制试验，进行了所谓的分散试验。本试验的目的是判断钻井流体系统对粘土分散和页岩水合解体的抑制特性。
在热的滚动储气瓶(体积500ml)中，将100g碾碎和干燥的粘土小片悬浮于钻井流体(钻井流体的组成不同)。储气瓶用氮气加压。然后在以约40rpm滚动的所谓热轧炉中在95℃(203°F)下将储气瓶热滚动16小时。
在陈化之后，降温样品并且当储气瓶达到室温时释放压力，打开储气瓶。将内容物倒在1.18mm的有接收器的筛子上。然后用冷的淡水洗涤筛子上的小片以便从小片上清除粘连的泥。然后在烘箱内干燥小片直到恒重。
筛上回收的物质越多，钻井流体的抑制作用越强。
除非试验介质相同，这种试验方法不能用于比较一种泥系统与另一种泥系统。实际上，只有同时进行试验的样品，其结果才能彼此比较。
用此描述的分散试验检验了上面提到的实施例中产生的样品。在所有试验中，将4.5g样品加入350ml钻井流体。结果列于表2。
表2.实施例1和对比的实施例4的样品(工业样品)的页岩抑制试验结果
| 产物 | 回收wt.％ |
| 实施例1的样品 | 70.6 |
| 实施例4的样品(0-样品) | 53.5 |
表3.实施例2和实施例3的样品(纯化样品)的页岩抑制试验结果
| 产物 | 回收wt.％ |
| 实施例2的样品(0-样品) | 65.5 |
| 实施例3的样品 | 73 |
表4.实施例4和实施例5的样品(工业样品)的页岩抑制试验结果
| 产物 | 回收wt.％ |
| 实施例4的样品(0-样品) | 60.8 |
| 实施例5的样品 | 63.6 |
Claims (14)
1.一种配体改性的纤维素产物，包含纤维素醚，如羧甲基纤维素、羧甲基羟乙基纤维素或羧甲基化淀粉，其特征在于它进一步包含至少一种钙盐和至少一种选自次氮基三乙酸、乙二胺四乙酸、1，2-环己烷二胺-N，N，N’，N’-四乙酸、二亚乙基三胺五乙酸、亚乙二氧基二(亚乙次氮基)四乙酸、N-(2-羟乙基)-乙二胺-N，N’，N”-三乙酸、三亚乙基四胺六乙酸、N-(羟乙基)乙二胺三乙酸及其混合物的配体。
2.权利要求1的产物，其中使用的钙盐量在0.1-20wt-％，优选0.1-15wt-％，最优选0.1-5wt-％的范围，以干纤维素计算。
3.前面任意一项权利要求的产物，其中使用的配体量在0.1-20wt-％，优选0.1-5wt-％的范围，以干纤维素计算。
4.前面任意一项权利要求的产物，其中配体为次氮基三乙酸。
5.前面任意一项权利要求的产物，其中纤维素醚为羧甲基纤维素。
6.前面任意一项权利要求的产物，其中它是以工业形式存在，含如2-45wt-％的氯化钠和/或甘醇酸钠。
7.前面任意一项权利要求的产物，其中它是以纯化形式存在，活性成分的含量优选为95-100wt-％。
8.一种制备配体改性的纤维素产物的方法，其特征在于纤维素醚与至少一种钙盐和至少一种选自次氮基三乙酸、乙二胺四乙酸、1，2-环己烷二胺-N，N，N’，N’-四乙酸、二亚乙基三胺五乙酸、亚乙二氧基二(亚乙次氮基)四乙酸、N-(2-羟乙基)-乙二胺-N，N’，N”-三乙酸、三亚乙基四胺六乙酸、N-(羟乙基)乙二胺三乙酸及其混合物的化合物反应。
9.一种钻井流体，其特征在于它含有权利要求1-7的任意一项的改性的纤维素产物或根据权利要求8制备的改性的纤维素产物。
10.权利要求9的钻井流体，其中改性的纤维素产物的浓度为0.1-15kg/m3。
11.权利要求9或10的钻井流体，其中它进一步含1，2-乙二醇。
12.权利要求9-11的任意一项的钻井流体，其中它进一步含一种盐，如KCl，用以增强页岩抑制。
13.一种抑制钻孔过程中页岩水合的方法，其特征在于使用了权利要求9-12的任意一项的钻井流体。
14.一种配体改性的纤维素产物，包含纤维素醚如羧甲基纤维素、羧甲基羟乙基纤维素或羧甲基化淀粉，其特征在于它进一步包含至少一种选自次氮基三乙酸、乙二胺四乙酸、1，2-环己烷二胺-N，N，N’，N’-四乙酸、二亚乙基三胺五乙酸、亚乙二氧基二(亚乙次氮基)四乙酸、N-(2-羟乙基)-乙二胺-N，N’，N”-三乙酸、三亚乙基四胺六乙酸、N-(羟乙基)乙二胺三乙酸及其混合物的配体。
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| FI20002039A FI111732B (fi) | 2000-09-15 | 2000-09-15 | Ligandimodifioitu selluloosatuote |
| EP01660148A EP1188772B1 (en) | 2000-09-15 | 2001-08-15 | Ligand-modified cellulose products |
| CA2374417A CA2374417C (en) | 2000-09-15 | 2002-03-04 | Ligand-modified cellulose products |
| US10/086,627 US6586587B1 (en) | 2000-09-15 | 2002-03-04 | Ligand-modified cellulose products |
| JP2002063785A JP4324720B2 (ja) | 2000-09-15 | 2002-03-08 | リガンド変性製品 |
| CN02107098.9A CN1229392C (zh) | 2000-09-15 | 2002-03-13 | 配体改性的纤维素产物 |
| BR0200773-8A BR0200773A (pt) | 2000-09-15 | 2002-03-13 | Produtos de celulose modificados por um ligando |
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| FI20002039A FI111732B (fi) | 2000-09-15 | 2000-09-15 | Ligandimodifioitu selluloosatuote |
| CA2374417A CA2374417C (en) | 2000-09-15 | 2002-03-04 | Ligand-modified cellulose products |
| US10/086,627 US6586587B1 (en) | 2000-09-15 | 2002-03-04 | Ligand-modified cellulose products |
| JP2002063785A JP4324720B2 (ja) | 2000-09-15 | 2002-03-08 | リガンド変性製品 |
| CN02107098.9A CN1229392C (zh) | 2000-09-15 | 2002-03-13 | 配体改性的纤维素产物 |
| BR0200773-8A BR0200773A (pt) | 2000-09-15 | 2002-03-13 | Produtos de celulose modificados por um ligando |
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| EP (1) | EP1188772B1 (zh) |
| JP (1) | JP4324720B2 (zh) |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101014681B (zh) * | 2004-08-06 | 2011-04-06 | 蓝宝迪有限公司 | 用于钻探工业的粘土抑制剂 |
| CN102773942A (zh) * | 2012-07-23 | 2012-11-14 | 北京中科日升科技有限公司 | 一种改性淀粉的处理方法 |
| CN103814104A (zh) * | 2011-08-30 | 2014-05-21 | 斯比凯可芬兰公司 | 纤维素产物的可选择的配体制剂 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2006013595A1 (en) * | 2004-08-06 | 2006-02-09 | Lamberti S.P.A. | Shale inhibitors for the petroleum industry |
| US9027647B2 (en) | 2006-08-04 | 2015-05-12 | Halliburton Energy Services, Inc. | Treatment fluids containing a biodegradable chelating agent and methods for use thereof |
| US9127194B2 (en) | 2006-08-04 | 2015-09-08 | Halliburton Energy Services, Inc. | Treatment fluids containing a boron trifluoride complex and methods for use thereof |
| US9120964B2 (en) | 2006-08-04 | 2015-09-01 | Halliburton Energy Services, Inc. | Treatment fluids containing biodegradable chelating agents and methods for use thereof |
| US8567504B2 (en) | 2006-08-04 | 2013-10-29 | Halliburton Energy Services, Inc. | Composition and method relating to the prevention and remediation of surfactant gel damage |
| WO2008139164A1 (en) * | 2007-05-10 | 2008-11-20 | Halliburton Energy Services, Inc. | Methods for stimulating oil or gas production |
| US8071511B2 (en) | 2007-05-10 | 2011-12-06 | Halliburton Energy Services, Inc. | Methods for stimulating oil or gas production using a viscosified aqueous fluid with a chelating agent to remove scale from wellbore tubulars or subsurface equipment |
| US20120161067A1 (en) * | 2010-12-22 | 2012-06-28 | Far Eastern New Century Corporation | Dental etching gel composition and method of use thereof |
| US8881823B2 (en) | 2011-05-03 | 2014-11-11 | Halliburton Energy Services, Inc. | Environmentally friendly low temperature breaker systems and related methods |
| US9334716B2 (en) | 2012-04-12 | 2016-05-10 | Halliburton Energy Services, Inc. | Treatment fluids comprising a hydroxypyridinecarboxylic acid and methods for use thereof |
| US20140186626A1 (en) * | 2012-09-19 | 2014-07-03 | Sinopec Research Institute Of Petroleum Engineering | Modified starch, preparation method and use of the same, and drilling fluid |
| US9670399B2 (en) | 2013-03-15 | 2017-06-06 | Halliburton Energy Services, Inc. | Methods for acidizing a subterranean formation using a stabilized microemulsion carrier fluid |
| US9164018B2 (en) * | 2013-04-01 | 2015-10-20 | Saudi Arabian Oil Company | Method for prediction of inhibition durability index of shale inhibitors and inhibitive drilling mud systems |
| CN115819629B (zh) * | 2022-11-21 | 2024-01-30 | 重庆力宏精细化工有限公司 | 一种耐高温抗盐纤维素醚及其制备方法和应用 |
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| US3762476A (en) * | 1972-01-03 | 1973-10-02 | Phillips Petroleum Co | Subterranean formation permeability correction |
| US4018286A (en) * | 1975-11-06 | 1977-04-19 | Phillips Petroleum Company | Controlled well plugging with dilute polymer solutions |
| US4657944A (en) * | 1984-02-09 | 1987-04-14 | Phillips Petroleum Company | CO2 -induced in-situ gelation of polymeric viscosifiers for permeability contrast correction |
| RU2001936C1 (ru) * | 1990-10-29 | 1993-10-30 | Волго-Уральский научно-исследовательский и проектный институт по добыче и переработке сероводородсодержащих газов | Буровой раствор |
| US5466680A (en) * | 1992-03-26 | 1995-11-14 | Cytologics, Inc. | Method and compositions for enhancing white blood cell functioning on a mucosal or cutaneous surface |
| DE69614555T2 (de) * | 1995-09-11 | 2002-04-11 | M-I L.L.C., Houston | Auf glykol basierende bohrflüssigkeit |
| FI114990B (fi) * | 1999-03-16 | 2005-02-15 | Noviant Oy | Modifioidut selluloosatuotteet |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101014681B (zh) * | 2004-08-06 | 2011-04-06 | 蓝宝迪有限公司 | 用于钻探工业的粘土抑制剂 |
| CN103814104A (zh) * | 2011-08-30 | 2014-05-21 | 斯比凯可芬兰公司 | 纤维素产物的可选择的配体制剂 |
| CN102773942A (zh) * | 2012-07-23 | 2012-11-14 | 北京中科日升科技有限公司 | 一种改性淀粉的处理方法 |
| CN102773942B (zh) * | 2012-07-23 | 2015-07-01 | 北京中科日升科技有限公司 | 一种改性淀粉的处理方法 |
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| Publication number | Publication date |
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| FI20002039A0 (fi) | 2000-09-15 |
| EP1188772A3 (en) | 2002-12-04 |
| CA2374417C (en) | 2010-11-30 |
| EP1188772B1 (en) | 2011-03-30 |
| US6586587B1 (en) | 2003-07-01 |
| EP1188772A2 (en) | 2002-03-20 |
| JP4324720B2 (ja) | 2009-09-02 |
| BR0200773A (pt) | 2003-10-21 |
| JP2003268002A (ja) | 2003-09-25 |
| CA2374417A1 (en) | 2003-09-04 |
| FI20002039A (fi) | 2002-03-16 |
| FI111732B (fi) | 2003-09-15 |
| CN1229392C (zh) | 2005-11-30 |
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