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Oil-based drilling fluids, favored for their superior stability and inhibitive properties in complex deep oil and gas strata, is constrained by a scarcity of efficient materials for leak prevention and plugging, thereby limiting their utilization. In response to this challenge, a homogenous and stable polymer, SMHDVD, was synthesized via solution polymerization, using acrylate monomers as the primary chain and incorporating functional monomers that offer resistance to high temperatures and enhanced bonding with the formation. The impact of different concentrations (0.1%, 0.3%, and 0.5%) of the crosslinking agent divinylbenzene on the polymer SMHDVD was also investigated. In-house plugging experiments have shown that SMHDVD significantly contributes to the plugging efficacy of oil-based drilling fluid systems, with a maximum reduction in cumulative drilling fluid loss of up to 68.7%, surpassing the performance of conventional plugging materials. It was observed through comparative studies that the incorporation of a crosslinking agent diminishes the sealing capacity of SMHDVD, and an increase in the crosslinking agent's concentration leads to a decline in the polymer's plugging performance. The polymeric plugging agent developed in this research offers a novel perspective for the prevention of oil-based drilling fluid leakage, with promising prospects for practical field application.

, correspAuthors=Yi-fu LONG, authorNote=null, correspAuthorsNote=null, copyrightStatement=null, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, authorCompany=null, fund=null, authors=null, authorsList=Yi-fu LONG, Jin-sheng SUN, Ren-tong LIU, Da-peng ZOU, Xiao-xiao NI, Jian-hua WANG, Xiao-bo CUI, Li-li YANG), CN=ArticleExt(id=1149773909454709737, articleId=1149773874411299836, tenantId=1146029695717560320, journalId=1146123166801305609, language=CN, title=油基钻井液用聚合物防漏剂的制备与应用, columnId=1156262729603207500, journalTitle=科学技术与工程, columnName=论文·石油、天然气工业, runingTitle=null, highlight=null, articleAbstract=

油基钻井液体系因其良好的稳定性和抑制性多应用于深层油气复杂的地层,但是高效防漏堵漏材料的匮乏限制了油基钻井液的使用。针对上述问题,首次提出以丙烯酸酯单体为主链,引入抗高温、增强与地层黏结性的功能单体,采用溶液聚合方法合成了均一稳定的聚合物防漏剂,同时引入不同浓度的交联剂乙二烯基苯,并研究其浓度对于聚合物防漏剂的影响。室内防漏实验结果评价表明,聚合物防漏剂对油基钻井液体系具有良好的防漏作用,钻井液累计漏失量降低率最高可达68.7%,明显优于常规防漏材料。通过对比实验,发现交联剂的引入会降低防漏剂的封堵能力,且随着交联剂浓度的增大,聚合物防漏效果呈变差趋势。所制备的聚合物防漏剂为预防油基钻井液漏失问题提供了新的思路,具有较高的现场应用潜力。

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龙一夫(1990—),男,汉族,黑龙江大庆人,博士,高级工程师。研究方向:钻井液智能材料研发、井筒强化、防漏堵漏、储层保护等。E-mail:

, authorsList=龙一夫, 孙金声, 刘人铜, 邹大鹏, 倪晓骁, 王建华, 崔小勃, 杨丽丽)}, authors=[Author(id=1175114045125443730, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1149773874411299836, orderNo=0, firstName=null, middleName=null, lastName=null, nameCn=null, orcid=null, stid=null, country=null, authorPic=null, dead=0, email=longyfdr@cnpc.com.cn, emailSecond=null, emailThird=null, correspondingAuthor=0, authorType=1, ext={EN=AuthorExt(id=1175114045200941207, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1149773874411299836, authorId=1175114045125443730, language=EN, stringName=Yi-fu LONG, firstName=Yi-fu, middleName=null, lastName=LONG, prefix=null, suffix=null, authorComment=null, nameInitials=null, affiliation=null, department=null, xref=1, 2, address=1 China Petroleum Engineering Technology Research Institute Co. , Ltd. , Beijing 102206, China
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龙一夫(1990—),男,汉族,黑龙江大庆人,博士,高级工程师。研究方向:钻井液智能材料研发、井筒强化、防漏堵漏、储层保护等。E-mail:

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龙一夫(1990—),男,汉族,黑龙江大庆人,博士,高级工程师。研究方向:钻井液智能材料研发、井筒强化、防漏堵漏、储层保护等。E-mail:

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figureFileBig=HVMc9QSutaas6qbmUNMRSQ==, tableContent=null), ArticleFig(id=1175114048812237052, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1149773874411299836, language=EN, label=Fig.7, caption=Comparison of OBDF with SMHDVD and conventional materials, figureFileSmall=wKQc+XZz3TGdLJ0aR5l7og==, figureFileBig=IGXOvdR5r3Hj2t6juqpMJw==, tableContent=null), ArticleFig(id=1175114048896123134, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1149773874411299836, language=CN, label=图7, caption=SMHDVD和常规防漏材料封堵效果对比, figureFileSmall=wKQc+XZz3TGdLJ0aR5l7og==, figureFileBig=IGXOvdR5r3Hj2t6juqpMJw==, tableContent=null), ArticleFig(id=1175114048996786432, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1149773874411299836, language=EN, label=Fig.8, caption=Experimental results of API filtration loss and mud cake of OBDF, figureFileSmall=3iqhFy05MsDadfylVsPZ7A==, figureFileBig=HwhUPBPwRee+XpwWQJr0gw==, tableContent=null), ArticleFig(id=1175114049059700994, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1149773874411299836, language=CN, label=图8, caption=不同OBDF的中压滤失性能和泥饼照片, figureFileSmall=3iqhFy05MsDadfylVsPZ7A==, figureFileBig=HwhUPBPwRee+XpwWQJr0gw==, tableContent=null), ArticleFig(id=1175114049193918724, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1149773874411299836, language=EN, label=Fig.9, caption=Experimental results of HTHP filtration loss and mud cake of OBDF, figureFileSmall=dVNSV+xfVD5g9uueonqZjA==, figureFileBig=uRYhOaMhhCjQ77eJiXcCGw==, tableContent=null), ArticleFig(id=1175114049256833286, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1149773874411299836, language=CN, label=图9, caption=不同OBDF的高温高压滤失性能和泥饼照片, figureFileSmall=dVNSV+xfVD5g9uueonqZjA==, figureFileBig=uRYhOaMhhCjQ77eJiXcCGw==, tableContent=null), ArticleFig(id=1175114049328136456, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1149773874411299836, language=EN, label=Fig.10, caption=Filtration loss of field OBDF with 1% SMHDVD in different sand disks, figureFileSmall=P2ZyBWpcMtwqWAGFmjNyFw==, figureFileBig=sEzT3sG0tewld7uXdaKkew==, tableContent=null), ArticleFig(id=1175114049386856714, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1149773874411299836, language=CN, label=图10, caption=添加1% SMHDVD的OBDF在不同砂盘中的降漏失性能, figureFileSmall=P2ZyBWpcMtwqWAGFmjNyFw==, figureFileBig=sEzT3sG0tewld7uXdaKkew==, tableContent=null), ArticleFig(id=1175114049479131404, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1149773874411299836, language=EN, label=Table1, caption=

Rheology performance of OBDF with different SNHDVD polymers

, figureFileSmall=null, figureFileBig=null, tableContent=
OBDF
类型
测试
时间
转速/
(r·min-1)
表观
黏度/
(mPa·s)
PV/
(mPa·s)
YP/
Pa
破乳
电压
/V
基浆 老化前 59/38
29/20
7/6
29.5 21 8.5 792
老化后 57/37
28/20
7/6
28.5 20 8.5 771
+1%SMHDVD,
+0%DVB
老化前 90/56
44/30
12/11
41.5 30 11.5 980
老化后 94/58
45/30
12/11
47.5 36 11.5 746
+1%SMHDVD,
+0.1%DVB
老化前 97/61
46/32
12/11
43.5 31 12.5 868
老化后 111/68
51/32
8/7
46 34 12 708
+1%SMHDVD,
+0.3%DVB
老化前 96/62
45/30
12/11
45 34 11 854
老化后 107/65
49/31
9/8
49.5 37 12.5 694
+1%SMHDVD,
+0.5%DVB
老化前 95/60
46/31
9/8
47.5 35 12.5 982
老化后 102/64
50/34
13/11
51 38 13 727
), ArticleFig(id=1175114049571406094, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1149773874411299836, language=CN, label=表1, caption=

OBDF的流变性能数据表

, figureFileSmall=null, figureFileBig=null, tableContent=
OBDF
类型
测试
时间
转速/
(r·min-1)
表观
黏度/
(mPa·s)
PV/
(mPa·s)
YP/
Pa
破乳
电压
/V
基浆 老化前 59/38
29/20
7/6
29.5 21 8.5 792
老化后 57/37
28/20
7/6
28.5 20 8.5 771
+1%SMHDVD,
+0%DVB
老化前 90/56
44/30
12/11
41.5 30 11.5 980
老化后 94/58
45/30
12/11
47.5 36 11.5 746
+1%SMHDVD,
+0.1%DVB
老化前 97/61
46/32
12/11
43.5 31 12.5 868
老化后 111/68
51/32
8/7
46 34 12 708
+1%SMHDVD,
+0.3%DVB
老化前 96/62
45/30
12/11
45 34 11 854
老化后 107/65
49/31
9/8
49.5 37 12.5 694
+1%SMHDVD,
+0.5%DVB
老化前 95/60
46/31
9/8
47.5 35 12.5 982
老化后 102/64
50/34
13/11
51 38 13 727
), ArticleFig(id=1175114049697235216, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1149773874411299836, language=EN, label=Table 2, caption=

Comparison of electrical stability of different OBDF

, figureFileSmall=null, figureFileBig=null, tableContent=
老化时
间/h
老化
温度/℃
测试
时间点
破乳电压/V
未加入
SMHDVD
1%
SMHDVD
16 120 老化前 792 806
老化后 771 846
32 120 老化前 786 798
老化后 754 812
48 120 老化前 802 820
老化后 788 852
), ArticleFig(id=1175114049802092819, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1149773874411299836, language=CN, label=表2, caption=

不同OBDF的电稳定性对比

, figureFileSmall=null, figureFileBig=null, tableContent=
老化时
间/h
老化
温度/℃
测试
时间点
破乳电压/V
未加入
SMHDVD
1%
SMHDVD
16 120 老化前 792 806
老化后 771 846
32 120 老化前 786 798
老化后 754 812
48 120 老化前 802 820
老化后 788 852
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油基钻井液用聚合物防漏剂的制备与应用
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龙一夫 1, 2 , 孙金声 1, 2 , 刘人铜 1 , 邹大鹏 3 , 倪晓骁 1, 2 , 王建华 1, 2 , 崔小勃 1 , 杨丽丽 4
科学技术与工程 | 论文·石油、天然气工业 2025,25(13): 5400-5407
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科学技术与工程 | 论文·石油、天然气工业 2025, 25(13): 5400-5407
油基钻井液用聚合物防漏剂的制备与应用
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龙一夫1, 2 , 孙金声1, 2, 刘人铜1, 邹大鹏3, 倪晓骁1, 2, 王建华1, 2, 崔小勃1, 杨丽丽4
作者信息
  • 1 中国石油集团工程技术研究院有限公司, 北京 102206
  • 2 油气钻完井技术国家工程研究中心, 北京 102206
  • 3 大庆钻探工程公司钻井液公司, 大庆 163453
  • 4 中国石油大学(北京)安全与海洋工程学院, 北京 102249
  • 龙一夫(1990—),男,汉族,黑龙江大庆人,博士,高级工程师。研究方向:钻井液智能材料研发、井筒强化、防漏堵漏、储层保护等。E-mail:

Preparation and Application of Polymer Plugging Gel for Oil-based Drilling Fluid
Yi-fu LONG1, 2 , Jin-sheng SUN1, 2, Ren-tong LIU1, Da-peng ZOU3, Xiao-xiao NI1, 2, Jian-hua WANG1, 2, Xiao-bo CUI1, Li-li YANG4
Affiliations
  • 1 China Petroleum Engineering Technology Research Institute Co. , Ltd. , Beijing 102206, China
  • 2 National Engineering Research Center for Petroleum Drilling and Completion Technology, Beijing 102206, China
  • 3 Drilling Fluid Company of CNPC Daqing Drilling Engineering Company, Daqing 163453, China
  • 4 College of Safety and Ocean Engineering, China University of Petroleum(Beijing), Beijing 102249, China
出版时间: 2025-05-08 doi: 10.12404/j.issn.1671-1815.2403852
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油基钻井液体系因其良好的稳定性和抑制性多应用于深层油气复杂的地层,但是高效防漏堵漏材料的匮乏限制了油基钻井液的使用。针对上述问题,首次提出以丙烯酸酯单体为主链,引入抗高温、增强与地层黏结性的功能单体,采用溶液聚合方法合成了均一稳定的聚合物防漏剂,同时引入不同浓度的交联剂乙二烯基苯,并研究其浓度对于聚合物防漏剂的影响。室内防漏实验结果评价表明,聚合物防漏剂对油基钻井液体系具有良好的防漏作用,钻井液累计漏失量降低率最高可达68.7%,明显优于常规防漏材料。通过对比实验,发现交联剂的引入会降低防漏剂的封堵能力,且随着交联剂浓度的增大,聚合物防漏效果呈变差趋势。所制备的聚合物防漏剂为预防油基钻井液漏失问题提供了新的思路,具有较高的现场应用潜力。

油基钻井液  /  聚合物  /  防漏剂  /  降滤失剂  /  交联剂

Oil-based drilling fluids, favored for their superior stability and inhibitive properties in complex deep oil and gas strata, is constrained by a scarcity of efficient materials for leak prevention and plugging, thereby limiting their utilization. In response to this challenge, a homogenous and stable polymer, SMHDVD, was synthesized via solution polymerization, using acrylate monomers as the primary chain and incorporating functional monomers that offer resistance to high temperatures and enhanced bonding with the formation. The impact of different concentrations (0.1%, 0.3%, and 0.5%) of the crosslinking agent divinylbenzene on the polymer SMHDVD was also investigated. In-house plugging experiments have shown that SMHDVD significantly contributes to the plugging efficacy of oil-based drilling fluid systems, with a maximum reduction in cumulative drilling fluid loss of up to 68.7%, surpassing the performance of conventional plugging materials. It was observed through comparative studies that the incorporation of a crosslinking agent diminishes the sealing capacity of SMHDVD, and an increase in the crosslinking agent's concentration leads to a decline in the polymer's plugging performance. The polymeric plugging agent developed in this research offers a novel perspective for the prevention of oil-based drilling fluid leakage, with promising prospects for practical field application.

oil-based drilling fluid  /  polymer  /  loss circulation material  /  filtrate reducer  /  crosslinker
龙一夫, 孙金声, 刘人铜, 邹大鹏, 倪晓骁, 王建华, 崔小勃, 杨丽丽. 油基钻井液用聚合物防漏剂的制备与应用. 科学技术与工程, 2025 , 25 (13) : 5400 -5407 . DOI: 10.12404/j.issn.1671-1815.2403852
Yi-fu LONG, Jin-sheng SUN, Ren-tong LIU, Da-peng ZOU, Xiao-xiao NI, Jian-hua WANG, Xiao-bo CUI, Li-li YANG. Preparation and Application of Polymer Plugging Gel for Oil-based Drilling Fluid[J]. Science Technology and Engineering, 2025 , 25 (13) : 5400 -5407 . DOI: 10.12404/j.issn.1671-1815.2403852
井漏是指井下作业中各种工作液在压差作用下直接进入地层的一种井下复杂情况。钻井液漏失事故不仅会延误钻井工程进度,还会对油气储层造成损害,从而带来不可估量的经济损失[1]。目前,针对不同的漏失情况,专家学者们提出很多堵漏理论,并已研制出多种堵漏材料来解决钻井液漏失事故[2]。然而由于井漏问题的复杂多样性,尤其是在泥页岩地层、湿陷性地层以及宽度较大的裂缝性地层中,目前还没有成熟有效的预防和治理井漏的方法[3]。油基钻井液具有良好的润滑性、泥页岩抑制性和高效的井眼清洁效率,已广泛应用于高温深层和复杂区块的非常规油气资源开采[4]。然而,由于缺乏合适的防漏堵漏材料,油基钻井液(oil based drilling fluid, OBDF)的漏失问题难以解决。目前针对OBDF的漏失问题主要以预防为主,虽然有不少将有效水基钻井液(water based drilling fluid, WBDF)用防漏堵漏材料直接应用于油基钻井液的尝试,但由于配伍性差、不抗温、不抗盐等因素,效果均不理想[5-6]。因此,借鉴现有水基防漏材料的封堵机理,开发适用于OBDF的堵漏材料意义重大。
目前国内外堵漏材料种类多样,但主要应用于WBDF[7],主要包括桥接堵漏材料、无机胶凝堵漏材料、高失水堵漏材料、化学堵漏材料及复合体系堵漏材料[5]。其中,桥接堵漏材料主要通过不同形状、尺寸、浓度的材料复配,实现对地层的桥堵作用,在油基和水基钻井液中均可使用[6]。常用的水泥堵剂通过固化,形成承压能力较高的堵漏带以实现堵漏目的,但存在被地层中的液相冲蚀、稀释而失去效果的风险,主要用于WBDF [8]。高失水堵漏材料通过快速失水作用形成渗透率较低的堵漏层,从而降低漏失速率[9]
化学类堵漏材料对不同孔隙度的地层适用性好、种类多、热稳定性和润滑性好、不会出现假堵现象,应用非常广泛[10]。王照辉等[11]采用自由基聚合的方法,引入耐温性单体,研制了热稳定性良好的聚丙烯酰胺型树脂,封堵承压能力超过10 MPa。李红梅等[12]研发了一种耐温性超过150 ℃的高分子吸油树脂YDLJ-1,其在室温下5 h可膨胀5倍,承压能力大于15 MPa,应用于堵漏体系可大幅缩短作业时间,缓解钻井液漏失情况。张新民等[13]针对恶性漏失研发了新型特种凝胶ZND,其作用机理是聚合物链在水溶剂中通过相互作用发生缠绕,在漏失通道中失去流动性而形成凝胶,阻隔地层流体和WBDF。该材料已在多个区块应用,堵漏效果显著。文献[14-17]针对传统堵漏剂滞留能力差、承压能力低、易复漏等不足,研发了智能堵漏材料——自修复凝胶堵漏剂,通过动态链形成的交联的三维聚合物网络体系,具有温度、压力双重响应特性,在进入漏失层后可吸水膨胀、充填堆积。该材料在井下自发愈合,在裂缝中胶结形成一体化的、无缝隙的整体,有效提高一次堵漏成功率。其温度、压力响应范围分别为40~150 ℃、2~10 MPa,自修复时间可在6~14 h范围内调控。总的来说,目前聚合物防漏堵漏材料的合成单体多为丙烯酰胺、丙烯酸等,主要用于WBDF防漏堵漏,而可用于油基堵漏的化学防漏材料还不多见。
基于现有WBDF防漏堵漏机理[18-21],现研发一种适用于OBDF的聚合物防漏剂,通过系统的表征、评价和优化,形成科学高效的OBDF防漏体系。由于目前聚合物防漏材料在OBDF中的应用甚少,所研发的具有多极性的共聚物SMHDVD在OBDF中显示出巨大的应用潜力,有望应用于钻井现场防止井漏问题,对类似领域开发高性能防漏材料和技术具有重大意义。
受聚合物防漏材料在钻井过程中能够防止WBDF漏失的启发,采用一锅法制备了聚合物防漏剂来预防、减缓OBDF的漏失。针对高温高压地层的防漏需求,创新设计并合成了防漏聚合物聚苯乙烯-6-甲基庚基甲基丙烯酸-N,N-二甲基丙烯酰胺-乙烯基醋酸-二乙烯基苯(styrene-6-methyl heptyl methacrylate-N, N dimethyl acrylamide-vinyl acetate-divinylbenzene,SMHDVD),通过微观形貌观察、粒径分析、傅里叶变换红外光谱仪(Fourier transform infrared spectrometer,FTIR)分析和热稳定性分析系统地研究了SMHDVD的物理化学性质。
化学试剂:过硫酸铵[(NH4)2S2O8,≥98%]、氢氧化钠(NaOH,≥98%)无水氯化钙(CaCl2,≥98%)、氧化钙(CaO,≥98%)等试剂由萨恩化学有限公司提供,丙烯酸酯类单体(≥99%)和乙二烯基苯(DVB)由北京华威锐科化工有限公司提供,功能性单体由北京伊诺凯科技有限公司提供,有机土、沥青、碳酸钙、橡胶颗粒、弹性石墨、白油(3#)、重晶石均由石大博城科技有限公司提供。
实验仪器:高温高压失水仪、电动六速黏度计等均购自青岛同春石油仪器有限公司,高温老化罐及变频滚子加热炉购自江苏拓创科研仪器有限公司。
采用溶液聚合法合成了聚合物SMHDVD,首先将丙烯酸酯类单体和功能性单体加入装有机械搅拌棒(400 r/min)的去离子水中,充分混合。缓慢滴加(NH4)2S2O8水溶液引发聚合反应,滴加速率均为0.5滴/s。最后,在65 ℃、氮气气氛下恒温反应8 h,将所得聚合物离心后置于烘箱中烘干至恒重,即得聚合物SMHDVD。分别引入不同浓度(0.1%、0.3%和0.5%)的交联剂DVB来合成不同聚合物,通过表征和评价实验研究交联剂对聚合物SMHDVD性能的影响。聚合物示意图如图1所示。
通过光学显微镜(DM4M,Leica,Germany)观察SMHDVD的微观结构。4种不同交联剂浓度的聚合物微观形貌如图2所示。聚合物SMHDVD呈球形或不规则形状的颗粒,分布均匀。
通过激光粒度仪(LA-960S,Horiba,Japan)表征了SMHDVD的粒径分布。所有样品的浓度约为10.0 g/L。4种不同交联剂浓度的聚合物的粒径分布曲线如图3所示。不含交联剂DVB的聚合物颗粒平均粒径为0.5 μm,而含有DVB的聚合物颗粒尺寸较大,含有0.1%、0.3%和0.5%DVB的SMHDVD平均粒径分别为148.9、158.6和178.0 μm,随着交联剂加量的增加,SMHDVD的粒径呈递增趋势。这是因为高浓度的交联剂会提供更多的交联位点,各个单体会聚合成体积较大的聚合物颗粒。而不含交联剂的聚合物则是凭借功能性单体引入不相溶的聚合物序列,通过较高的极性形成相互连接的结构域,促进网络结构的形成。
聚合物SMHDVD的化学结构通过傅里叶变换红外光谱(FT-IR,Magna IR 560,Nicolet,USA)表征,波数范围为400~4 400 cm-1,分辨率为4 cm-1。不同交联剂浓度的聚合物的FT-IR曲线如图4所示。
由于不含DVB和含有DVB的聚合物结构以及官能团相似,因此红外图谱上的特征峰出现的位置也高度一致。位于2 956.9、2 927.4和2 858.9 cm-1附近的峰分别代表不对称甲基C—H的伸缩振动、不对称亚甲基C—H的伸缩和对称亚甲基C—H的伸缩振动;1 722.8 cm-1处的C=O特征振动峰证实了SMHDVD中功能单体的存在;1 460 cm-1处的峰与DVB中苯环骨架的伸缩振动有关。3 000~3 600 cm-1的峰为吸收水峰。此外,1 380~1 490 cm-1处的峰为亚甲基的面内弯曲振动吸收峰。因此,SMHDVD的特征峰表明所有单体都成功发生聚合反应。
聚合物SMHDVD干样的热稳定性通过热重分析(TGA,STA 449F5,Netzsch,Germany)进行探究,温度范围为20~600 ℃,加热速率为10 ℃/min,在氮气气氛中测试。不同交联剂浓度的聚合物的热重分析(thermogravimetric analysis, TGA)和微分热重(DTG)曲线如图5所示。不含交联剂的SMHDVD在温度达到325.5 ℃时开始热分解,聚合物中的官能团开始分解,主链和侧链发生断裂降解,基本结构逐渐被破坏。而含有交联剂的SMHDVD在温度达到347.8 ℃时开始热分解,略高于前者。由此可见,交联剂DVB的引入对聚合物的热稳定性影响不大。
通过砂盘来模拟OBDF在弱胶结地层中的漏失情况,借助电动六速黏度计、破乳电压测试仪、高温高压滤失仪和中压滤失仪来系统评价聚合物SMHDVD对OBDF防漏性能以及其他性能的影响。出于环保因素考虑,使用由饱和烷烃组成的白油作为基础油用于OBDF性能评价和机理研究。如无特殊说明,所使用OBDF基浆配方为:3#白油+3%主乳化剂+3%辅乳化剂+1.5%润湿剂+3%有机土+2%CaO+25%盐水+重晶石。
钻井液流变性是钻井液的一项基本性能,合理稳定的流变性对于携带岩屑,保证井底和井眼的清洁、悬浮岩屑与重晶石、提高机械钻速和安全高-效钻井至关重要。通过电动六速黏度计分别记录了120 ℃下老化16 h前后OBDF的三、六转读数,计算出表观黏度(AV)、塑性黏度(PV)和动切力(YP),并使用电稳定测试仪测定OBDF的电稳定性,结果如表1所示。
基浆的流变性能在老化前后保持稳定,加入1% SMHDVD并在120 ℃下老化16 h后,几乎所有的流变参数均有所增加,并且随着交联剂加量的增加,黏度增加幅度更大。这是由于聚合物SMHDVD的加入不仅产生了与3#白油之间一定强度的相互作用,增强了形成空间网架结构的能力,还增加了OBDF中固体颗粒之间运动产生的摩擦力。含有高浓度交联剂的SNHDVD与白油之间的相互作用力更大,吸油膨胀后对OBDF的流变性能影响更大。
为了研究含有不同浓度DVB的聚合物SMHDVD对OBDF封堵性能的影响,通过砂盘封堵实验,采用40 μm和150 μm的砂盘模拟120 ℃高温下OBDF在固结地层中的漏失情况,记录60 min的OBDF累计漏失量。实验结果如图6所示。
实验结果表明,聚合物SMHDVD对不同孔隙度的地层均有高效的封堵能力。对于40 μm砂盘,含有SMHDVD的OBDF累计漏失量降低率由高到低依次为:不含DVB(68.7%)>0.1%DVB(67.2%)>0.3%DVB(53.1%)>0.5%DVB(51.6%),说明封堵能力随着交联剂加量的增加而减弱。另外,在150 μm砂盘中含有SMHDVD的OBDF也呈现出相似规律,累计漏失量降低率由高到低依次为:不含DVB(53.7%)>0.1%DVB(26.8%)>0.3%DVB(19.5%)>0.5%DVB(17.1%)。由此可见,交联剂的引入对SMHDVD的封堵性能有一定的削弱,这可能是因为DVB在一定程度上破坏了聚合物的化学结构,导致SMHDVD与油溶剂的相互作用减弱。
为了进一步评价SMHDVD的封堵能力,将封堵能力最优的不含DVB的聚合物SMHDVD与目前常见的防漏材料进行对比,包括超细碳酸钙(以600目∶800目∶1 000目=1∶1∶1的比例复配)、氧化沥青、弹性石墨和橡胶颗粒。分别选用40 μm和150 μm的砂盘,通过砂盘漏失实验记录基浆和含各种LCM的OBDF老化16 h后在120 ℃下的60 min累计漏失量。实验结果如图7所示。
实验结果表明所有材料均能起到填充和封堵地层孔隙的作用,然而它们的封堵效果存在一定差异。对于40 μm砂盘,含聚合物SMHDVD、氧化沥青、复配超细碳酸钙、弹性石墨和橡胶颗粒的OBDF累计漏失量降低率分别为68.7%、15.6%、53.1%、29.7%和25.0%。当砂盘孔隙尺寸为150 μm时,只有SMHDVD显著降低了漏失量,其他材料对地层的封堵效果甚微。含聚合物SMHDVD、氧化沥青、复配超细碳酸钙、弹性石墨和橡胶颗粒的OBDF累计漏失量降低率分别为53.66%、19.51%、21.95%、12.20%和7.32%。由此可知,含有聚合物SMHDVD的OBDF的封堵效果明显优于其他防漏材料。
滤失性能是钻井液的重要性能,在OBDF循环过程中须将滤失量控制在合理范围内。在120 ℃下将所有OBDF老化16 h后,进行中压滤失(API)和高温高压滤失(HTHP)实验,以此来评价聚合物SMHDVD的降滤失性能。实验结果如图8图9所示。
图8(a)可知,不同交联剂加量的OBDF的API滤失量分别为不含DVB(83.3%)、0.1%DVB (50.3%)、0.3%DVB(33.3%)、0.5%DVB(33.4%),结果表明SMHDVD能够明显的降低OBDF体系的滤失量,同时随着交联剂DVB的升高,其滤失量升高,可见降滤失效果变差。由图8(b)图8(c)可知,纯OBDF和含1% SMHDVD的OBDF产生的滤饼都很薄且光滑。因此,加入聚合物SMHDVD有利于提高OBDF的滤失性能。
为了考察OBDF体系在高温条件下的滤失造壁性能,采用高温高压滤失仪对聚合物SMHDVD的降滤失性能进行进一步研究。从图9(a)HTHP滤失量来看,不同类型的OBDF累计滤失量降低率分别为不含DVB(62.5%)、0.1%DVB(60.9%)、0.3%DVB(57.8%)、0.5%DVB(56.3%),结果表明SMHDVD可以显著降低OBDF的HTHP滤失量,并且交联剂加量对其滤失性能影响不大。由图9(b)图9(c)可知,实验过程中产生的滤饼薄且光滑致密,显示出OBDF良好的失水造壁性能。因此,以上实验结果表明聚合物SMHDVD加入OBDF体系中具有降滤失的作用,聚合物SMHDVD的加入可以高效降低OBDF体系的HTHP滤失量。
中压滤失和高温高压滤失实验表明聚合物SMHDVD不仅是一种高效的防漏剂,还具备降滤失和维持井壁稳定的作用。
上述实验结果表明,不含DVB的聚合物SMHDVD的防漏性能最为优异。为了探究SMHDVD与井浆的配伍性,选用不含DVB的聚合物SMHDVD,加入多次循环后的井浆中并评价SMHDVD的防漏能力。加入1% SMHDVD在120 ℃下老化16 h后,分别进行不同尺寸的砂盘堵漏实验,对比评价聚合物SMHDVD对钻井现场老浆封堵能力的影响。
砂盘堵漏实验结果如图10所示。对于40 μm砂盘,纯OBDF和含有聚合物SMHDVD的OBDF的累计漏失量分别为3.5 mL和1.5 mL,OBDF累计漏失量降低率为58.24%;而对于150 μm砂盘,纯OBDF和含有聚合物SMHDVD的OBDF的累计漏失量分别为4.2 mL和3 mL,OBDF累计漏失量降低率为28.57%,由此可见,聚合物SMHDVD可以井浆在弱胶结地层中钻进、循环过程中的封堵能力。
防漏剂除了需要具备优良配伍性、封堵性和降滤失性之外,还需要长期稳定以保证长时间循环后钻井液性能稳定。通过电稳定性测试考察了纯OBDF和含聚合物SMHDV的OBDF在120 ℃老化16、32和48 h前后的乳液稳定性,记录电极击穿OBDF乳液时的电压,实验结果如表2所示。随着老化时间的延长,纯OBDF和含聚合物SMHDVD的OBDF的电稳定性在120 ℃下老化前后的波动范围为14~22 V,处于正常范围,相同条件下含聚合物SMHDVD的OBDF电稳定性比纯OBDF略高一点。因此,可以认为聚合物SMHDVD对OBDF的长期稳定性有一定积极影响。
聚合物SMHDVD防漏剂随OBDF一同循环进入高温漏失通道后,聚丙烯酸酯烷基链开始剧烈运动,在分子间相互作用力下白油逐渐进入聚合物颗粒的亲油内核,聚合物SMHDVD颗粒因此随OBDF进入高温地层后吸油膨胀,相互缠绕,形成具有一定机械强度的大体积油凝胶,充填地层孔隙,增加OBDF的黏附性,使地层-聚合物以及地层-地层之间更加牢固地结合在一起,提升地层的承压能力,和井壁表面形成的泥饼一起高效减缓OBDF的漏失,维持井壁稳定,大大减少OBDF向地层中渗漏。聚合物SMHDVD随着交联剂加量的增加,形成的聚合物颗粒平均粒径更大,SMHDVD对地层的适应能力下降,封堵能力有所减弱。总而言之,超分子聚合物SMHDVD作为防漏剂引入OBDF体系显示出巨大的应用潜力,也为钻井现场的防漏堵漏工作提供了一些思路。
(1)采用溶液聚合物合成了聚合物防漏剂SMHDVD,热稳定性良好,防漏效果显著,可以满足120 ℃环境下的防漏需求。
(2)交联剂DVB在一定程度上削弱SMHDVD的封堵能力,随着DVB加量加大,聚合物颗粒粒径变大,防漏能力变差。
(3)SMHDVD加入OBDF体系中能够起到降低体系的滤失量的作用。
(4)聚合物SMHDVD的加入可以提升钻井现场长时间使用后的OBDF对弱交接地层的封堵能力。
(5)聚合物SMHDVD合成工艺简单,具有“广谱封堵”的特性,显示出作为油基钻井液防漏材料的巨大应用潜力。
  • 油气钻完井技术国家工程研究中心2023年度科学研究基金(F2023181)
  • 国家重点研发计划重点专项(2023YFF0611104)
  • 中国石油集团工程技术研究院有限公司科学研究与技术开发课题(CPET202316)
  • 中国石油重大科技专项(2023ZZ20)
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2025年第25卷第13期
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doi: 10.12404/j.issn.1671-1815.2403852
  • 接收时间:2024-05-24
  • 首发时间:2025-07-09
  • 出版时间:2025-05-08
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  • 收稿日期:2024-05-24
  • 修回日期:2025-01-15
基金
油气钻完井技术国家工程研究中心2023年度科学研究基金(F2023181)
国家重点研发计划重点专项(2023YFF0611104)
中国石油集团工程技术研究院有限公司科学研究与技术开发课题(CPET202316)
中国石油重大科技专项(2023ZZ20)
作者信息
    1 中国石油集团工程技术研究院有限公司, 北京 102206
    2 油气钻完井技术国家工程研究中心, 北京 102206
    3 大庆钻探工程公司钻井液公司, 大庆 163453
    4 中国石油大学(北京)安全与海洋工程学院, 北京 102249
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2种不同金属材料的力学参数

Family
属数
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genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)

Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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