CN105408444A - 具有增强的颗粒间结合的支撑剂 - Google Patents
具有增强的颗粒间结合的支撑剂 Download PDFInfo
- Publication number
- CN105408444A CN105408444A CN201480040505.9A CN201480040505A CN105408444A CN 105408444 A CN105408444 A CN 105408444A CN 201480040505 A CN201480040505 A CN 201480040505A CN 105408444 A CN105408444 A CN 105408444A
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- Prior art keywords
- silane
- coating
- propping agent
- cas
- agent
- Prior art date
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- 238000000576 coating method Methods 0.000 claims abstract description 231
- 239000011248 coating agent Substances 0.000 claims abstract description 202
- 229920000642 polymer Polymers 0.000 claims abstract description 27
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 243
- -1 amino, sulfydryl Chemical group 0.000 claims description 59
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 57
- 229910000077 silane Inorganic materials 0.000 claims description 51
- 229920002396 Polyurea Polymers 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 36
- 239000000126 substance Substances 0.000 claims description 35
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 33
- 150000001412 amines Chemical class 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 30
- 150000002148 esters Chemical class 0.000 claims description 25
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 20
- MCEBKLYUUDGVMD-UHFFFAOYSA-N [SiH3]S(=O)=O Chemical compound [SiH3]S(=O)=O MCEBKLYUUDGVMD-UHFFFAOYSA-N 0.000 claims description 16
- 125000004122 cyclic group Chemical group 0.000 claims description 16
- 125000005113 hydroxyalkoxy group Chemical group 0.000 claims description 16
- 229920000570 polyether Polymers 0.000 claims description 16
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 15
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical class S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 125000003545 alkoxy group Chemical group 0.000 claims description 10
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 8
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- 239000004814 polyurethane Substances 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 6
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 6
- 125000001072 heteroaryl group Chemical group 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 claims description 5
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 4
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 claims description 4
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 4
- SCPWMSBAGXEGPW-UHFFFAOYSA-N dodecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OC)(OC)OC SCPWMSBAGXEGPW-UHFFFAOYSA-N 0.000 claims description 4
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- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 4
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 4
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 claims description 4
- 125000001188 haloalkyl group Chemical group 0.000 claims description 4
- NHBRUUFBSBSTHM-UHFFFAOYSA-N n'-[2-(3-trimethoxysilylpropylamino)ethyl]ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCNCCN NHBRUUFBSBSTHM-UHFFFAOYSA-N 0.000 claims description 4
- 229920003986 novolac Polymers 0.000 claims description 4
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 claims description 4
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 claims description 4
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 3
- 125000004103 aminoalkyl group Chemical group 0.000 claims description 3
- 150000004756 silanes Chemical class 0.000 claims description 3
- JEDWHBKGOBWWFS-UHFFFAOYSA-N 1-amino-1-benzylurea Chemical group NC(=O)N(N)CC1=CC=CC=C1 JEDWHBKGOBWWFS-UHFFFAOYSA-N 0.000 claims description 2
- WGRZHLPEQDVPET-UHFFFAOYSA-N 2-methoxyethoxysilane Chemical compound COCCO[SiH3] WGRZHLPEQDVPET-UHFFFAOYSA-N 0.000 claims description 2
- RWLDCNACDPTRMY-UHFFFAOYSA-N 3-triethoxysilyl-n-(3-triethoxysilylpropyl)propan-1-amine Chemical compound CCO[Si](OCC)(OCC)CCCNCCC[Si](OCC)(OCC)OCC RWLDCNACDPTRMY-UHFFFAOYSA-N 0.000 claims description 2
- TZZGHGKTHXIOMN-UHFFFAOYSA-N 3-trimethoxysilyl-n-(3-trimethoxysilylpropyl)propan-1-amine Chemical compound CO[Si](OC)(OC)CCCNCCC[Si](OC)(OC)OC TZZGHGKTHXIOMN-UHFFFAOYSA-N 0.000 claims description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 2
- 125000001118 alkylidene group Chemical group 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 125000005133 alkynyloxy group Chemical group 0.000 claims description 2
- 125000004104 aryloxy group Chemical group 0.000 claims description 2
- NFCHYERDRQUCGJ-UHFFFAOYSA-N dimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[SiH](OC)CCCOCC1CO1 NFCHYERDRQUCGJ-UHFFFAOYSA-N 0.000 claims description 2
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 claims description 2
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims description 2
- CPGWZINPVVVFFG-UHFFFAOYSA-N n'-[3-[3-aminopropoxy(dimethoxy)silyl]propyl]ethane-1,2-diamine Chemical compound NCCCO[Si](OC)(OC)CCCNCCN CPGWZINPVVVFFG-UHFFFAOYSA-N 0.000 claims description 2
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 claims description 2
- XCOASYLMDUQBHW-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)butan-1-amine Chemical compound CCCCNCCC[Si](OC)(OC)OC XCOASYLMDUQBHW-UHFFFAOYSA-N 0.000 claims description 2
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 claims description 2
- NESLVXDUKMNMOG-UHFFFAOYSA-N triethoxy-(propyltetrasulfanyl)silane Chemical compound CCCSSSS[Si](OCC)(OCC)OCC NESLVXDUKMNMOG-UHFFFAOYSA-N 0.000 claims description 2
- UDUKMRHNZZLJRB-UHFFFAOYSA-N triethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OCC)(OCC)OCC)CCC2OC21 UDUKMRHNZZLJRB-UHFFFAOYSA-N 0.000 claims description 2
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 claims description 2
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 claims description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 2
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Abstract
用于水力压裂油井和气井的聚合物涂覆的支撑剂,其具有外层部分,该外层部分包含有机官能的偶联剂,优选为有机官能的硅烷偶联剂。在支撑剂涂层的外层部分中优先选择使用有机官能的硅烷偶联剂,以暴露将与相邻的和类似涂覆的支撑剂的相似官能团反应的官能团,使得当被引入井下时,这些支撑剂在井下压裂地层中存在的温度和裂缝闭合压力下形成颗粒间结合。这样的增强的颗粒间结合有助于将支撑剂保持在裂缝中并维持传导率和降低返排。本发明还有助于针对低温井设计的支撑剂更牢固地结合并能够使针对高温井设计的支撑剂即使在较低的井下温度下也很好地结合,从而扩大它们的使用范围。
Description
发明领域
本发明涉及用于生产具有促进颗粒间结合的外涂层的支撑剂的组合物和方法。
发明背景
经涂覆的支撑剂通常用于水力井压裂中,以提高井的生产率。商业化的“标准”涂层通常是酚醛树脂热固性涂层的形式。部分固化的酚醛树脂支撑剂通常用于低温井中(即,具有小于约150°F(66℃)的井底温度的那些),其通常显示低的裂缝闭合应力(例如,2000-6000psi)。支持其应用的理论是部分固化的酚醛树脂涂层的残留反应性连同表面活性剂活化剂(其像塑化剂一样起作用)以及在大多数井中发现的存在的水将允许涂层软化和流动,从而在“关井”期期间使支撑剂固结并形成颗粒间结合。认为井下条件的地层温度会在支撑的地层中原位完成固化反应。外部活化剂流体被用于软化这些部分固化的涂覆的支撑剂的外表面,以试图促进固结和颗粒间结合。然而,活化剂本身产生与压裂流体和破胶流体的相容性的另外问题,以及对支撑剂填充的压裂地层的持续传导率的不良影响的可能性。
对于高温井,如井底温度在约200°F(93℃)以上的那些,通常使用部分固化的酚醛树脂涂覆的支撑剂(以及活化剂)或预固化的酚醛树脂涂层。在预固化的涂覆的支撑剂的情况下,裂缝/裂纹闭合应力通常在6,000psi以上,用作用于将支撑剂保留在破裂的地层中的主要机理。
然而,在实践中,多种因素可以不利地影响该部分固化的酚醛树脂涂层的性能和有效性。这些中最重要的是,涂层中的部分固化的酚醛树脂由于在引入压裂的地层之前暴露于高温而过早固化。即使是在装货码头上和在船运集装箱中存在的地上高温也足以在期望的涂层固化之前早就实现涂层的固化。当在高温深井中使用部分固化的酚醛树脂涂层时,这尤其是个造成影响的问题。在低温应用中,部分固化的酚醛树脂涂层只不过是用太长的时间来固化以产生粘合强度。如果活化剂与部分固化的涂覆的支撑剂连用,则粘合强度可在合理的时间范围内形成。然而,使用活化剂需要在正确的时间下以受控的方式计量地加入到压裂流体中。这增加了压裂处理的复杂性。即使在适当的浓度和时间下加入该活化剂,也仍然存在压裂流体相容性和前述的降低裂缝传导率的问题。
两项已公布的专利申请讨论了异氰酸酯用于支撑剂涂层的用途。Tanguay等人的2011/0297383提出了由砂上的聚碳二亚胺涂层制成的高温支撑剂涂层的实例。据说该涂层由单体异氰酸酯和聚合异氰酸酯的反应制成。催化剂为磷基催化剂,在实施例1中由3-甲基-l-苯基-2-环磷烯氧化物例示。
Tanguay等人的2012/0018162涉及用于高温应用的聚酰胺酰亚胺支撑剂涂层。实施例描述了使用聚合二苯基甲烷二异氰酸酯、偏苯三甲酸酐、三种不同类型的胺中的一种、作为催化剂的三乙胺、助粘剂和润湿剂。描述的涂层/反应过程持续约10分钟,接着是1-3小时的固化后加热。
最近已发现,可以采用多元醇和异氰酸酯的聚氨酯或聚脲反应产物来将固化的、商业上可接受的涂层施加至支撑剂。这些方法的细节公开于共同未决的申请号为13/099,893(名称为“涂覆和固化的支撑剂”)、13/188,530(名称为“涂覆和固化的支撑剂”)、13/626,055(名称为“涂覆和固化的支撑剂”)、13/224,726(名称为“双功能支撑剂”)、13/355,969(名称为“聚合物涂覆的支撑剂的制备”)以及13/837,396(名称为“具有聚脲型涂层的支撑剂”)的美国专利申请,将其公开内容引入本文作为参考。使用这样的涂层的可商购支撑剂可以商品名PEARL和GARNET从PreferredSands,Inc.获得。出于许多理由,这样的基于聚氨酯和聚脲的支撑剂涂层在经济和环境方面都是期望的。重要的是,出于处理、运输和引入压裂的油田内的目的,每种均像完全固化的涂层一样起作用,而且呈现出在井下温度和压力下形成颗粒间结合的固有能力,用于提高传导率和支撑剂返排控制。
尽管在新近的支撑剂涂层中已经看到了由颗粒间结合带来的益处,但在行业内仍存在对这样的支撑剂涂层的不断需要,即该支撑剂涂层将在很多种预期的井下温度和压力条件下可控地形成颗粒间结合强度,而不会因过早地暴露于升高的温度或高温而对形成这样的颗粒间结合强度造成损害。
发明概述
本发明提供一种聚合物涂覆的支撑剂,其具有外层部分,该外层部分包括有机官能的偶联剂,优选为有机官能的硅烷偶联剂。在支撑剂涂层的外层部分中优先选择使用对涂层聚合物有反应性的有机官能的偶联剂,以使得当被引入井下时,该支撑剂的外层在压裂地层中井下存在的温度和裂纹闭合压力下是相互反应的并形成增强的颗粒间结合。这样的增强的颗粒间结合有助于将支撑剂保持在裂缝中并维持传导率和降低的返排。
本发明的偶联剂增强的支撑剂涂层通过增强由常规UCS测试体现的所显示的颗粒间结合强度来使低温涂层在低温井中更加有效。还通过呈现出以前未呈现或仅少量呈现的颗粒间结合强度来使高温涂层对低温井和中温井变得有用。
发明详述
本发明涉及支撑剂涂层,其至少包括包含有机聚合物涂层和偶联剂的外层部分。与芯固体紧邻的内层部分可由相同的聚合物或不同的聚合物或树脂制成。该内层部分和外层部分可以在一个基本连续的涂覆工艺中形成(例如形成单一类型的聚合物涂层或具有变化的比例或成分以形成两种不同的层部分或聚合物)或在相继的涂覆工艺中形成(例如用聚氨酯或聚脲基聚合物涂覆已固化的或可固化的酚醛树脂涂覆的支撑剂以增加加强的颗粒间结合)。优选地,在形成这样的一类聚合物支撑剂的单一的基本连续的涂覆操作的后期期间加入偶联剂,所述聚合物支撑剂具有紧邻芯固体的内部部分和提供这样的硅烷官能团的外层部分,所述硅烷官能团可用于与其它类似涂覆的支撑剂结合以形成在常规UCS测试中展现结合强度的大量支撑剂。甚至更优选地,在涂覆操作的早期阶段添加硅烷偶联剂,以帮助将该涂层结合至支撑剂芯,并在涂覆工艺的后期再次添加硅烷偶联剂以形成将提供增强的颗粒间结合的外层。然而,还可能的是,使用一种类型的偶联剂以增强在支撑剂芯固体与任何施加的涂层之间的结合,并使用与聚合物涂层相容的第二种不同类型的偶联剂以用于增强嵌入压裂油田的裂纹中的邻近支撑剂之间的结合强度。
硅烷通常具有四种主要功能:
1、交联:一旦附着至聚合物主链,硅烷便能通过硅氧烷键的形成将聚合物分子连接在一起,形成三维网格。该“交联”通过环境湿度激活并能在室温下发生。硅烷能够为涂层、粘合剂和密封剂提供改善的热稳定性、抗蠕变性、硬度和耐化学性。
2、助粘:硅烷能够提供在粘合剂、密封剂和涂层内的改善的基底粘合,尤其是在热和潮湿的条件下。硅烷通常可被用于改善对玻璃和金属的粘附,但它们也可以是对有难度的基底如聚酰胺、SMC、丙烯酸树脂、聚氯乙烯(PVC)和其它基底有益的。
3、偶联:硅烷能够将无机颜料和填料偶联至有机树脂。偶联通常改善涂层或粘合剂的湿度和耐化学性。
4、分散:硅烷能够帮助无机颜料和填料在涂层和密封剂中的分散。这能导致在配制的产品中较低的粘度并能够改善涂层的遮盖力。
在本发明中,偶联剂被加到整个支撑剂涂层的外涂层的外部以提供这样的暴露的偶联剂官能团,即该暴露的偶联剂官能团将与邻近支撑剂上的暴露的偶联剂官能团结合,以在井下温度和裂纹闭合应力下,增强在这些邻近的涂覆的支撑剂之间的颗粒间结合。优选地,使用与用作支撑剂外涂层的聚合物或多种聚合物相容的或与之反应的有机官能的硅烷。该有机官能的硅烷以靶向方式被结合到涂层外层内的皮层形成中。当暴露在外层上并且因此在固体-空气界面上的烷氧基时,该烷氧基硅烷的官能度(有机反应性)被设计成匹配聚合物体系并最优化与其的反应(接枝),这将在压裂地层中井下存在水的情况下增强在颗粒间接触点处的粘着性和交联/结合。
有机官能的硅烷为双官能分子,因为它们通常具有两种类型的反应性来构建它们的结构-有机的和无机的。在本发明中有用的有机官能的硅烷可展现任何数量的可能的官能团-聚合物的离散部分-条件是加入的官能团是与聚合物和/或支撑剂涂层的聚合物组分相容的。例如,如果该支撑剂涂层是聚氨酯聚合物,优选的有机官能团是与多元醇组分相容的。
可用于本发明的一种类型的有机官能的硅烷可以由以下式1表示,其示出了典型的有机官能的硅烷的共有要素。
式1
X—R—Si—(Z1)(Z2)(Z3)
其中:
X=反应性有机基团
R=连接基团
Zl、Z2和Z3=可水解基团
该有机端(X)被设计用于与有机树脂反应。可得的反应性有机基团包括伯氨基和取代的氨基、环氧基、甲基丙烯酰基、乙烯基、巯基、脲和异氰酸酯。选择有机基团以与树脂反应或共聚到树脂中或者参与树脂体系的固化反应。
连接基团在有机基团和硅原子之间,一般为“三亚甲基链”。该连接基团的硅-碳键对于大多数环境条件是稳定的。该分子的无机端通过连接至硅的可水解基团(Zl、Z2、Z3)反应。该可水解基团通常是烷氧基,如甲氧基、乙氧基或异丙氧基。每个以不同的速率水解并且在与环境水分反应时释放出不同的醇。尽管三基团的构型是更便于合成的并且通常提供更多的抗水分键,但在一些情况下,仅存在两个可水解基团。大多数偶联剂仅具有一个硅原子,但一些硅烷可具有多个硅。
可用作偶联剂的优选的硅烷可以是有机硅,其可衍生自具有式2的化学结构的有机硅烷。
在式2的化学结构中,X可以是选自以下的官能团:氢、氨基、多氨基烷基、巯基、硫氰基、环氧基、乙烯基、卤素、丙烯酰氧基和甲基丙烯酰氧基。在该化学结构中,Y可以是等于或大于0的整数。在该化学结构中,Z1、Z2和Z3可以各自独立地选自氢、烷氧基、卤素和羟基。
在本发明中使用的适合的有机官能的硅烷具有上述式1的通用结构。对于本发明有用的示例性有机官能的硅烷偶联剂包括具有结构Si(R1)(R2)(R3)(R4)的那些,其中,R1、R2、R3和R4可以相同或不同并且独立地选自氢、烷基、卤代烷基、亚烷基、炔基、烷氧基、炔氧基、芳基、芳氧基、取代芳基、杂芳基、氨基、氨基烷基、芳氨基、环氧化物、硫醇和卤代烷基、醚、酯、尿烷、酰胺,条件是R1、R2、R3和R4中的至少一个包含有机部分。优选地,所述有机官能的硅烷偶联剂包括选自甲基、环氧化物、用环氧化物官能化的或与环氧树脂共聚的三聚氰胺、氨基、巯基、氯丙基、甲基丙烯酰基、甲基丙烯酰氧基、乙烯基、苄氨基、脲基、四硫代和C1-C4烷氧基的有机官能团。甚至更优选地,有机官能的硅烷选自具有至少一个羟基烷氧基甲硅烷基和/或环状二烷氧基甲硅烷基的巯基硅烷;具有至少一个羟基烷氧基甲硅烷基和/或环状二烷氧基甲硅烷基的嵌段巯基硅烷;巯基硅烷,其中巯基硅烷单元的硅原子通过桥接二烷氧基而彼此键合,每个硅烷单元任选地具有至少一个羟基烷氧基甲硅烷基或环状二烷氧基甲硅烷基;嵌段巯基硅烷二聚体,其中,嵌段巯基硅烷单元的硅原子通过桥接二烷氧基而彼此键合,每个硅烷单元任选地具有至少一个羟基烷氧基甲硅烷基或环状二烷氧基甲硅烷基;硅烷二聚体,其具有巯基硅烷单元,所述巯基硅烷单元的硅原子通过桥接二烷氧基被键合至嵌段巯基硅烷单元的硅原子,每个硅烷单元任选地具有至少一个羟基烷氧基甲硅烷基或环状二烷氧基甲硅烷基;巯基硅烷低聚物,其中,邻近的巯基硅烷单元的硅原子通过桥接二烷氧基彼此键合,末端巯基硅烷单元具有至少一个羟基烷氧基甲硅烷基或环状二烷氧基甲硅烷基;嵌段巯基硅烷低聚物,其中,邻近的嵌段巯基硅烷单元的硅原子通过桥接二烷氧基彼此键合,末端巯基硅烷单元具有至少一个羟基烷氧基甲硅烷基或环状二烷氧基甲硅烷基;以及硅烷低聚物,其具有至少一个巯基硅烷单元和至少一个嵌段巯基硅烷单元,邻近的硅烷单元的硅原子通过桥接二烷氧基彼此键合,末端硅烷单元具有至少一个羟基烷氧基甲硅烷基或环状二烷氧基甲硅烷基。
用在根据本发明的支撑剂的外涂层中的有用的有机官能的硅烷偶联剂的具体实例包括3-缩水甘油氧基丙基三甲氧基硅烷、3-缩水甘油氧基丙基三乙氧基硅烷、2-(3,4-环氧基环己基)乙基三乙氧基硅烷和2-(3,4-环氧基环己基)乙基三乙氧基硅烷;3-[2-(2-氨基乙基氨基)乙基氨基]丙基-三甲氧基硅烷(CAS号35141-30-1)、3-巯基丙基三甲氧基硅烷(CAS号4420-74-0)、正丙基三甲氧基硅烷(CAS号1067-25-0)、[3-(2-氨基乙基)氨基丙基]三甲氧基硅烷(CAS号1760-24-3)、硅烷正十二烷基三甲氧基硅烷(CAS号3069-21-4)、双(三乙氧基甲硅烷基丙基)胺(CAS号82985-35-1)、1,2-双(三甲氧基甲硅烷基)乙烷(CAS号18406-41-2)、乙烯基三(2-甲氧基乙氧基)硅烷(CAS号1067-53-4)、正辛基三乙氧基硅烷(CAS号2943-75-1)、双-[3-(三乙氧基甲硅烷基)丙基]-四硫化物(CAS号40372-72-3)、乙烯基三乙氧基硅烷(CAS号78-08-0)、3-缩水甘油氧基丙基三甲氧基硅烷(CAS号2530-83-8)、3-巯基丙基三乙氧基硅烷(CAS号14814-09-6)、3-缩水甘油氧基丙基三乙氧基硅烷(CAS号2602-34-8)、2-(3,4-环氧基环己基)乙基三甲氧基硅烷(CAS号3388-04-3)、3-氨丙基三甲氧基硅烷(CAS号13822-56-5)、2-(3,4-环氧基环己基)乙基三乙氧基硅烷(CAS号10217-34-2)、3-氨基丙基三乙氧基硅烷(CAS号919-30-2)、3-缩水甘油氧基丙基甲基二甲氧基硅烷(CAS号65799-47-5)、双[三乙氧基甲硅烷基丙基]胺(CAS号13497-18-2)、3-(2-氨基乙基氨基)丙基二甲氧基甲基硅烷(CAS号3069-29-2)、N-(正丁基)-3-氨基丙基三甲氧基硅烷(CAS号31024-56-3)、正丙基三乙氧基硅烷(CAS号2550-02-9)、乙烯基三甲氧基硅烷(CAS号2768-02-7)、3-脲基丙基三乙氧基硅烷(CAS号23779-32-0)、3-甲基丙烯酰氧基丙基三甲氧基硅烷(CAS号2530-85-0)。
在本发明中,胺官能的硅烷化合物特别优选地作为助粘剂。参见第6,071,990号和第US8,349,911号美国专利,其公开内容被在此引入作为参考。这样的胺官能的硅烷优选为由通用式3表示的(氨基烷基)烷氧基硅烷。
式3:(R4)NH(R3)Si(R2)b(O)(RI)3-b
其中R1和R2是具有1至4个碳的一价烃基,它们独立地选自甲基、乙基、丙基或丁基,以及
b的值为0或1;
R3是由式(CH2)X表示的二价烃基,其中x是3至10的正整数;以及
R4选自包含氢的基团、具有一至四个碳的单价烃基或由式(R5)NH(R3)表示的基团,其中,R3是如上定义的并且R5是氢或具有1至4个碳的单价烃基。由R4表示的基团的实例包括甲基、乙基、丙基、丁基、氨甲基、氨乙基、氨丙基、氨基丁基、乙氨基丙基和氨乙基氨乙基。
在上述通式内的通常可得的胺官能的硅烷化合物的实例包括氨丙基三乙氧基硅烷(来自EvonikIndustries的AMEO)、氨丙基三甲氧基硅烷(AMMO)、氨乙基氨丙基三甲氧基硅烷(AEAPTMS)和氨乙基氨乙基氨丙基三甲氧基硅烷(TAS)。
可用在本发明中的另一种类型的有机官能的硅烷是硅烷封端聚合物,如硅烷封端聚醚和硅烷封端聚氨酯。这些聚合物由例如具有异氰酸酯封端的聚醚聚合物与氨基硅烷反应,或由具有氨基封端和/或羟基封端的聚醚聚合物与异氰酸酯封端的硅烷反应形成。反应性基团与组合物中的其它物质的反应也能形成其它交联。硅烷封端的聚合物(STP)或硅烷改性的聚合物(MS)可均为预聚物,其在链末端或侧面携带具有至少一个可水解键的甲硅烷基,但其在聚合物骨架中并未呈现硅酮的典型硅氧烷键(SiR2O)n。两种优选的硅烷封端的聚合物由式4(二甲氧基(甲基)甲硅烷基氨基甲酸甲酯封端的聚醚)和5示出:
其中,对于式4:聚醚是指具有1-200个碳原子的聚醚链。还参见公开的第3,971,751和6,207,766号美国专利以及第US2007/0088137号美国公开专利申请,其公开内容在此被引入作为参考。
其中,对于式5:R是氨基;式5中的每个X可各自独立地选自氢、烷氧基、卤素和羟基;并且n是大于0的整数。这样的试剂可从德国慕尼黑Hanns-Seidel-Platz4,81737的WackerChemieAG以商品名STP-E商购。
式4-5的双足硅烷封端的聚醚基聚合物是可与可用作制备聚氨酯支撑剂涂层的多元醇组分的聚醚多元醇相容的或相混的。这样的硅烷封端的聚醚基聚合物作为最后一步的表面涂层与聚醚多元醇简单共混,以为根据本发明的涂覆的支撑剂提供粘合剂涂层。式4的呈双(3-三甲氧基甲硅烷基丙基)胺形式的双足氨基硅烷已经在支撑剂行业中作为针对“有难度的”基底的偶联剂使用。在本发明中,这种硅烷能够为每一个胺(-NC=O)接枝部分提供两个硅烷、类似粘合剂的官能团。
烷氧基部分中的碳链的长度(例如甲氧基相对乙氧基相对丙氧基相对丁氧基)决定了硅烷的水解速率。因此,烷氧基碳链的长度的选择可用于提供对得到的抗湿性和抗水性的控制。看到抗性随烷基链的增加而增强。较长长度的碳链还将延迟水解,并因此延迟了在裂缝中的支撑剂的结合性能。
许多种聚合物可被用作本发明的支撑剂的内涂层和/或外涂层。事实上,涂层可以是热固性的或热塑性的并且可以与其他和任意中间支撑剂涂层相同、不同、或是其他和任意中间支撑剂涂层的类似物或同系物。示例性聚合物涂层包括聚氨酯、聚脲型聚合物、酚醛树脂、苯酚甲醛树脂和聚碳二亚胺。
用于本发明和它们的制造的优选的支撑剂涂层是聚氨酯和聚脲型涂层。这些涂层在共同未决的申请号为13/099,893(名称为“涂覆和固化的支撑剂”)、13/188,530(名称为“涂覆和固化的支撑剂”)、13/626,055(名称为“涂覆和固化的支撑剂”)、13/224,726(名称为“双功能支撑剂”)、13/355,969(名称为“聚合物涂覆的支撑剂的制备”)、以及13/837,396(名称为“具有聚脲型涂层的支撑剂”)的美国专利申请中被更详细地描述,其公开内容被引入本文作为参考。
作为内层和/或外层的特别优选的支撑剂涂层是使用聚脲基或聚氨酯基聚合物的那些。聚脲型涂层优选地在支撑剂上由动态反应混合物形成,所述动态反应混合物包含在支撑剂核的存在下同时接触和混合的异氰酸酯、水和固化剂(优选含有固化剂或催化剂的水溶液)。虽然不希望受工作原理的约束,但是认为基本上同时的水和异氰酸酯的可控的速率使得水由异氰酸酯形成反应性胺物质,该新形成的胺然后与其它未转化的异氰酸酯反应以直接在支撑剂固体的外表面上形成期望的聚脲型涂层。因此,成分之间的同时接触形成反应混合物,其聚合以直接在支撑剂芯的外表面上形成薄的、硬的、基本上无泡沫的涂层。如果在接触之前砂已被加热,则反应可以在小于约四分钟内基本上进行到完成,从而形成硬的、基本上完全固化的涂层,其不需要后固化以形成无粘性或基本上无粘性的外表面。
供选择地且不太优选地,可以通过连续向混合器中加入聚脲型前体组分在支撑剂芯上形成聚脲型涂层。然而,这样的方法可能会需要充分搅拌和混合以避免来自第一加入的组分的边界层效应,所述第一加入的组分将覆盖支撑剂芯的表面到一定的深度,其可能抑制所有第一材料向下与支撑剂芯固体的表面完全反应。充分搅拌将用于迫使第二组分进入第一组分的边界层,以使第一组分边界层从其外表面朝向支撑剂芯的外表面向下反应,以形成紧密粘附到支撑剂芯表面的连接。
如果支撑剂芯已在外部条件下储存并已变得湿润,则会产生类似的担心。期望的是将支撑剂芯加热到约100℃以上,可能更低,使流动的空气穿过固体,直到支撑剂基本上干燥,之后使其第一次与聚脲型前体的可反应的或反应混合物接触。这样的干燥方法通常用于处理甚至未涂覆的砂支撑剂,该涂覆方法优选地在与干燥操作相同或邻近的设备中进行,以使引入到砂的用于干燥的显热也可以用于促进在处理的支撑剂砂的至少一部分上的固化涂层的形成。
确定涂层玻璃化转变温度(Tg)的对涂层的测试以及对结合强度的实验室规模的测试,如常规的UCS测试或传导率,可以用于评价通过特定涂覆方法制备的任何特定涂层制剂的适合性。具体地,Tg可以用作预言热塑性涂层(例如,本发明的那些,以上描述并且引入作为参考的我们的共同未决的专利申请中描述的聚氨酯,或之前提到的Tanguay等人的专利申请的那些)是否潜在地可用于给定的压裂地层的井下条件的指导。期望的是,支撑剂涂层的Tg是比井下占优势的温度低的温度,以使热塑性涂层在占优势的温度和压力组合下具有软化能力。对于本发明以及对于在高温井中的使用,支撑剂涂层的Tg优选高于约75℃但低于约200℃,甚至更优选在约100-165℃的范围内。对于较低温度的井,井下温度在20℃-52℃范围内的那些,支撑剂涂层的Tg期望在约20℃至60℃的范围内。
支撑剂性能的优选测试方法描述于ISO13503-5:2006(E)“用于测量支撑剂的长期传导率的方法(Proceduresformeasuringthelongtermconductivityofproppants)”,将其公开内容引入本文作为参考。ISO13503-5:2006提供了用于评价在水力压裂和砾石充填作业中使用的支撑剂的标准测试程序。ISO13503-5:2006提供了用于在水力压裂和/或砾石充填支撑剂上进行测试的一贯方法。此后在ISO13503-5:2006的该部分提及的“支撑剂”是指砂、陶瓷介质、树脂涂覆的支撑剂、砾石充填介质和用于水力压裂和砾石充填作业的其它材料。ISO13503-5:2006不适用于在井下储层条件下获得支撑剂充填传导率的绝对值,但其可以充当一致的方法,通过所述方法可以在实验室环境中模拟这样的井下条件并进行比较。
异氰酸酯组分
本发明的涂层的异氰酸酯官能组分包括具有至少2个反应性异氰酸酯基团的异氰酸酯官能组分。如果需要,可以使用其它含有异氰酸酯的化合物。适合的具有至少2个异氰酸酯基团的异氰酸酯的实例是具有至少2个异氰酸酯基团的脂肪族异氰酸酯或芳香族异氰酸酯(例如,二异氰酸酯、三异氰酸酯或四异氰酸酯),或可以优选地使用它们的低聚物或聚合物。这些具有至少2个异氰酸酯基团的异氰酸酯还可以是碳环的或杂环的和/或含有一个或多个杂环基团。
具有至少2个异氰酸酯基团的异氰酸酯官能组分优选为式(III)的化合物或式(III)化合物的聚合物或低聚物,或式(IV)的化合物:
在式(III)和(IV)中,A各自独立地为芳基、杂芳基、环烷基或杂环烷基。优选地,A各自独立地为芳基或环烷基。更优选地,A各自独立地为芳基,所述芳基优选为苯基、萘基或蒽基,最优选为苯基。仍然更优选地,A为苯基。
上述杂芳基优选为具有5个或6个环原子的杂芳基,其中1个、2个或3个环原子各自独立地为氧、硫或氮原子,并且其它环原子为碳原子。更优选地,所述杂芳基选自吡啶基、噻吩基、呋喃基、吡咯基、咪唑基、吡唑基、吡嗪基、嘧啶基、哒嗪基、噁唑基、异噁唑基或呋咱基。
上述环烷基优选为C3-10-环烷基,更优选为C5-7-环烷基。
上述杂环烷基优选为具有3至10个环原子(更优选地具有5至7个环原子)的杂环烷基,其中一个或多个(例如,1、2或3个)环原子各自独立地为氧、硫或氮原子,并且其它环原子为碳原子。更优选地,杂环烷基选自四氢呋喃基、哌啶基、哌嗪基、氮丙啶基、吖丁啶基(acetidinyl))、吡咯烷基、咪唑烷基、吗啉基、吡唑烷基、四氢噻吩基、八氢喹啉基、八氢异喹啉基、噁唑烷基或异噁唑烷基。仍然更优选地,杂环烷基选自四氢呋喃基、哌啶基、哌嗪基、吡咯烷基、咪唑烷基、吗啉基、吡唑烷基、四氢噻吩基、噁唑烷基或异噁唑烷基。
在式(III)和(IV)中,每个R1分别为共价键或C1-4-亚烷基(例如,亚甲基、亚乙基、亚丙基或亚丁基)。优选地,每个R2为氢或共价键。
在式(III)和(IV)中,每个R2各自独立地为氢、卤素(例如,F、Cl、Br或I)、C1-4-烷基(例如,甲基、乙基、丙基或丁基)或C1-4-烷氧基(例如,甲氧基、乙氧基、丙氧基或丁氧基)。优选地,每个R2独立地为氢或C1-4-烷基。更优选地,每个R2为氢或甲基。
在式(IV)中,R3为共价键、C1-4-亚烷基(例如,亚甲基、亚乙基、亚丙基或亚丁基)或基团–(CH2)R31-O-(CH2)R32-,其中R31和R32各自独立地为0、1、2或3。优选地,R3为-CH2-基团或-O-基团。
在式(III)中,p等于2、3或4,优选等于2或3,更优选等于2。
在式(III)和(IV)中,每个q独立地为0到4的整数,优选为0、1或2。当q等于0时,相应的基团A不具有取代基R2,但具有氢原子代替R2。
在式(IV)中,每个r和s独立地为0、1、2、3或4,其中r和s之和等于2、3或4。优选地,每个r和s独立地为0、1或2,其中r和s之和等于2。更优选地,r等于1,和s等于1。
具有至少2个异氰酸酯基团的异氰酸酯的实例为:甲苯-2,4-二异氰酸酯;甲苯-2,6-二异氰酸酯;1,5-萘二异氰酸酯;异丙苯-2,4-二异氰酸酯;4-甲氧基-1,3-苯基二异氰酸酯;4-氯-1,3-苯基二异氰酸酯;二苯基甲烷-4,4-二异氰酸酯;二苯基甲烷-2,4-二异氰酸酯;二苯基甲烷-2,2-二异氰酸酯;4-溴-1,3-苯基二异氰酸酯;4-乙氧基-1,3-苯基-二异氰酸酯;2,4’-二异氰酸酯二苯醚;5,6-二甲基-1,3-苯基-二异氰酸酯;亚甲基二苯基二异氰酸酯(包括2,2’-MDI、2,4’-MDI和4,4”-MDI);4,4-二异氰酸基-二苯醚;4,6-二甲基-1,3-苯基二异氰酸酯;9,10-蒽-二异氰酸酯;2,4,6-甲苯三异氰酸酯;2,4,4’-三异氰酸基二苯醚;1,4-四亚甲基二异氰酸酯;1,6-六亚甲基二异氰酸酯;1,10-十亚甲基-二异氰酸酯;1,3-亚环己基二异氰酸酯;4,4’-亚甲基-双-(环己基异氰酸酯);二甲苯二异氰酸酯;1-异氰酸基-3-甲基-异氰酸酯-3,5,5-三甲基环己烷(异佛尔酮二异氰酸酯);1,3-双(异氰酸基-1-甲基乙基)苯(m-TMXDI);1,4-双(异氰酸基-1-甲基乙基)苯(p-TMXDI);上述异氰酸酯化合物的低聚物或聚合物;或两种或多种上述异氰酸酯化合物或其低聚物或聚合物的混合物。多种聚合异氰酸酯可以用于本发明。适合的实例包括二苯基甲烷二异氰酸酯(MDI和pMDI)、甲苯二异氰酸酯(TDI)、六亚甲基二异氰酸酯(HDI)、异佛尔酮二异氰酸酯(IPDI)的聚合物和低聚物,及其组合。用于本发明的优选的聚合异氰酸酯是基于二苯基甲烷二异氰酸酯的聚合物和低聚物。
特别优选的具有至少2个异氰酸酯基团的异氰酸酯为甲苯二异氰酸酯、亚甲基二苯基二异氰酸酯、二苯基甲烷二异氰酸酯、基于甲苯二异氰酸酯的低聚物、基于亚甲基二苯基二异氰酸酯的低聚物(聚-MDI)或基于二苯基甲烷二异氰酸酯的低聚物及其聚合物。
多元醇组分
具有多羟基官能团的多元醇组分是在根据本发明的方法中用于制造在支撑剂固体上的聚氨酯涂层的一种组分,并且它可以作为第一组分或第二组分来施加。多元醇组分具有除与羧酸相关的羟基之外的两个或更多个官能的羟基部分(如基于起始分子如丙三醇、三羟甲基丙烷、山梨糖醇、甲基葡萄糖苷和蔗糖的二元醇、三元醇和更高的多元醇官能度),并且可以具有或可以没有反应性胺官能团。优选的多羟基多元醇包括聚醚(如聚氧化丙烯二元醇和三元醇),聚酯,脂肪族多元醇,芳族多元醇,脂肪族多元醇和芳族多元醇的混合物,合成多元醇,多羟基低聚物(参见US4554188和US4465815,其公开内容在此引入作为参考),天然油多元醇(如腰果油和蓖麻油)以及已经处理以引入多羟基成分取代不饱和键的天然油,如氧化豆油、氧化花生油和氧化菜籽油,如由生物质制得的多元醇。
优选的聚氨酯涂层由多元醇混合物制成,该多元醇混合物包括5-100wt%的一种或多种聚醚、聚酯、脂肪族和/或多羟基低聚物多元醇和0-95wt%的芳族多元醇。特别优选的多元醇包含0-50wt%的腰果油、0-60wt%的芳族多元醇以及20-100%的蓖麻油。看起来,在涂层混合物中的蓖麻油与异氰酸酯的最佳比例导致比在涂层中具有较低比例的蓖麻油的涂层更低的LOI损失且更高的颗粒间结合强度。
还是在另一实施方案中,多元醇组分为具有基于强心酚和/或腰果酚的单体单元的酚树脂。强心酚和腰果酚是由获得自腰果树种子的腰果油生产的。腰果油由约90%的漆树酸和约10%的强心酚组成。通过在酸环境中的热处理,由漆树酸脱羧来获得强心酚和腰果酚的混合物。强心酚和腰果酚具有以下示出的结构:
如上图所示,强心酚和/或腰果酚中的烃基(-C15H31-n)可以具有1(n=2)、2(n=4)或3(n=6)个双键。强心酚具体是指化合物CAS号57486-25-6,腰果酚具体是指化合物CAS号37330-39-5。
强心酚和腰果酚都可以在酚树脂中单独使用或者以任意特定的混合比使用。也可使用脱羧的腰果油。
强心酚和/或腰果酚可以缩合成上述的酚树脂,例如,缩合成可溶或酚醛清漆型酚树脂。为了该目的,强心酚和/或腰果酚可以例如与酚缩合或与一种或多种以上限定的式(I)的化合物缩合,并且还可以与醛,优选为甲醛缩合。
在酚醛树脂中缩合的强心酚和/或腰果酚的量不受具体限制,并且相对于100wt%的在酚树脂中使用的酚醛树脂起始产物的量计,优选为约1wt%至约99wt%,更优选为约5wt%至约60wt%,和还更优选为约10wt%至约30wt%。
在另一个实施方案中,多元醇组分为通过强心酚和/或腰果酚与醛,优选为甲醛缩合而获得的酚树脂。
含有基于如上所述的强心酚和/或腰果酚的单体单元的酚树脂,或者可以通过强心酚和/或腰果酚与醛缩合来获得的酚树脂,具有特别低的粘度并且因此可以优选地在低添加或不添加反应性稀释剂(thinner)的情况下使用。另外,这种长链、取代的酚树脂比较疏水,这导致通过根据本发明的方法获得的涂覆的支撑剂的良好的保存期。另外,这种酚树脂还由于强心酚和腰果酚是可再生原料而是有利的。
除了酚树脂以外,多元醇组分可以还含有其它包含羟基基团的化合物。其它包含羟基基团的化合物可以选自已知可用于制备聚氨酯的包含羟基基团的化合物,例如,羟基官能的聚醚、羟基官能的聚酯、醇或二醇。一种优选的包含羟基基团的化合物例如为蓖麻油。包含羟基基团如醇或二醇的化合物,特别是强心酚和/或腰果酚,可以用作反应性稀释剂。
固化剂和催化剂
本发明的涂层可以使用各种固化剂中的至少一种来固化,所述固化剂包括反应性的、非反应性的(例如,“催化剂”)和部分反应性的促进聚脲型连接形成的试剂。一般地,优选的固化剂选自基于胺的固化剂,并以约0.0001%至约30总wt%范围内的总量加入到聚脲型前体的反应混合物中。如果期望另外的交联能力以利用井下的热和压力条件,则基于胺的固化剂还可以用作快速作用的第一固化剂和第二潜伏性固化剂的混合物。这些第一和/或第二基于胺的固化剂中任何一个可以是反应性的、非反应性的或部分反应性的。然而,如果胺固化剂是反应性的,则优选地选择利于通过与异氰酸酯的反应形成聚脲的胺。烷醇胺也可促进聚脲的形成,同时也提供羟基官能团,所述羟基官能团将促进加入的偶联剂结合在根据本发明的支撑剂涂层的外层中。
用于促进聚脲形成的合适的单一的基于胺的固化剂或基于胺的固化剂的混合物可以包括但不限于,2,2'-二吗啉基二乙醚;双-二甲氨基乙基醚;乙二胺;己二胺;1-甲基-2,6-环己基二胺;2,2,4-和2,4,4-三甲基-1,6-己二胺;4,4'-双-(仲丁氨基)-二环己基甲烷及其衍生物;1,4-双-(仲丁氨基)-环己烷;1,2-双-(仲丁氨基)-环己烷;4,4'-二环己基甲烷二胺;1,4-环己烷-双-(甲胺);1,3-环己烷-双-(甲胺)、其异构体及混合物;二甘醇双-(氨丙基)醚;2-甲基戊二胺;环己二胺、其异构体及混合物;二亚乙基三胺;三亚乙基四胺;四亚乙基五胺;丙二胺;1,3-二氨基丙烷;二甲氨基丙胺;二乙氨基丙胺;亚氨基-双-(丙胺);单乙醇胺,二乙醇胺;三乙醇胺;单异丙醇胺;二异丙醇胺;异佛尔酮二胺;4,4'-亚甲基双-(2-氯苯胺);3,5-二甲基硫代-2,4-甲苯二胺;3,5-二甲基硫代-2,6-甲苯二胺;3,5-二乙基硫代-2,4-甲苯二胺;3,5-二乙基硫代-2,6-甲苯二胺;4,4'-双-(仲丁氨基)-苯;及其衍生物;1,4-双-(仲丁氨基)-苯;1,2-双-(仲丁氨基)-苯;N,N'-二烷基氨基-二苯基甲烷;丙二醇-二-对氨基苯甲酸酯(trimethyleneglycol-ci-p-aminobenzoate);聚四氢呋喃-二-对氨基苯甲酸酯;4,4'-亚甲基双-(3-氯-2,6-二亚乙基苯胺);4,4'-亚甲基双-(2,6-二乙基苯胺);间苯二胺;对苯二胺;N,N'-二异丙基-异佛尔酮二胺;聚氧亚丙基二胺;基于环氧丙烷的三胺;3,3'-二甲基-4,4'-二氨基环己基甲烷(3,3'-dimethyl-4,4'-ciaminocyclohexylmethane);及其混合物。在一个实施方案中,胺封端的固化剂为4,4'-双-(仲-丁氨基)-二环己基甲烷。用于与本发明一起使用的有助于-NCO-和水反应以形成聚脲型连接的优选的基于胺的固化剂和催化剂包括三亚乙基二胺;双(2-二甲基氨基乙基)醚;四甲基乙二胺;五甲基二亚乙基三胺;1,3,5-三(3-(二甲氨基)丙基)-六氢-均三嗪和亚烷基胺的其它叔胺产物。
另外,本发明中可以使用行业已知的促进异氰酸酯与羟基化合物和胺的反应的其它催化剂,例如,用于聚脲型泡沫的第III族或第IV族过渡金属催化剂。特别优选的金属催化剂包括二月桂酸二丁基锡,并在涂覆过程期间加入水中用于施加。
与其它反应机制相比,促进异氰酸酯三聚的催化剂也是优选的。参见,例如,第5,264,572号美国专利(氟化铯或氟化四烷基铵(tetraalkylammoniumfluoride)),第3,817,939号美国专利(有机碳酸盐)和第6,127,308号美国专利(锂盐,氢氧化锂,水铝英石催化剂,如2-乙基己酸亚锡(tin-2-ethylhexanoate)或辛酸亚锡,以及含有至少一个羟基基团的有机化合物),将其公开内容引入本文作为参考。基于磷的催化剂已用于促进聚碳二亚胺的形成(参照Tanguay等人的US2011/0297383中的实施例),并不优选用于本发明中。
基于胺的固化剂可以具有约64或更高的分子量。在一个实施方案中,胺固化剂的分子量为约2000或更低,并且是伯胺或仲胺。叔胺通常将不用作用于形成聚脲型涂层的反应物。
在以上列表中,适合用于制备根据本发明的聚脲型涂层的饱和的基于胺的固化剂包括但不限于,乙二胺;己二胺;1-甲基-2,6-环己基二胺;2,2,4-和2,4,4-三甲基-1,6-己二胺;4,4'-双-(仲丁氨基)-二环己基甲烷;1,4-双-(仲丁氨基)-环己烷;1,2-双-(仲丁氨基)-环己烷;4,4'-双-(仲丁基氨基)-二环己基甲烷的衍生物;4,4'-二环己基甲烷二胺;1,4-环己烷-双-(甲胺);1,3-环己烷-双-(甲胺);二甘醇双-(氨丙基)醚;2-甲基戊二胺;环己二胺;二亚乙基三胺;三亚乙基四胺;四亚乙基五胺;丙二胺;二亚丙基三胺;1,3-二氨基丙烷;二甲基氨基丙胺;二乙氨基丙胺;亚氨基-双-(丙胺);单乙醇胺;二乙醇胺;单异丙醇胺,二异丙醇胺;三异丙醇胺;异佛尔酮二胺;Ν,Ν'-二异丙基异佛尔酮二胺及其混合物。
在一个实施方案中,与预聚物一起使用的固化剂包括3,5-二甲基硫代-2,4-甲苯二胺、3,5-二甲基-硫代-2,6-甲苯二胺、4,4'-双-(仲丁氨基)-二苯基甲烷、N,N'-二异丙基-异佛尔酮二胺;聚氧亚丙基二胺;基于环氧丙烷的三胺;3,3'-二甲基-4,4'-二氨基环己基甲烷;及其混合物。
由于未受阻的伯二胺导致异氰酸酯基团和胺基团之间的快速反应,因此在某些情况下,受阻的仲二胺可以更适合使用。不受任何特定理论的束缚,认为具有高水平的空间位阻的胺,例如在氮原子上的叔丁基,具有比没有位阻或具有低水平的位阻的胺更慢的反应速率,并且进一步增加终产物的水解稳定性和热稳定性。例如,4,4'-双-(仲丁氨基)-二环己基甲烷(CLEARLINK来自Texas的TheWoodlands的HuntsmanCorporation)可以适合与异氰酸酯组合使用,以形成聚脲型涂层。此外,也可得自HuntsmanCorporation的、商品名为的N,N'-二异丙基-异佛尔酮二胺可以用作仲二胺固化剂。
此外,三官能的固化剂可以用于帮助改善交联,并且因此进一步改善涂层的抗化学性和/或抗磨损性。在一个实施方案中,二亚乙基三胺或三亚乙基四胺均是高反应性的,并且期望地与另一种相容性组分一起添加到涂覆过程中。
本发明的固化剂可以与任一种其它组分同时加到涂层制剂中,或预涂覆在支撑剂上。优选地,基本上在异氰酸酯被加入的同时,将固化剂与任一种其它组分共施加至固体支撑剂芯,例如加入固化剂和多元醇组分。
添加剂
本发明的支撑剂涂层组合物还可以包含加入涂层或固化产品的各种添加剂,所述添加剂能够作为支撑剂或在压裂流体或破胶流体中改变所述涂层的外观、性能、处理特性或性能。例如,本发明的涂层还可以包含一定量的颜料、染色剂、染料和填料以提供在涂层中可见的着色。其它材料包括但不限于,冲击强度增强剂、补强剂、反应速率增强剂或催化剂、交联剂、光增白剂、碳酸丙烯酯、着色剂、荧光剂、增白剂、UV吸收剂、受阻胺光稳定剂、消泡剂、加工助剂、云母、滑石、纳米填料、硅烷偶联剂、防滑剂、亲水或斥水组分、水活化剂、增粘剂、流动助剂、防结块剂、润湿剂、增韧剂如一种或多种嵌段共聚物,以及起到去除地下水中存在的重金属和/或不期望的溶质中的至少一些部分的作用的组分。参见于2011年9月1日提交的、名称为"双功能支撑剂"的共同未决的申请号为13/224726的美国专利申请,将其公开内容引入本文作为参考。
添加剂优选是以约15重量%或更少的量存在的。在一个实施方案中,添加剂是以涂层组合物的重量计约5%或更少的、非零的量存在的。
可以另外地使用表面活性剂,抗结块剂或助剂,如滑石粉或硬脂酸盐或其它加工助剂,如细无定形二氧化硅处理涂覆的支撑剂以改进涂覆产品的可浇注性、可润湿性(甚至达到可以省去水润湿表面活性剂的程度)、分散性、降低的静电、粉化倾向和储存特性。一组优选的添加剂是防结块剂,其有助于涂覆的和固化的支撑剂的操作特性以避免结块并改善流动。这样的防结块剂包括无定形二氧化硅(例如,二氧化硅粉、火成二氧化硅和二氧化硅分散体)和二氧化硅替代物(例如在喷砂中用作二氧化硅或有机官能硅烷的替代物的那些,像来自PA的Chester的EvonikDegussaCorporation的DYNASYLAN流体)。这些试剂可以以粉末或分散体获得。它们被施加到涂覆的支撑剂固体的外表面,以防止在包装和运输期间形成团块。无定形二氧化硅的优选的施加量通常为基于干的支撑剂重量计约0.001wt%至约1wt%。
助粘剂可以用于提高支撑剂芯固体的外表面与所施加的聚合物涂层之间的结合强度。硅烷是特别优选类型的助粘剂,其提高涂层树脂对支撑剂芯固体表面的亲和力,并且当砂为支撑剂芯时是特别有用的。在涂覆陶瓷芯固体时,也可使用有机官能的钛酸盐和锆酸盐。助粘剂可在涂覆工艺的初始阶段作为添加剂被混入或以对所述芯固体的独立的预处理步骤被施加。助粘剂还可从在支撑剂涂层中使用的多元醇组分或异氰酸酯组分的反应性成分原位转化。官能硅烷如氨基硅烷、环氧基-、芳基-或乙烯基硅烷可商购。氨基硅烷是优选的。
任选的另外的添加剂是污染物去除组分,其将去除、隔绝(sequester)、螯合或以其它方式清除来自压裂地层内的地下水或烃沉积物的至少一种污染物,尤其是溶解的或另外的离子形式的重金属和天然存在的辐射性材料(NORMS),而同时还撑开所述压裂地层中的裂缝。优选地,污染物去除组分作为化学上不同的固体与支撑剂固体相关联,该化学上不同的固体是作为以下组分与支撑剂固体一起被引入的:(a)用涂层制剂固定到支撑剂固体的外或内表面的不溶固体,该涂层制剂将固体粘合在一起,(b)作为停留(lodge)在支撑剂固体的孔内的固体或者(c)作为混入支撑剂固体的涂层或结构中或与支撑剂固体的涂层或结构整合的化合物或化学部分。参见于2011年9月2日提交的、名称为“双功能支撑剂”的共同未决的申请号为13/224726的美国专利申请,将其公开内容引入本文作为参考。另外的附加功能还可以是压裂流体破坏剂、去乳化剂和杀菌剂的形式。
辅助颗粒对支撑剂的附加功能还可以是离子交换树脂的形式,该离子交换树脂经预处理或者其自身构成用于缓慢释放腐蚀抑制剂或阻垢剂的可溶固体。这样的缓慢释放材料可证明是有益于且有利于井的整个运行和维护。
支撑剂涂层的或施加至固化的涂层的外表面的其它有用的添加剂包括防垢剂、防蜡剂、杀菌剂、破胶剂、硫化氢吸收剂或在压裂地层中存在的其它不期望组分的清除剂。
支撑剂芯固体
支撑剂实质上可以是具有足够的压碎强度并缺乏化学反应性的任何小的固体。合适的实例包括砂、陶瓷颗粒(如氧化铝、二氧化硅、二氧化钛、氧化锌、二氧化锆、二氧化铈、二氧化锰、氧化铁、氧化钙、氧化镁或矾土),或还有其它粒状材料。
支撑砂是用于本发明的优选类型的支撑剂。砂主要用于天然气井和油井的水力压裂工艺,以提高其有价值的天然资源的生产力。支撑砂是具有至少80wt%的高二氧化硅含量的单晶体,更典型地具有高于约97wt%的二氧化硅的二氧化硅含量。
美国石油学会规范对适合用于水力压裂的支撑剂的筛分布(sievedistribution)进行了以下限制:
·至少90%的材料必须落入两种筛目尺寸之间,
·不多于10%的材料可以比最大筛目尺寸更粗,
·不多于0.1%的材料可以比下一个最大的筛目尺寸更粗,例如,对于20/40,高达10%的支撑剂可以在16到20目之间,但是不多于0.1%的支撑剂可以超过16目,和
·不多于1%的材料允许落在盘上。
当大批确定时,支撑剂被分为低密度、中密度、高密度。支撑剂压碎强度分为52Mpa、69Mpa、86Mpa和103Mpa系列。支撑砂的尺寸规格通常为12-18目、12-20目、16-20目、16-30目、20-40目、30-50目、40-60目、40-70目和更小。待涂覆的支撑剂优选具有约50μm至约3000μm范围内的平均粒径,更优选具有约100μm至约2000μm范围内的平均粒径。
涂覆方法
本发明的涂覆方法在支撑剂芯固体上产生聚脲型或聚氨酯型涂层,其在压裂的地下地层中井下存在的高热、搅拌、磨损和水的苛刻组合下是坚硬、耐用的并且抗溶解。优选地,固化的涂层显示足够的抗性(如10天高压釜测试或10天传导率测试所反映的),以使涂层抗热水中溶解导致的损失(LOI损失)小于25wt%,更优选小于15wt%,以及甚至更优选小于5wt%的损失。因此本发明的基本上固化的涂层抵抗在压裂地层中的溶解,同时还显示足够的固结以及对返排的抗性,而不需使用添加的结合活化剂,同时还显示足够高的压碎强度,以撑开裂缝并在延长的期间保持其传导率。
用于制备聚氨酯型涂层的优选方法在共同未决的申请号为13/355,969美国专利申请(名称为“聚合物涂覆的支撑剂的制造(ManufactureofPolymerCoatedProppants)”中有所描述,将其引入本文作为参考。简单地概述,该发明的涂覆方法是在固体支撑剂芯上形成聚氨酯基涂层,以形成自由流动的、涂覆的支撑剂固体,其中,水在涂覆步骤中作为加工助剂加入以用于形成涂覆的支撑剂。水加入的速率或量足以在涂覆工艺进行时维持支撑剂固体的离散的自由流动特性并且还避免形成大量泡沫。水还有助于减少或消除支撑剂固体的粘性的树脂团块或污垢团的形成,所述支撑剂固体仅涂覆有聚氨酯反应物之一(例如多元醇或异氰酸酯)或涂覆有两种组分,但它们的比例不利于快速形成期望的聚氨酯涂层。由于尚未最终确定产生这种效果的准确机理,因此,本发明不应当被任何具体的工作原理限定,本发明人相信,水能够使反应容易形成聚脲结构并且减少未反应的-NCO键的数量,这提高了涂层的热性能并有助于迅速增大交联密度。可能的是,水充当了这些反应的反应性稳定流体,因为最终的产品是干燥的且自由流动的。
除了对安全和组分完整性的实际考虑之外,涂覆工艺的温度没有特别限制。本发明的涂覆/固化步骤的优选条件通常是在约50°至约175℃范围的条件下,更优选在约75℃至约150℃范围的温度下,并且最优选在约80℃至约135℃范围的温度下。如上所述,通过加热或使用加热的支撑剂固体便利地达到该温度。优选的温度范围避免了许多排放问题,减少了涂覆工艺中消耗能量的量,并且还减少了用于进一步操作和包装的涂覆的支撑剂的冷却时间。
可以在连续或不连续的基础上,使用单一混合器顺序地或在数轮中进行混合,但是认为用于涂覆支撑剂的具体的混合器对于本发明不是关键的。可以使用适合的混合器,包括滚动式混合器、流化床、拌合机(pugmill)混合器或搅动混合器。例如,可以使用圆筒混合器,板型混合器,管式混合器,槽式混合器或圆锥形混合器。最容易的方式是在转筒中混合。作为连续混合器,例如可以使用蜗轮(wormgear)。
优选的混合器类型是滚动式混合器,其利用由电机驱动的转筒。电机上的负载可以用作翻滚固体的粘度以及固体在混合器内形成团块或树脂沉积物的程度的量度:电机上的电力负载随着团块和污垢的增加而升高。将水加入混合固体或加入水溶液、乳液或混悬液中的一种或多种聚脲前体组分可以帮助降低该负载升高,并保持混合固体的自由流动性质,从而能够实现来自混合器的甚至更高的生产率。
如上文在描述聚脲型涂层的形成中所述的,水优选以足以形成反应性胺物质的速率加入异氰酸酯,所述反应性胺物质然后几乎马上与邻近的异氰酸酯反应形成聚脲。优选地,水和含异氰酸酯的组分的使用量在约5-30%的水,95-70%的ISO的范围内,其与催化剂的需求一致以促进ISO的水解,以及与在定时加入到支撑剂基底上的过程中的基底温度一致。水和异氰酸酯以足以保持5-30比95-70的比例加入,以便于促进由异氰酸酯原位形成反应性胺组分,所述反应性胺组分然后与未转化的异氰酸酯反应以制备本发明的聚脲型涂层。这些比例还控制制备的聚脲的最终性质,不论是否驱使其预固化,还是控制以保持可固化水平。
用于涂层的大多数组分优选地与水、多元醇或异氰酸酯一起添加,以促进组分的适当的混合以及计量。优选地,将硅烷助粘剂添加到加热的砂中以制备用于粘附至被施加的聚合物涂层的表面。着色剂在涂覆工艺中通过注入管线添加到涂层混合器中。添加的量以及添加组分的时间能够影响所得到的涂层与芯固体的结合强度(早期或在芯固体预处理时添加的助粘剂)和/或在相邻的涂覆的支撑剂之间形成的颗粒间结合的程度(在涂覆工艺的后期添加的助粘剂)。表面活性剂和/或流动助剂可以在支撑剂已被涂覆之后分别添加,以提高可润湿性和提高流动特性,同时具有更低的细料生成。
用于制备根据本发明的涂覆的支撑剂的方法可以在不使用溶剂的情况下实施。因此,在该方法的一个实施方案的步骤(a)中获得的混合物是不含溶剂的,或基本上是不含溶剂的。如果混合物含有相对于混合物的组分的总质量低于20wt%,优选低于10wt%,更优选低于5wt%,和仍然更优选低于3wt%,以及最优选低于1wt%的溶剂,那么该混合物是基本上不含溶剂的。
涂覆优选与支撑剂上的涂层的固化同时进行。在本发明中,涂覆的支撑剂在小于约5分钟的时间内,优选在1-4分钟的范围内,更优选在1-3分钟的范围内,和最优选在1-2分钟的范围内变得自由流动,以形成涂覆的、基本上固化的、自由流动的、涂覆的支撑剂。该短周期时间与相对适中的涂覆温度结合,以形成涂覆/固化工艺,所述涂覆/固化工艺提供更低的能源消耗、更小的设备、降低的来自工艺和相关的洗气设备(scrubbingequipment)的排放和总体升高的涂层设备产量。
涂层材料或不同的涂层材料的组合可以以一层以上施加。例如,涂覆工艺可以根据需要重复(例如,1-5次、2-4次或2-3次)以获得期望的涂层厚度。
供选择地,根据本发明的包含加入了助粘剂的外层的聚脲型或聚氨酯型涂层可作为最外层施加至已存在的涂层,例如预固化的或可固化的酚醛树脂涂层上。这样的分层方法可利用酚醛树脂涂层的潜在的抗压碎性和其它特性,同时增加本发明的聚脲型或聚氨酯型涂层的结合能力。这样的外涂层将避免对在低温应用,例如50℃且较高达约100℃的低温井中使用的酚醛树脂涂层通常需要添加的活化剂或表面活性剂化合物的需要,从而还避免了与用于水力井压裂中配制的压裂流体或破胶流体的化学不相容性或干扰的可能性。最终的涂覆的支撑剂的典型尺寸范围期望在约16至约100目的范围内。
包含加入的助粘剂的聚脲型和聚氨酯型涂层还可以施加到先前已涂覆有聚脲或聚氨酯的支撑剂,或像所认为的那样,作为连续涂覆工艺的最后一步来原位形成为支撑剂涂层的最外面的“皮”层。涂层的该皮层可增强表面粘着性。可采用添加防结块剂如二氧化硅粉或类似物的方式来保持在所得到的支撑剂的自由流动特性。
类似地,利用该聚脲体系的高反应性,聚脲可以形成为底涂层,接着是加入了助粘剂或偶联剂的酚醛树脂或环氧树脂、聚氨酯或其它涂层的外涂层。
相对于支撑剂的质量为100wt%,施加到支撑剂的作为聚脲或聚氨酯组分的涂层树脂的量优选为约0.5至约10wt%,更优选为约1%至约5wt%。加入的助粘剂的量可以是相对于支撑剂质量的约0.0001wt%至约5wt%。
使用根据本发明的方法,支撑剂可以在约50℃至约175℃,优选在约75℃-125℃范围内的温度下被涂覆,以及优选地以不含溶剂的方式被涂覆。涂覆工艺需要相对小的设备,并且如果需要,还可以在砂或陶瓷基底来源附近、在生产现场(producingfield)的地理位置附近或在井本身处/附近进行。
如果是期望的而决不是必需的,涂覆的支撑剂可烘烤或加热一段时间,这段时间足以进一步增强涂覆的颗粒的最终性能并进一步使可能残留在涂覆的支撑剂中的可用的异氰酸酯、羟基、胺和反应性助粘剂基团反应。即使在第一涂层之后或在层间使用另外的与催化剂接触时间,这样的涂覆后固化也可能发生。通常地,涂覆后固化步骤像烘烤步骤那样在约100°-200℃范围内的温度下进行约1分钟至4小时,优选地,温度为约125°-200℃,进行约1-30分钟。
甚至更优选地,涂覆的支撑剂的固化时间和条件足以制备这样的涂覆的支撑剂,该涂覆的支撑剂当按照在ISO13503-5:2006(E)下的模拟井下条件测试时,显示出小于25wt%,优选小于15wt%,和甚至更优选小于5wt%的涂层损失。甚至更优选地,本发明的涂覆的支撑剂显示出常规的预固化的支撑剂的低粉尘和操作特性(参见APIRP60),而且也显示出小于10%,更优选小于5%,和尤其小于2%的10,000psi下的压碎测试结果。本发明的涂覆的支撑剂优选还具有大于20psi,和更优选大于500psi的无侧限抗压强度,其在给定闭合应力下的裂缝传导率基本等于或大于在相同产品应用范围内使用的酚醛树脂涂层的传导率。
使用涂覆的支撑剂
本发明还包括涂覆的支撑剂与压裂液联合使用以提高石油或天然气的产量。包括注入固结流体的用于压裂疏松地层的技术在本领域也是熟知的。参见第6,732,800号美国专利,将其公开内容引入本文作为参考。一般来讲,流体在小于地层的压裂压力的压力下,通过钻井孔注入地层。待注入到地层中的固结流体的体积是待处理的地层孔隙体积和固结流体渗透地层的能力的函数,并且其可以容易地由本领域普通技术人员确定。作为指导,待处理的地层体积与期望的处理的区域的高度和期望的渗透深度相关,并且渗透深度优选地为径向地进入地层至少约30cm。请注意,由于固结流体是通过穿孔注入的,因此处理的区域实际上来自对齐的穿孔。
用于水力压裂地下地层的技术将为本领域普通技术人员已知,并且会涉及将压裂流体泵入钻孔中并泵出进入周围地层。流体压力在最小原位岩石应力以上,从而在地层中产生或延伸裂缝。为了在释放流体压力之后保持在地层中形成的裂缝,压裂流体携带支撑剂,所述支撑剂的目的是防止裂缝在泵送完成后闭合。
压裂流体无具体限制,可以选自具体领域已知的压裂液、泡沫和气体。合适的压裂液描述于例如WCLyons,GJPlisga,“StandardHandbookOfPetroleumAndNaturalGasEngineering”,GulfProfessionalPublishing(2005)。压裂流体可以是,例如,与聚合物胶凝的水、与聚合物胶凝的水包油乳液、与聚合物胶凝的油包水乳液或液化石油气。在一个优选的实施方案中,压裂液包含所显示的比例的以下成分:1000升水、20kg氯化钾、0.120kg乙酸钠、3.6kg瓜尔豆胶(水可溶性聚合物)、(根据需要)调节pH值到9-11的氢氧化钠、0.120kg硫代硫酸钠和0.180kg过硫酸铵,和任选地用于增强粘度的交联剂,如硼酸钠或硼酸钠与硼酸的组合。
此外,本发明涉及用于产生石油或天然气的方法,所述方法包括使用压裂液将涂覆的支撑剂注入压裂的地层中,即将含有涂覆的支撑剂的压裂液注入含有石油或天然气的岩层中,和/或将其引入含有石油或天然气的岩层中的裂缝内。该方法无具体限制,可以以具体领域中已知的方式实施。压裂液中的支撑剂的浓度可以是本领域已知的任意浓度,并且通常会为每加仑的洁净流体约0.5至约20磅的加入的支撑剂。
压裂流体可以含有加入的支撑剂助留剂,例如,纤维材料、涂覆在支撑剂上的可固化树脂、薄片、可变形的颗粒或粘性支撑剂涂层,以将支撑剂颗粒保留在裂缝中并防止其穿过钻井孔产生。浓度优选为按支撑剂重量计约0.1%至约5.0%的纤维,例如选自天然有机纤维、合成有机纤维、玻璃纤维、碳纤维、陶瓷纤维、无机纤维、金属纤维及其混合物,与可固化的树脂涂覆的支撑剂的组合是特别优选的。支撑剂助留剂旨在将支撑剂固体保持在裂缝中,并且支撑剂和支撑剂助留剂防止在被称为“返排”的过程中重新从井中产生地层颗粒。
本发明的加强的支撑剂尤其充分适合用于增强为低温井设计的支撑剂的颗粒间结合特性,所述低温井例如为井下温度在约75-125°F范围内且裂纹闭合应力在约3000-6000psi范围内的那些。采用本发明,颗粒间结合能够从可忽略的结合强度增强至良好的结合。根据在涂层中使用的聚合物,本发明可相对于没有在支撑剂涂层的外层部分加入偶联剂的相同聚合物引入100-1000%或更大的改进的弯曲(供选择地,这可以被测量为5-100psi或更大的结合强度增加)。
在涂层的外层部分中添加偶联剂对高温支撑剂涂层也有益处。这样的加强的高温涂层通常将在具有200-350°F和6000-12,000psi的裂纹闭合应力水平的井下条件的高温井中使用。在200°F下,根据常规UCS测试,这样的支撑剂呈现出0-5psi的颗粒间结合强度。然而,对于本发明,在150°F下,这些相同的支撑剂将呈现40-60psi的颗粒间结合强度,从而将使用范围扩大至范围更宽的井下条件。
实施例
实施例1-聚脲涂覆工艺
以下为制备根据本发明的聚氨酯基涂层的顺序的实施例,该聚氨酯基涂层在支撑剂芯和支撑剂聚合物涂层的内层之间具有硅烷助粘剂,并且相同的硅烷助粘剂在添加顺序的后期期间加入,以将助粘剂加入到支撑剂涂层的外层中。
添加循环(低温聚氨酯涂层)
在本实施例中的制剂的优点是,由于异氰酸酯-硅烷外层的粘合剂样性质,使得“结合能力”增强,其是在所得到的产品上进行的无侧限抗压强度(UCS)试验中体现出的。这种特殊涂层的粘性增加了在储存和处理时的“结块”的风险,因此,二氧化硅防结块剂在该循环的最后加入以防止产品在储存过程中结块和聚结。
一旦本领域技术人员得到本发明的教导,在不背离本文公开的发明构思的前提下,许多变化和修改是可能的。因此,本发明不受除所附权利要求的精神以外的限制。
Claims (22)
1.一种涂覆的支撑剂,其包括:芯和邻近所述芯的聚合物内涂层部分以及包括有机官能的硅烷偶联剂的外涂层部分。
2.根据权利要求1所述的涂覆的支撑剂,其中所述有机官能的硅烷偶联剂具有通用结构:Si(R1)(R2)(R3)(R4),其中R1、R2、R3和R4可以相同或不同,并且可以独立地选自氢、烷基、卤代烷基、亚烷基、炔基、烷氧基、炔氧基、芳基、芳氧基、取代的芳基、杂芳基、氨基、氨基烷基、芳氨基、环氧化物、硫醇和卤代烷基、醚、酯、尿烷、酰胺,条件是R1、R2、R3和R4中的至少一个包含有机部分。
3.根据权利要求1所述的涂覆的支撑剂,其中所述有机官能的硅烷包括选自甲基、氨基、巯基、氯丙基、甲基丙烯酰基、甲基丙烯酰氧基、乙烯基、苄氨基、脲基、四硫代和C1-C4烷氧基的有机官能团。
4.根据权利要求1所述的涂覆的支撑剂,其中所述有机官能的硅烷是氨基官能的硅烷。
5.根据权利要求4所述的涂覆的支撑剂,其中所述有机官能的硅烷选自氨丙基三乙氧基硅烷、氨丙基三甲氧基硅烷、氨乙基氨丙基三甲氧基硅烷和氨乙基氨乙基氨丙基三甲氧基硅烷。
6.根据权利要求1所述的涂覆的支撑剂,其中所述有机官能的硅烷选自3-[2-(2-氨基乙基氨基)乙基氨基]丙基-三甲氧基硅烷(CAS号35141-30-1)、3-巯基丙基三甲氧基硅烷(CAS号4420-74-0)、正丙基三甲氧基硅烷(CAS号1067-25-0)、[3-(2-氨基乙基)氨基丙基]三甲氧基硅烷(CAS号1760-24-3)、硅烷正十二烷基三甲氧基硅烷(CAS号3069-21-4)、双(三甲氧基甲硅烷基丙基)胺(CAS号82985-35-1)、1,2-双(三甲氧基甲硅烷基)乙烷(CAS号18406-41-2)、乙烯基三(2-甲氧基乙氧基)硅烷(CAS号1067-53-4)、正辛基三乙氧基硅烷(CAS号2943-75-1)、双-[3-(三乙氧基甲硅烷基)丙基]-四硫化物(CAS号40372-72-3)、乙烯基三乙氧基硅烷(CAS号78-08-0)、3-缩水甘油氧基丙基三甲氧基硅烷(CAS号2530-83-8)、3-巯基丙基三乙氧基硅烷(CAS号14814-09-6)、3-缩水甘油氧基丙基三乙氧基硅烷(CAS号2602-34-8)、2-(3,4-环氧基环己基)乙基三甲氧基硅烷(CAS号3388-04-3)、3-氨丙基三甲氧基硅烷(CAS号13822-56-5)、2-(3,4-环氧基环己基)乙基三乙氧基硅烷(CAS号10217-34-2)、3-氨基丙基三乙氧基硅烷(CAS号919-30-2)、3-缩水甘油氧基丙基甲基二甲氧基硅烷(CAS号65799-47-5)、双(三乙氧基甲硅烷基丙基)胺(CAS号13497-18-2)、3-(2-氨基乙基氨基)丙基二甲氧基甲基硅烷(CAS号3069-29-2)、N-(正丁基)-3-氨基丙基三甲氧基硅烷(CAS号31024-56-3)、正丙基三乙氧基硅烷(CAS号2550-02-9)、乙烯基三甲氧基硅烷(CAS号2768-02-7)、3-脲基丙基三乙氧基硅烷(CAS号23779-32-0)、3-甲基丙烯酰氧基丙基三甲氧基硅烷(CAS号2530-85-0)。
7.根据权利要求1所述的涂覆的支撑剂,其中所述有机官能的硅烷选自:具有至少一个羟基烷氧基甲硅烷基和/或环状二烷氧基甲硅烷基的巯基硅烷;具有至少一个羟基烷氧基甲硅烷基和/或环状二烷氧基甲硅烷基的嵌段巯基硅烷;巯基硅烷,其中巯基硅烷单元的硅原子通过桥接二烷氧基而彼此键合,每个硅烷单元任选地具有至少一个羟基烷氧基甲硅烷基或环状二烷氧基甲硅烷基;嵌段巯基硅烷二聚体,其中嵌段巯基硅烷单元的硅原子通过桥接二烷氧基而彼此键合,每个硅烷单元任选地具有至少一个羟基烷氧基甲硅烷基或环状二烷氧基甲硅烷基;硅烷二聚体,其具有巯基硅烷单元,所述巯基硅烷单元的硅原子通过桥接二烷氧基被键合至嵌段巯基硅烷单元的硅原子,每个硅烷单元任选地具有至少一个羟基烷氧基甲硅烷基或环状二烷氧基甲硅烷基;巯基硅烷低聚物,其中邻近的巯基硅烷单元的硅原子通过桥接二烷氧基彼此键合,末端巯基硅烷单元具有至少一个羟基烷氧基甲硅烷基或环状二烷氧基甲硅烷基;嵌段巯基硅烷低聚物,其中邻近的嵌段巯基硅烷单元的硅原子通过桥接二烷氧基彼此键合,末端巯基硅烷单元具有至少一个羟基烷氧基甲硅烷基或环状二烷氧基甲硅烷基;以及硅烷低聚物,其具有至少一个巯基硅烷单元和至少一个嵌段巯基硅烷单元,邻近的硅烷单元的硅原子通过桥接二烷氧基彼此键合,末端硅烷单元具有至少一个羟基烷氧基甲硅烷基或环状二烷氧基甲硅烷基。
8.根据权利要求1所述的涂覆的支撑剂,其中所述有机官能的硅烷包括硅烷的混合物。
9.根据权利要求1所述的涂覆的支撑剂,其中所述内层和所述外层基于相同的聚合物。
10.根据权利要求9所述的涂覆的支撑剂,其中所述内层和所述外层基于聚氨酯。
11.根据权利要求9所述的涂覆的支撑剂,其中所述内层和所述外层基于聚脲聚合物。
12.根据权利要求1所述的涂覆的支撑剂,其中所述内层和所述外层基于不同的聚合物。
13.根据权利要求12所述的涂覆的支撑剂,其中所述内层是酚醛聚合物且所述外层是聚氨酯基或聚脲基聚合物。
14.根据权利要求12所述的涂覆的支撑剂,其中所述内层是酚醛聚合物且所述外层是聚氨酯基聚合物。
15.根据权利要求12所述的涂覆的支撑剂,其中所述内层是酚醛聚合物且所述外层是聚脲基聚合物。
16.根据权利要求1所述的涂覆的支撑剂,其中所述有机官能的硅烷包括硅烷封端的聚合物。
17.根据权利要求16所述的涂覆的支撑剂,其中所述有机官能的硅烷包括硅烷封端的聚醚或硅烷封端的聚氨酯。
18.根据权利要求16所述的涂覆的支撑剂,其中所述有机官能的硅烷是硅烷封端的聚醚。
19.根据权利要求16所述的涂覆的支撑剂,其中所述有机官能的硅烷是硅烷封端的聚氨酯。
20.一种用于撑开压裂地层的方法,该方法通过包括向所述压裂地层引入涂覆的支撑剂的过程来实现,所述涂覆的支撑剂包括:(a)芯;以及(b)聚合物涂层,该聚合物涂层具有(i)邻近所述芯的内涂层部分和(ii)包括有机官能的硅烷偶联剂的外涂层部分。
21.根据权利要求20所述的方法,其中所述压裂地层的井下条件包括在约75°F至约125°F范围内的温度。
22.根据权利要求20所述的方法,其中所述压裂地层的井下条件包括在约150°F至约350°F范围内的温度。
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Publication number | Priority date | Publication date | Assignee | Title |
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CN108949140A (zh) * | 2018-09-30 | 2018-12-07 | 重庆长江造型材料(集团)股份有限公司 | 一种自悬浮式支撑剂 |
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BR112015028846A2 (pt) | 2017-07-25 |
MX2015015703A (es) | 2016-07-21 |
US20190249077A1 (en) | 2019-08-15 |
US20210403801A1 (en) | 2021-12-30 |
US11760924B2 (en) | 2023-09-19 |
WO2014186220A1 (en) | 2014-11-20 |
HK1221731A1 (zh) | 2017-06-09 |
CA2912663C (en) | 2021-08-03 |
US11098242B2 (en) | 2021-08-24 |
US20140338906A1 (en) | 2014-11-20 |
US10100247B2 (en) | 2018-10-16 |
CA2912663A1 (en) | 2014-11-20 |
AR096264A1 (es) | 2015-12-16 |
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