CN104592958B - 一种油基钻井液用粉状乳化剂 - Google Patents

一种油基钻井液用粉状乳化剂 Download PDF

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CN104592958B
CN104592958B CN201410602478.1A CN201410602478A CN104592958B CN 104592958 B CN104592958 B CN 104592958B CN 201410602478 A CN201410602478 A CN 201410602478A CN 104592958 B CN104592958 B CN 104592958B
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drilling fluid
oil base
cooh
base drilling
emulsified dose
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CN104592958A (zh
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刘明华
王阳
张滨
孙举
王中华
万龙
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China Petrochemical Corp
Drilling Engineering Technology Research Institute of Sinopec Zhongyuan Petroleum Engineering Co Ltd
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China Petrochemical Corp
Drilling Engineering Technology Research Institute of Sinopec Zhongyuan Petroleum Engineering Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/02Well-drilling compositions
    • C09K8/03Specific additives for general use in well-drilling compositions
    • C09K8/035Organic additives
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D213/00Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/72Nitrogen atoms
    • C07D213/75Amino or imino radicals, acylated by carboxylic or carbonic acids, or by sulfur or nitrogen analogues thereof, e.g. carbamates
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/02Well-drilling compositions
    • C09K8/32Non-aqueous well-drilling compositions, e.g. oil-based

Abstract

本发明涉及一种油基钻井液用粉状乳化剂,属于油田钻井液用处理剂合成技术领域,由2,6二氨基吡啶、COOH—(CH2b—COOH二元酸、NH2—(CH2a—NH2二元胺和CH3(CH2c—COOH脂肪酸按照摩尔比1:2:2:1的比例混合后,控制反应温度140℃~150℃,3次共聚反应时间皆为3~5h,常温下粉碎得到粉状乳化剂,本发明通过基团间的氢键作用力,形成内作用力强、聚集态结构固体乳化剂。在0℃~120℃条件下为固体粉末,乳化能力强,抗温达180℃,产品易包装和运输,现场容易操作,能够更好地满足现场施工需要。

Description

一种油基钻井液用粉状乳化剂
技术领域
本发明涉及一种油基钻井液用粉状乳化剂,属于油田钻井液用处理剂合成技术领域。
背景技术
油基钻井液具有润滑性好、抗高温、抗污染能力强、抑制性好及保护油气层的优势,成为钻遇强水敏地层、易坍塌地层及巨厚盐膏层的首选体系。乳化剂是油基钻井液的核心处理剂,用于保证钻井液的乳化稳定性、流变性,对油基钻井液的性能好坏起到了重要作用。
目前国内油基钻井液用乳化剂多为液态,CN1597836A公布了一种油基钻井液用液态可转向乳化剂,该乳化剂在使用时形成油包水乳液,在清洗时可以转变为具有亲水性质,含油钻屑易于清洗;党庆功等在《油田化学》2008年25卷4期的“油基钻井液用乳化剂CET的研制”介绍了乳化剂CET,采用的是Ru2199570公布的专利技术,由油脂加工废料与有机碱为原料合成的可降解液态乳化剂,用其配制的油基钻井液体系,滤失量较低,乳化稳定性较好。但液态乳化剂现场应用中存在低温下增稠,现场操作困难,包装运输困难,增加了运输成本,且产品不易储存和计量等问题。
发明内容
本发明的目的在于克服现有液态乳化剂低温下增稠、现场操作困难、运输成本高等问题,而提供了一种油基钻井液用粉状乳化剂。
本发明由2,6二氨基吡啶、二元酸、二元胺和脂肪酸按照摩尔比1:2:2:1的比例混合后,控制反应温度140℃~150℃,3次共聚反应时间皆为3~5h,常温下粉碎得到粉状乳化剂,具有以下结构式为:
式中,
R1是通式为NH2—(CH2)a—NH2的二元胺,a=2,3,……10;
R2是通式为COOH—(CH2)b—COOH的二元酸,b=1,3,……8;
R3是通式为CH3(CH2)c—COOH的脂肪酸,c=10,11,12,13。
所述的二元胺类单体R1是通式为NH2—(CH2)a—NH2的二元胺,a=2,3,……10中的一种。
所述的二元酸类单体R2是通式为COOH—(CH2)b—COOH的二元酸,b=1,3,……8中的一种。
所述脂肪酸类单体R3是通式为CH3(CH2)c—COOH(c=10,11,12,13)的脂肪酸中的一种。
本发明的有益效果:本发明通过基团间的氢键作用力,形成内作用力强、聚集态结构固体乳化剂。在0℃~120℃条件下为固体粉末,乳化能力强,抗温达180℃,产品易包装和运输,现场容易操作,能够更好地满足现场施工需要。
具体实施方式
下面结合具体实施例对本发明及其效果做进一步说明。
实施例1
将0.5mol的乙二胺与0.5mol的葵二酸混合均匀,在140℃条件下,共聚反应3h,然后加入0.25mol的2,6二氨基吡啶在140℃条件下,共聚反应3h,再加入0.25mol十二酸共聚反应3h,自然冷却后得固体产物,粉碎即可得油基钻井液用粉状乳化剂,其结构式为:
实施例2
将1.0mol的葵二胺与1.0mol的丁二酸混合均匀,在140℃条件下,共聚反应4h,然后加入0.5mol的2,6二氨基吡啶在140℃条件下,共聚反应4h,再加入0.5mol十三酸共聚反应4h,自然冷却后得固体产物,粉碎即可得油基钻井液用粉状乳化剂,其结构式为:
实施例3
将0.8mol的己二胺与0.8mol的己二酸混合均匀,在150℃条件下,共聚反应5h,然后加入0.4mol的2,6二氨基吡啶在150℃条件下,共聚反应5h,再加入0.4mol十四酸共聚反应5h,自然冷却后得固体产物,粉碎即可得油基钻井液用粉状乳化剂,其结构式为:
实施例4-9的反应物成分如表1所示:
表1 实施例4-9反应组分表(以单位为摩尔mol)
为了进一步说明本发明的效果,将实施例样品进行综合评价。
1、理化指标
表2 本发明产品的理化指标
项目 指标
外观 浅黄色流动性粉末
密度,g/cm<sup>3</sup> 0.98~1.0
熔点,℃ 120
HLB值 1.5~2.5
破乳电压,V &gt;600
乳化率,% &gt;90
2、乳化性能
将实施例1反应得到的本发明产品配制不同油水比的乳状液,乳状液配方:240mL柴油(0号)+60mL蒸馏水+2%实施例1产品+2%有机土,180℃老化16h后,50℃测定破乳电压和乳化率,然后乳状液倒入500mL量筒中,静置24h,观察分离出油层的体积V(mL),按照乳化率=(300-V)/300×100%计算;不同油水比乳化效果如表3所示,破乳电压大于625V,乳化率为100%。
表3 实施例1产品对不同油水比乳液的影响
油水比 破乳电压,V 乳化率,%
9:1 1056 100
8:2 984 100
7:3 625 100
3、配浆性能
按照GB/T16783.2-2013的要求测定油基钻井液的各项性能,将实施例1反应得到的本发明产品配制油基钻井液,基本配方:300mL油水体积比为8:2的基液+3%实施例1产品+3%有机土+4%氧化沥青+3%CaO+400g重晶石,密度1.6g/cm3,180℃老化16h后,实验结果见表4。
表4 实施例1产品在柴油基不同油水比钻井液性能
注:AV为表观粘度,PV为塑性粘度,YP为动切力,FL为常压虑失量,ES为破乳电压,Q10s/Q10min为初终切。
由表4可知,当实施例1产品加量为3%、油水比为7:3时,钻井液动塑比为0.433,剪切稀释性好,破乳电压为456V,乳液稳定性好,由此可见,本发明具有良好的流变性和乳液稳定性。
综上所述,本发明在0℃~120℃条件下为固体粉末,乳化能力强,乳化率为100%,抗温达180℃,在不同油水比钻井液中具有良好的流变性和乳液稳定性。

Claims (4)

1.油基钻井液用粉状乳化剂,其特征在于:由2,6二氨基吡啶、二元酸、二元胺和脂肪酸按照摩尔比1:2:2:1的比例混合后,控制反应温度140℃~150℃,3次共聚反应时间皆为3~5h,常温下粉碎得到粉状乳化剂,具有以下结构式为:
式中,R1的通式为NH2—(CH2)a—NH,a=2,3,4,5,6,7,8,9,10;
R2的通式为OC—(CH2)b—CO,b=1,3,4,5,6,7,8;
R3的通式为CH3(CH2)c—CO,c=10,11,12,13;
R4的通式为NH—(CH2)a—NH,a=2,3,4,5,6,7,8,9,10。
2.根据权利要求1所述的油基钻井液用粉状乳化剂,其特征是:所述二元胺的通式为NH2—(CH2)a—NH2,a=2,3,4,5,6,7,8,9,10。
3.根据权利要求1所述的油基钻井液用粉状乳化剂,其特征是:所述二元酸的通式为COOH—(CH2)b—COOH,b=1,3,4,5,6,7,8。
4.根据权利要求1所述的油基钻井液用粉状乳化剂,其特征是:所述脂肪酸的通式为CH3(CH2)c—COOH,c=10,11,12,13。
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CN107916093A (zh) * 2016-10-08 2018-04-17 中石化石油工程技术服务有限公司 一种乳化剂及其制备方法和油基钻井液
CN109517587A (zh) * 2017-09-19 2019-03-26 中石化石油工程技术服务有限公司 一种生物质合成基钻井液及其制备方法
CN107652951A (zh) * 2017-11-06 2018-02-02 中国石油集团川庆钻探工程有限公司 一种用于钻井液的聚酰胺抑制剂的制备方法
CN109097005B (zh) * 2018-08-09 2021-06-04 大庆市北华化工厂 一种油基钻井液乳化剂
CN114605973A (zh) * 2020-12-08 2022-06-10 中石化石油工程技术服务有限公司 一种高密度、高动塑比的油基钻井液
CN113684008B (zh) * 2021-09-26 2022-11-11 荆州嘉华科技有限公司 一种油基钻井液用固体乳化剂及其制备方法和应用

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