CN1487985A - 两性离子表面活性剂与阴离子型含醚表面活性剂一起作为减阻剂的应用 - Google Patents
两性离子表面活性剂与阴离子型含醚表面活性剂一起作为减阻剂的应用 Download PDFInfo
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- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
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Abstract
本发明涉及两性离子表面活性剂与醚硫酸盐或醚羧酸盐表面活性剂组合在水基体系中作为减阻剂的应用。该组合物除具有高减阻效果外,还具有对硬水的低敏感性。
Description
本发明涉及两性离子表面活性剂与醚硫酸盐或醚羧酸盐表面活性剂一起在水基体系中作为减阻剂的应用。
近年来,能形成特别长的圆柱形胶束的表面活性剂作为循环水体系,特别是旨在加热或冷却的配水体系的减阻添加剂引起了人们很大兴趣。
产生这种兴趣的一个重要原因在于,虽然人们希望管道中保持层流,但同时人们还希望在热交换器中存在湍流从而在其中实现每单位面积的高热转移。
如容易理解的那样,纤维或链形聚合物不能提供这样的双重功能,然而,用线形胶束则可以实现这样的双重功能,因为可导致减阻的胶束在热交换器内或者就在进入热交换器以前可通过机械装置破坏。这样,将在所述热交换器内产生湍流。在交换器后面的管道中,胶束将相当迅速地再次形成,于是恢复了减阻作用。
线状胶束的特点在于,在低雷诺数(低于104)下以完全无序的方式操作,对于流阻没有或只有很轻微的影响。在较高雷诺数(高于104)时,胶束平行排列,从而导致很接近于理论上可能的减阻作用。在甚至更高的雷诺数(例如,高于105)时,液体中的剪切力变得如此高,以致随着雷诺数增大到高于该值,胶束开始被破坏而减阻效果迅速降低。
表面活性剂具有显著减阻效果的雷诺数范围取决于浓度,该范围随浓度的增大而增大。
通过选定表面活性剂的正确浓度以及热交换器前方或热交换器内管道中合适的流速和适当的装置,就有可能建立管道内的层流和热交换器内的湍流。因此,管道的尺寸可保持在较低水平,或者,在保持相同的管道尺寸下,可以减小泵大小或泵站数,因而减小泵所作的功。
在WO 96/28527中公开了一种减阻剂,它包含与磺酸盐或硫酸盐表面活性剂组合的甜菜碱表面活性剂。该减阻剂在较大温度范围内是有效的。然而,硫酸盐表面活性剂对硬水相当敏感,而人们认为磺酸盐表面活性剂在厌氧条件下不容易被生物降解。
现在意外地发现,通过具有下式的两性离子表面活性剂,
其中R是含10~24个碳原子的饱和或不饱和脂族基或酰基的基团,R6和R7彼此独立是1~4个碳原子的烷基或2~4个碳原子的羟烷基,而R4是1~4个碳原子的亚烷基,优选是CH2或如下的基团
其中,R5是1~3个碳原子的烷基,与具有下列通式结构的阴离子醚表面活性剂或其混合物,
R1(OA)nB,R1O(AO)nCmH2mD或R3NH(AO)nCmH2mD其中,R1是10~24个碳原子的烃基,R3是10~24个碳原子的酰基,A是2~4个碳原子的亚烷基,n是1~10的数,m是1~4,B是硫酸盐基OSO3M,D是羧酸盐基COOM,而且M是阳离子的、优选是一价的基团,按两性离子表面活性剂与阴离子醚表面活性剂或醚表面活性剂的重量比为100∶1~1∶1、优选50∶1~2∶1的比例组合,作为减阻剂应用于流动的水基液体体系中,实现了实质性的改善。“水基”表示水基液体体系的至少50wt%、优选至少90wt%由水构成。所述两性离子表面活性剂和阴离子醚表面活性剂的总量可根据条件在宽范围内变动,但通常是0.1~10kg/m3水基体系。所述两性离子表面活性剂和阴离子醚表面活性剂的组合特别适用于在长管道中流动的用于散热或冷却的水基体系。
合适地,所述两性离子表面活性剂中的基团R是脂族基团或基团R′NHC3H6,其中R′表示10~24个碳原子的酰基。优选地,所述两性离子表面活性剂具有如下通式
其中,R是脂族基团或基团R′NHC3H6-,其中R′具有上述含义。在阴离子醚表面活性剂中,疏水基R1可以是脂族的或芳族的、直链的或支化的、饱和的或不饱和的。此外,基团A优选是1,2-亚乙基,n优选是1~5的数,而CmH2m优选是亚甲基或是基团
其中,R8是1~3个碳原子的烷基。基团M优选是钠和钾。
所述两性离子表面活性剂和阴离子醚表面活性剂都容易生物降解,并能耐硬水和电解质,而且所述组合物在宽温度范围内给出优良的减阻效果。因此,当使用其中基团R和R′具有12~16个碳原子的表面活性剂时,所述减阻添加剂可用于温度低于20℃的冷却介质中;当使用其中基团R和R′含有18、20或22或更多个碳原子的表面活性剂时,所述减阻添加剂可用于温度在50~120℃范围内的传热介质中。疏水基R、R′、R1和R3中的碳原子数将影响所述混合物的适用温度范围,结果,高碳数将给出适合高温度的产物,反之亦然。基团R和R1可以适当地是十二烷基、十四烷基、十六烷基、十八烷基、油基、二十烷基、二十二烷基、菜子油烷基和牛油烷基,而基团R′和R3是相应的酰基。还可应用芳族基,例如,壬基苯基。
此外,以这样一种方式合适地选择所述两性离子表面活性剂和阴离子型表面活性剂,使得所述组合物的结晶温度适当地低于预期的水基体系的最低温度。适当地,将所述两性离子表面活性剂与其中n是1~5,而OA是氧化乙烯的阴离子醚硫酸盐表面活性剂组合,因为醚硫酸盐容易生产,而且与两性离子表面活性剂组合可给出优良的减阻效果。
所述两性离子表面活性剂可这样生产,即,通过将式RNR6R7(其中,R具有上述含义)的化合物与氯乙酸钠在低级醇和水的介质中,在70~80℃和9.5的恒定pH值下反应。为了达到良好的减阻效果,重要的是,在使用的两性离子表面活性剂产品中胺反应物的量较低。如果要求产物中的氯化物含量较低,优选反应在具有尽可能低水含量的异丙醇中进行,这样反应时生成的氯化钠将从产物中结晶析出,并且可通过过滤或离心除去。获得无氯化物的产物的另一条途径是,在酸催化剂存在下使所述胺反应物与环氧乙烷季铵化,然后使生成的产物脱氢而得所需的两性离子表面活性剂。
适用于本发明的阴离子醚表面活性剂是人们熟知的产品,生产方法也是人们熟知的。典型实例有,通过用SO3硫酸化而得自乙氧基化醇的脂族单(氧化乙烯)硫酸盐、烷基二(氧化乙烯)硫酸盐和烷基三(氧化乙烯)硫酸盐,和通过所述乙氧基化醇与具有式HalCmH2mCOOM的卤代羧酸盐反应获得的相应的羧酸盐,其中Hal是氯或溴,而且M和m具有上述含义。酰氨基醚羧酸盐可按人们熟知的方法生产,包括所述卤代羧酸盐与酰氨基烷氧化物R3NH(AO)nH(其中,R3、A和n具有上述含义)的反应。
两性离子表面活性剂和阴离子醚表面活性剂的选择将取决于水基体系的温度。低温下的碳原子数通常将低于高温下的碳原子数,而在较低温度下的氧亚烷基数通常将比较高温度下的更高。
对于某种水来说,一种确定所述两性离子表面活性剂和阴离子表面活性剂的合适比率的简便方法是:在磁力搅拌下,在50ml玻璃烧杯中配制所述两性离子表面活性剂在适当水中的例如0.500kg/m3的溶液,并且将温度保持在该体系预期的温度范围的中间点。用浓度为10kg/m3的所述阴离子醚表面活性剂在适当水中的溶液滴定,直至原来形成的漩涡消失。
除了所述两性离子表面活性剂和阴离子表面活性剂以外,该水基体系还可包含一些常规组分,例如缓蚀剂、防冻剂和杀菌剂。
现在将借助于如下实施例进一步阐述本发明。
实施例1
减阻温度范围是在上述烧杯试验中确定的。在烧杯试验中,利用磁力搅拌器和加热板组合,以700r/min的恒定旋转速率搅拌所述表面活性剂混合物。不存在漩涡或最大2mm的漩涡等于减阻条件。在高于100℃的温度下,应用了玻璃耐压反应器。
制备了甜菜碱和阴离子表面活性剂的储备液混合物。在50ml烧杯中,用具有下表所示硬度的水稀释该混合物至1000ppm甜菜碱和40ml总体积。括号中以ppm为单位给出了阴离子表面活性剂的量。用氨水调节pH至9~10。
表1.用于加热体系的N-二十二烷基甜菜碱(1000ppm)
阴离子表面活性剂 | 减阻范围(700r/min) | ||
0°dH | 3°dH | 8°dH | |
十二烷基硫酸钠 | 55-120 (30) | 55-68 (30) | 55-68 (30) |
十二烷基-(EO)3-硫酸钠 | 55-123 (40) | 55-108 (40) | 50-78 (40) |
十二烷基酰胺-(EO)2-羧酸盐 | 55-104 (40) | 48-95 (40) | 49-86 (40) |
壬基酚-(EO)3-羧酸盐 | 53-97 (40) | 49-94 (40) | 49-74 (40) |
含阴离子醚表面活性剂的减阻剂在3°dH和8°dH水中比含烷基硫酸盐的减阻剂表现出本质上更好的减阻效果。
实施例2
该实施例是按前述筛选试验进行的。
为了确定阴离子表面活性剂的合适量,在试验烧杯中,在700r.p.m磁力搅拌下将所述甜菜碱溶液保持在13℃,并用所述阴离子表面活性剂水溶液滴定直至漩涡消失。在发现组合物给出减阻效果的温度范围后方的括号内以ppm为单位给出了阴离子表面活性剂的最后浓度。以℃为单位给出了溶液的澄清点(CP)。
该实施例的所有试验中应用的两性离子表面活性剂N-肉豆蔻基-甜菜碱的浓度是1000ppm。
表2.用于冷却体系的N-肉豆蔻基-甜菜碱(1000ppm)与阴离子表面活性剂混合物
阴离子表面活性剂 | 减阻范围(700r/min) | ||
0°dH | 3°dH | 8°dH | |
十二烷基苯磺酸盐 | 无效果(0-1130)CP 0℃ | 0-29 (430)CP 0℃ | 3-25 (980)CP 35℃ |
十二烷基-(EO)3-硫酸钠 | 0-43 (288)CP 0℃ | 0-27 (550)CP 0℃ | 2-25 (510)CP 2℃ |
十二烷基硫酸钠 | 6-43 (400)CP 6℃ | 0-39 (336)CP 14℃ | 4-43 (360)CP 20℃ |
这些配方旨在适配温度范围通常是4~15℃的冷却环路。
可以看到,十二烷基乙二醇醚硫酸盐在该温度范围内效果良好,而十二烷基苯磺酸盐配方在去离子水中没有给出减阻作用,而且十二烷基硫酸钠在低温下在8°dH的水中效果并不令人满意。
此外,在实际应用中,十二烷基硫酸钠的应用由于钠盐和钙盐的沉淀而受到阻碍。
Claims (10)
1.如下物质的组合作为减阻剂在流动的水基液体体系中的应用:
具有下式的两性离子表面活性剂
其中R是含10~24个碳原子的饱和或不饱和脂族基或酰基的基团,R6和R7彼此独立地是1~4个碳原子的烷基或2~4个碳原子的羟烷基,而R4是1~4个碳原子的亚烷基,
和具有下列通式结构的阴离子醚表面活性剂或其混合物
R1(OA)nB,R1O(AO)nCmH2mD或R3NH(AO)nCmH2mD
其中,R1是10~24个碳原子的烃基,R3是10~24个碳原子的酰基,A是2~4个碳原子的亚烷基,n是1~10的数,m是1~4,B是硫酸盐基OSO3M,而且D是羧酸盐基COOM,其中M是阳离子基,
所述两性离子表面活性剂与阴离子醚表面活性剂或醚表面活性剂的重量比为100∶1~1∶1。
3.权利要求1或2的应用,其特征在于,所述组合物的结晶温度低于所述水基体系的预期最低温度。
4.权利要求1~3中任一项的应用,其特征在于,所述两性离子表面活性剂和阴离子醚表面活性剂的添加总量为0.1~10kg/m3水基体系。
5.权利要求1、2、3或4的应用,其特征在于,所述水基体系是温度在50~120℃范围内的传热介质。
6.权利要求1、2、3或4的应用,其特征在于,所述水基体系是温度低于20℃的冷却介质。
7.权利要求1~5中任一项的应用,其特征在于,基团R和R′包含18~24个碳原子。
8.权利要求1~4和6中任一项的应用,其特征在于,基团R和R1包含12~16个碳原子。
9.权利要求1~8中任一项的应用,其特征在于,基团R4和CmH2m表示亚甲基。
10.权利要求1~9中任一项的应用,其特征在于,所述阴离子醚表面活性剂是醚硫酸盐,其中n是1~5,而OA是氧化乙烯。
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Cited By (6)
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CN104277819A (zh) * | 2013-07-09 | 2015-01-14 | 中国石油化工股份有限公司 | 页岩气藏压裂液降阻剂及其制备方法 |
CN104560000A (zh) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | 压裂液降阻剂组合物 |
CN105025713A (zh) * | 2013-03-14 | 2015-11-04 | 阿克佐诺贝尔化学国际公司 | 在脂肪链的羟基上烷氧基化的含氮表面活性剂 |
CN105086983A (zh) * | 2014-05-14 | 2015-11-25 | 中国石油化工股份有限公司 | 含甜菜碱表面活性剂的压裂液减阻剂及其制备方法和应用 |
CN106590610A (zh) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | 水基压裂液减阻剂及其应用 |
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SE0202198L (sv) * | 2002-07-15 | 2004-01-16 | Akzo Nobel Nv | A drag-reducing agent for use in injection water at oil recovery |
EP2032242B1 (en) * | 2006-05-24 | 2014-10-01 | Marine 3 Technologies Holdings (Pty) Ltd | A surface active ingredient composition |
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US5143635A (en) * | 1990-02-02 | 1992-09-01 | Energy, Mines & Resources - Canada | Hydraulic drag reducing agents for low temperature applications |
SE467826B (sv) * | 1991-01-31 | 1992-09-21 | Berol Nobel Ab | Anvaendning av alkoxilerad alkanolamid som friktionsreducerande medel |
US5389304A (en) * | 1992-06-03 | 1995-02-14 | Colgate Palmolive Co. | High foaming nonionic surfactant base liquid detergent |
SE503485C2 (sv) * | 1994-10-03 | 1996-06-24 | Akzo Nobel | Användning av en alkoxilerad alkanolamid tillsammans med en jonisk tensid som friktionsreducerande medel |
SE504086C2 (sv) | 1995-03-09 | 1996-11-04 | Akzo Nobel Nv | Användning av en alkylbetain tillsammans med en anjonisk ytaktiv förening som friktionsreducerande medel |
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CN108006438B (zh) * | 2017-12-13 | 2020-02-14 | 常州大学 | 一种湍流减阻剂及其制备方法 |
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