CN114808448B - 改性纤维材料及其制备方法、油基钻井液用封堵剂 - Google Patents
改性纤维材料及其制备方法、油基钻井液用封堵剂 Download PDFInfo
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- CN114808448B CN114808448B CN202110083580.5A CN202110083580A CN114808448B CN 114808448 B CN114808448 B CN 114808448B CN 202110083580 A CN202110083580 A CN 202110083580A CN 114808448 B CN114808448 B CN 114808448B
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- monomer
- modified
- fiber material
- fiber
- acrylic
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- 239000002657 fibrous material Substances 0.000 title claims abstract description 75
- 238000005553 drilling Methods 0.000 title claims abstract description 66
- 239000012530 fluid Substances 0.000 title claims abstract description 62
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 140
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000000835 fiber Substances 0.000 claims abstract description 55
- 239000011159 matrix material Substances 0.000 claims abstract description 31
- 125000002091 cationic group Chemical group 0.000 claims abstract description 29
- 150000001408 amides Chemical class 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 16
- 229920001577 copolymer Polymers 0.000 claims abstract description 13
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- 210000004177 elastic tissue Anatomy 0.000 claims abstract description 6
- 239000010893 paper waste Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000000839 emulsion Substances 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000003995 emulsifying agent Substances 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 15
- 230000001804 emulsifying effect Effects 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 14
- -1 dimethyl diacrylamide propane sulfonic acid Chemical compound 0.000 claims description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 11
- 239000003431 cross linking reagent Substances 0.000 claims description 11
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 10
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000010008 shearing Methods 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 5
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 claims description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 4
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 4
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical group [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 claims description 4
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 claims description 3
- BYMHXIQVEAYSJD-UHFFFAOYSA-M sodium;4-sulfophenolate Chemical compound [Na+].OC1=CC=C(S([O-])(=O)=O)C=C1 BYMHXIQVEAYSJD-UHFFFAOYSA-M 0.000 claims description 3
- LWZFANDGMFTDAV-BURFUSLBSA-N [(2r)-2-[(2r,3r,4s)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O LWZFANDGMFTDAV-BURFUSLBSA-N 0.000 claims description 2
- 238000005253 cladding Methods 0.000 claims description 2
- 235000011067 sorbitan monolaureate Nutrition 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 15
- 238000001179 sorption measurement Methods 0.000 abstract description 12
- 239000011148 porous material Substances 0.000 abstract description 11
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- 239000011248 coating agent Substances 0.000 abstract description 6
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- 239000002131 composite material Substances 0.000 abstract description 3
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 7
- 230000018109 developmental process Effects 0.000 description 7
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- 239000000203 mixture Substances 0.000 description 6
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- 239000007789 gas Substances 0.000 description 4
- 230000001737 promoting effect Effects 0.000 description 4
- 239000004971 Cross linker Substances 0.000 description 3
- 125000005396 acrylic acid ester group Chemical group 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 1
- IUHFWCGCSVTMPG-UHFFFAOYSA-N [C].[C] Chemical group [C].[C] IUHFWCGCSVTMPG-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 229940077386 sodium benzenesulfonate Drugs 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
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- D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
- D06M14/08—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of synthetic origin
- D06M14/10—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of synthetic origin of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
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- D06M14/02—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of natural origin
- D06M14/04—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of natural origin of vegetal origin, e.g. cellulose or derivatives thereof
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- D06M14/08—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of synthetic origin
- D06M14/12—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of synthetic origin of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
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- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
- D06M15/29—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides containing a N-methylol group or an etherified N-methylol group; containing a N-aminomethylene group; containing a N-sulfidomethylene group
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- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
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- Chemical Kinetics & Catalysis (AREA)
- Textile Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
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- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
本发明提供了一种改性纤维材料及其制备方法、油基钻井液用封堵剂。该改性纤维材料包括基体纤维以及通过物理包覆和/或化学键连接在其表面的丙烯酸类单体、酰胺类单体、丙烯酸酯类单体及阳离子单体的共聚物。其中,基体纤维为改性胶粘纤维、废纸浆植物纤维和弹性纤维中一种或多种。本发明的改性纤维材料,其一,具有更佳的亲油性,从而在油基钻井液中适应性更佳、配伍性更好;其二,具有更佳的吸附作用,可以在地层孔道中有效驻留;其三,具有更佳的抗高温性能,可以更好地适应井下高温地层环境。在后续作为油基钻井液用封堵剂使用时,封堵性能更佳,封堵尺度更广,能够有效“架桥”封堵,满足对微裂缝、微孔隙和层理发育地层的封堵需求。
Description
技术领域
本发明涉及油基钻井液领域,具体而言,涉及一种改性纤维材料及其制备方法、油基钻井液用封堵剂。
背景技术
根据国外页岩油气藏开发经验,油基钻井液具有良好的抑制、润滑等能力,因而国内目前普遍采用油基钻井液进行长水平段页岩气井的钻进。油基钻井液可解决泥页岩的水化问题,但由于页岩地层微裂缝、层理发育,钻井液易沿着微裂隙进入页岩内部,造成钻井液的循环损耗量大,同时可引起近井壁地带孔隙压力提高,从而导致井壁周围的岩石崩落掉块直至坍塌。因此可通过提高油基钻井液的封堵能力,阻止钻井液侵入地层,形成致密封堵层,增强近井壁地带的岩石强度,达到井壁稳定、安全钻进的目的。目前使用的封堵材料多是仅具亲水性能的桥塞类随钻防漏材料,但桥塞类随钻防漏材料种类单一,且在油基钻井液中的适应性差,粒径匹配能力不足,也无法满足对深部地层高温的抵抗能力。
总之,现有的常规油基钻井液封堵剂存在以下缺点:(1)亲油性差,在油基钻井液中适应性差,无法有效分散,从而导致封堵强度低;(2)常规封堵剂难以在地层孔道中有效驻留,封堵强度低;(3)抗温性能不足,无法适应井下高温地层环境。
发明内容
本发明的主要目的在于提供一种改性纤维材料及其制备方法、油基钻井液用封堵剂,以解决现有技术中常规油基钻井液封堵剂存在的以下问题:(1)亲油性差,在油基钻井液中适应性差,无法有效分散,从而导致封堵强度低;(2)常规封堵剂难以在地层孔道中有效驻留,封堵强度低;(3)抗温性能不足,无法适应井下高温地层环境。
为了实现上述目的,根据本发明的一个方面,提供了一种改性纤维材料。改性纤维材料包括基体纤维以及通过物理包覆和/或化学键连接在其表面的丙烯酸类单体、酰胺类单体、丙烯酸酯类单体及阳离子单体的共聚物;其中,基体纤维为改性胶粘纤维、废纸浆纤维和弹性纤维中的一种或多种。
进一步地,基体纤维和丙烯酸酯类单体的重量比为(4:3)~(1:1)。
优选地,丙烯酸类单体、酰胺类单体、丙烯酸酯类单体和阳离子单体与的重量比为(10~15):(10~15):(15~20):(3~4)。
进一步地,基体纤维的长度为2~4mm,直径为10~20μm。
进一步地,丙烯酸类单体为丙烯酸和/或甲基丙烯酸。
进一步地,酰胺类单体选自己内酰胺、丙烯酰胺、二甲基二丙烯酰胺基丙磺酸、N-羟甲基丙烯酰胺中的一种或多种。
进一步地,丙烯酸酯类单体选自丙烯酸丁酯、丙烯酸十二酯、丙烯酸十八酯、甲基丙烯酸甲酯中的一种或多种。
进一步地,阳离子单体选自二甲基二烯丙基氯化铵和/或2-(甲基丙烯酰氧基)乙基三甲基氯化铵。
进一步地,形成共聚物的单体还包括抗温单体。
优选地,抗温单体选自N-乙烯基吡咯烷酮、苯乙烯、苯乙烯磺酸钠、4-羟基苯磺酸钠中的一种或多种。
优选地,抗温单体和纤维材料的重量比为(1:4)~(2:5)。
根据本发明的一个方面,提供了一种上述改性纤维材料的制备方法,制备方法包括以下步骤;S1,将丙烯酸类单体、酰胺类单体、丙烯酸酯类单体、阳离子单体、水及乳化剂混合,得到预乳液;S2,依次向预乳液中加入基体纤维、引发剂及交联剂进行乳液聚合反应,得到改性纤维材料。
进一步地,步骤S1包括:将丙烯酸类单体、酰胺类单体、阳离子单体、水及pH调节剂混合,得到混合液,其中,混合液pH为6.0~8.0;优选pH调节剂为氢氧化钠或其水溶液;将混合液与丙烯酸酯类单体、可选的抗温单体及乳化剂混合,通过剪切乳化机乳化得到预乳液。
优选地,乳化剂选自MS-1、OP-10、Span20中的一种。
进一步地,步骤S2中,乳液聚合反应温度为70~80℃,时间为3.5~4.5h。
优选地,引发剂选自过硫酸铵、过硫酸钾、过氧化氢、过氧化二苯甲酰、偶氮二异丁腈中的一种。
优选地,交联剂为N,N-亚甲基双丙烯酰胺、4-乙烯基吡啶、2-乙烯苯中的一种。
根据本发明的一个方面,提供了一种油基钻井液用封堵剂,油基钻井液用封堵剂为前述的改性纤维材料,或前述的改性纤维材料的制备方法制备得到的改性纤维材料。
本发明制备的改性纤维材料同时具有更佳的亲油性、吸附性和抗高温性能,从而在油基钻井液中适应性更佳,配伍性更好,可以在地层孔道中有效驻留,且可以更好地适应井下高温地层环境,在后续作为油基钻井液封堵剂使用时,封堵性能更佳。
具体实施方式
需要说明的是,在不冲突的情况下,本申请中的实施例及实施例中的特征可以相互组合。下面将结合实施例来详细说明本发明。
正如背景技术部分所描述的,现有技术中常规油基钻井液封堵剂存在的以下问题:(1)亲油性差,在油基钻井液中适应性差,无法有效分散,从而导致封堵强度低;(2)常规封堵剂难以在地层孔道中有效驻留,封堵强度低;(3)抗温性能不足,无法适应井下高温地层环境。
为了解决这一问题,本发明提供了一种改性纤维材料,改性纤维材料包括基体纤维以及通过物理包覆和/或化学键连接在其表面的丙烯酸类单体、酰胺类单体、丙烯酸酯类单体及阳离子单体的共聚物。其中,基体纤维为改性胶粘纤维、废纸浆植物纤维和弹性纤维中一种或多种。
具体地,改性胶粘纤维为聚丙烯改性纤维(上海邦维市政工程有限公司),废纸浆纤维为报纸纤维(河北丹煦矿产产品贸易有限公司),弹性纤维为束状合成聚酯纤维(上海邦维市政工程有限公司)。本发明对这些纤维进行改性,以促使其解决上述问题,在基体纤维表面物理或化学包覆了丙烯酸类单体、酰胺类单体、丙烯酸酯类单体及阳离子单体的共聚物。改性胶粘纤维、废纸浆纤维、弹性纤维通过纤维分子链上携带的羟基、氨基等,使至少部分共聚物通过化学键链接在其表面,也有部分共聚物物理包覆在其表面。
其中,共聚物中丙烯酸酯类单体、丙烯酸类单体及酰胺类单体作为共聚物单体主体(组成聚合物主链中占主要部分的单体),促使聚合后共聚物改性纤维材料中碳碳结构的主链更有利于提高材料的抗温性能,进而在后续作为油基钻井液用封堵剂使用时,可以更好地适应井下高温地层环境。而且,丙烯酸酯类单体具有亲油特性,可以加强材料的亲油性,促使材料具有更好的亲油效果,且在油基钻井液中适应性更佳,好的亲油性和适应性促使材料在油基钻井液中的分散效果更佳,好的分散性促使材料在油基钻井液中的配伍性更好,且长时间保存也不会聚结和沉降,进而在后续作为油基钻井液用封堵剂使用时封堵强度更高。阳离子单体具有吸附性,可以加强材料的吸附作用,从而可以实现材料在地层孔道中的有效驻留,进而促使改性纤维材料在后续作为油基钻井液用封堵剂使用时,封堵强度更高。纤维材料作为基质,一方面,原料来源更广,更易取材,且其具有物理上的弹性效果,能对不同尺度范围的微裂缝、微孔隙和层理发育进行封堵。另一方面,本发明选择的基体纤维材料,可以和丙烯酸类单体、酰胺类单体、丙烯酸酯类单体以及阳离子单体的共聚物通过化学键和/或物理包覆得到亲油性、吸附性及抗高温性能更佳、且各性能均一性更佳的改性纤维材料。
总之,本发明的改性纤维材料,其一,具有更佳的亲油性,从而在油基钻井液中适应性更佳、配伍性更好;其二,具有更佳的吸附作用,可以在地层孔道中有效驻留;其三,具有更佳的抗高温性能,可以更好地适应井下高温地层环境。在后续作为油基钻井液用封堵剂使用时,封堵性能更佳,封堵尺度更广,能够有效“架桥”封堵,满足对微裂缝、微孔隙和层理发育地层的封堵需求。并且,在常温和高温条件下均可大幅度封堵岩心,具有更好的封堵效果。
优选地,基体纤维和丙烯酸酯类单体的重量比为(4:3)~(5:3)。在此范围内,可以促使改性纤维材料的亲油性更佳,和油基钻井液的适应性更佳、配伍性更佳。优选地,丙烯酸类单体、酰胺类单体、丙烯酸酯类单体和阳离子单体的重量比为(8~10):(8~10):(15~20):(3~5)。在此范围内,可以促使改性纤维材料的吸附作用更佳,从而可以进一步实现材料在地层孔道中的有效驻留。同时,改性纤维材料的抗温性能更佳,且能更好的平衡材料的亲油性和吸附性。
优选地,基体纤维的长度为2~4mm,直径为10~20μm。基于此,一方面,可以促使基体纤维和聚合物的包覆效果和连接效果均更佳,进而能更好的平衡基体纤维本身性能和聚合物中各单体的性能,从而得到亲油性、吸附性及抗高温性能更佳的改性纤维材料。另一方面,在后续作为封堵剂使用时,封堵性能更佳,封堵尺度更广,能够有效“架桥”封堵,满足对微裂缝、微孔隙和层理发育地层的封堵需求。
基于进一步促使改性纤维材料抗高温性能更佳的目的,丙烯酸类单体为丙烯酸和/或甲基丙烯酸,酰胺类单体选自己内酰胺、丙烯酰胺、二甲基二丙烯酰胺基丙磺酸、N-羟甲基丙烯酰胺中的一种或多种。
基于进一步促使改性纤维材料亲油性和抗高温性能更佳的目的,丙烯酸酯类单体选自丙烯酸丁酯、丙烯酸十二酯、丙烯酸十八酯、甲基丙烯酸甲酯中的一种或多种。
基于进一步促使改性纤维材料吸附效果更好的目的,阳离子单体选自二甲基二烯丙基氯化铵和/或2-(甲基丙烯酰氧基)乙基三甲基氯化铵。
在一种优选的实施方案中,形成共聚物的单体还包括抗温单体,抗温单体选自N-乙烯基吡咯烷酮、苯乙烯、苯乙烯磺酸钠、4-羟基苯磺酸钠中的一种或多种。基于此,可以进一步更大幅度地提升改性纤维材料的抗温性能。
本发明提供了一种前述改性纤维材料的制备方法,制备方法包括以下步骤;S1,将丙烯酸类单体、酰胺类单体、丙烯酸酯类单体、阳离子单体、水及乳化剂混合,得到预乳液;S2,依次向预乳液中加入基体纤维、引发剂及交联剂进行乳液聚合反应,得到改性纤维材料。
本发明先将丙烯酸类单体、酰胺类单体、丙烯酸酯类单体、阳离子单体及乳化剂混合,得到预乳液,再依次向预乳液中加入纤维材料、引发剂及交联剂进行乳液聚合反应,得到改性纤维材料。这样操作,在原料混合均匀稳定后再加入基体纤维和引发剂及交联剂,可以促使乳液聚合反应更稳定,且丙烯酸类单体、酰胺类单体、丙烯酸酯类单体、阳离子单体能够在乳液聚合的过程中在基体纤维表面原位生长,对于表面携带有可反应基团的基体纤维,也能够在共聚物原位聚合的过程中直接反应形成化学连接,因此能够使共聚物在基体纤维表面形成更好的包覆,更有利于控制改性纤维材料包覆层的组成与尺寸的均一性,使其各方面性能更均一。且基于前文的各项原因,本发明的改性纤维材料:具有更佳的亲油性,从而在油基钻井液中适应性更佳、配伍性更好;具有更佳的吸附作用,可以在地层孔道中有效驻留;具有更佳的抗高温性能,可以更好地适应井下高温地层环境。在后续作为油基钻井液用封堵剂使用时,封堵效果更佳。
基于促使乳化效果更佳的目的,在一种优选的实施方案中,步骤S1包括:将丙烯酸类单体、酰胺类单体、阳离子单体、去离子水及pH调节剂混合,得到混合液,其中,混合液pH为6.0~8.0,其中pH调节剂为30wt%氢氧化钠。将混合液与丙烯酸酯类单体、抗温单体及乳化剂混合,通过剪切乳化机乳化得到预乳液,其中剪切乳化机转速为3000r/min。优选地,乳化剂选自MS-1、OP-10、Span80中的一种,乳化剂的用量为丙烯酸类单体重量的5~10%。
在一种优选的实施方案中,步骤S2中,先将上述预乳液置于三口烧瓶中预热搅拌,待达到55℃时再加入基体纤维,保持加热搅拌状态再逐滴加入引发剂溶液(0.1~0.2g引发剂溶于10~15mL去离子水中),反应30min后逐滴加入交联剂溶液(0.3~0.5g交联剂溶于10~15mL去离子水中),在70~80℃条件下保持反应状态3h~4h,得到改性纤维材料。这样操作,可以进一步促使乳液聚合反应更稳定,改性纤维材料的性能均一性更佳。更优选地,引发剂选自过硫酸铵、过硫酸钾、过氧化氢、过氧化二苯甲酰、偶氮二异丁腈中的一种,交联剂为N,N-亚甲基双丙烯酰胺、4-乙烯基吡啶、2-乙烯苯中的一种。
本发明还提供了一种油基钻井液用封堵剂,油基钻井液用封堵剂为前述改性纤维材料,或前述改性纤维材料的制备方法制备得到的改性纤维材料。
另外,本发明还提供了上述改性纤维材料作为油基钻井液用封堵剂的应用。
基于前文的各项原因,本发明的改性纤维材料同时具有更佳的亲油性、吸附作用和抗高温性能,从而在油基钻井液中适应性更佳,配伍性更好,可以在地层孔道中有效驻留,且可以更好地适应井下高温地层环境。本发明的改性纤维材料在作为油基钻井液用封堵剂使用时,封堵性能更佳,封堵尺度更广,能够有效“架桥”封堵,满足对微裂缝、微孔隙和层理发育地层的封堵需求。并且,在常温和高温条件下均可大幅度封堵实验岩心,具有更好的封堵效果。
以下结合具体实施例对本申请作进一步详细描述,这些实施例不能理解为限制本申请所要求保护的范围。
实施例1
将丙烯酸10g、己内酰胺5g、丙烯酰胺5g、二甲基二烯丙基氯化铵3g加入180mL去离子水中混合,并加入10mL 30wt%氢氧化钠溶液,得到pH为7.0的混合液。
在混合液中加入丙烯酸丁酯25g、丙烯酸十二酯10g、N-乙烯基吡咯烷酮3g、乳化剂MS-12g,通过剪切乳化机乳化得到预乳液,其中,剪切乳化机转速为3000r/min。
将预乳液置于三口烧瓶中预热搅拌,待温度达到55℃时加入聚丙烯改性纤维(购于上海邦维市政工程有限公司)20g,保持加热搅拌状态,逐滴加入引发剂溶液(0.1g过硫酸钾溶于2mL去离子水),反应30min后逐滴加入交联剂溶液(0.1g N,N-亚甲基双丙烯酰胺溶于2mL去离子水)。在70℃条件下反应4h,得到改性纤维材料。
其中,纤维材料、丙烯酸酯类单体、阳离子单体、丙烯酸类单体、酰胺类单体和抗温单体的重量比为:20:35:3:10:10:3。
实施例2
将甲基丙烯酸10g、己内酰胺5g、丙烯酰胺5g、2-(甲基丙烯酰氧基)乙基三甲基氯化铵4g加入180mL去离子水中混合,并加入10mL 30wt%氢氧化钠溶液,得到pH为7.0的混合液。
在混合液中加入丙烯酸十二酯22g、丙烯酸十八酯10g、苯乙烯5g、乳化剂MS-1 2g,通过剪切乳化机乳化得到预乳液,其中,剪切乳化机转速为3000r/min。
将预乳液置于三口烧瓶中预热搅拌,待温度达到55℃时加入报纸纤维(购于河北丹煦矿产产品贸易有限公司)20g,保持加热搅拌状态,逐滴加入引发剂溶液(0.1g过硫酸钾溶于2mL去离子水),反应30min后逐滴加入交联剂溶液(0.1g N,N-亚甲基双丙烯酰胺溶于2mL去离子水)。在70℃条件下反应4h,得到改性纤维材料。
其中,纤维材料、丙烯酸酯类单体、阳离子单体、丙烯酸类单体、酰胺类单体和抗温单体的重量比为:20:32:4:10:10:5。
实施例3
将丙烯酸8g、甲基丙烯酸5g、二甲基二丙烯酰胺基丙磺酸3g、N-羟甲基丙烯酰胺3g、2-(甲基丙烯酰氧基)乙基三甲基氯化铵4g加入180mL去离子水中混合,并加入13mL30wt%氢氧化钠溶液,得到pH为7.0的混合液。
在混合液中加入丙烯酸十八酯14g、甲基丙烯酸甲酯20g、苯乙烯磺酸钠3g、4-羟基苯磺酸钠2g、乳化剂MS-1 2g,通过剪切乳化机乳化得到预乳液,其中,剪切乳化机转速为3000r/min。
将预乳液置于三口烧瓶中预热搅拌,待温度达到55℃时加入束状合成聚酯纤维(购于上海邦维市政工程有限公司)20g,保持加热搅拌状态,逐滴加入引发剂溶液(0.1g过硫酸钾溶于2mL去离子水),反应30min后逐滴加入交联剂溶液(0.1g N,N-亚甲基双丙烯酰胺溶于2mL去离子水)。在70℃条件下反应4h,得到改性纤维材料。
其中,纤维材料、丙烯酸酯类单体、阳离子单体、丙烯酸类单体、酰胺类单体和抗温单体的重量比为:20:34:4:13:6:5。
对比例1
采用实施例1中未改性的基体纤维作为封堵剂。
性能表征:
油基钻井液基浆的配置:在高脚杯中加入400mL白油在高速搅拌的状态下按顺序加入12g主乳化剂HT-MUL、6g辅乳化剂HT-WEL和100mL 25%氯化钙水溶液高速搅拌20min,加入8g有机土高速搅拌20min,加入12g氧化钙高速搅拌30min,得到油基钻井液基浆。
在油基钻井液基浆中加入质量比例2%的实施例1至3中的改性纤维材料及对比例1中的封堵剂,配方如下表1。
表1
编号 | 配方 |
1 | 油基钻井液基浆 |
2 | 油基钻井液基浆+2%实施例1改性纤维 |
3 | 油基钻井液基浆+2%实施例2改性纤维 |
4 | 油基钻井液基浆+2%实施例3改性纤维 |
5 | 油基钻井液基浆+2%对比例1封堵剂 |
1、配伍性能测试
针对封堵剂是否能在油基钻井液良好的分散悬浮同时不影响油基钻井液的流变性能和油基钻井液的稳定性,对封堵剂在油基钻井液中的配伍性进行评价。
参照国标《GB/T 29170-2012石油天然气工业钻井液实验室测试》测试。将编号1至5中材料分别用利用滚子加热炉在180℃条件下老化16h,测定钻井液的高温及常温流变参数(AV表观粘度、PV塑性粘度、YP动切力),API滤失量、高温高压滤失量和破乳电压。流变性能测试结果如下表2,滤失性能测试结果如下表3。
表2
表3
2、亲油性表征
采用测定三相接触角的方法。即将部分液态药品烘干后称取10g的实施例1至3中的改性纤维材料及对比例1的封堵剂在7MPa的压力下用压片机制成薄片,利用静滴接触角测定仪,记录去离子水液滴到达薄片的全过程,找到液滴与薄片接触稳定的时刻,通过软件分析图片,计算得到接触角。测试结果如下表4所示:
表4
接触角 | |
实施例1 | 105° |
实施例2 | 107° |
实施例3 | 106° |
对比例1 | 95° |
3、封堵效果测定
将编号1至5中材料分别使用滚子加热炉在180℃条件下老化16h,采用岩心封堵实验来测定本发明研制的封堵剂在高温及常温下的封堵效果,选择渗透率为1000md的人造岩心用饱和水处理,用煤油驱替水,保持围压比气瓶提供的压力大0.5~1MPa,保证钻井液不会从岩心周围窜出,测试温度为50℃,污染压力为3.0MPa,时间为3h。用正向封堵率和反向封堵率来评价封堵剂对地层的封堵能力,测试结果见表5。
表5
从以上的描述中,可以看出,本发明上述的实施例实现了如下技术效果:
本发明的改性纤维材料,其一,具有更佳的亲油性,从而在油基钻井液中适应性更佳、配伍性更好;其二,具有更佳的吸附作用,可以在地层孔道中有效驻留;其三,具有更佳的抗高温性能,可以更好地适应井下高温地层环境。在后续作为油基钻井液用封堵剂使用时,封堵性能更佳,封堵尺度更广,能够有效“架桥”封堵,满足对微裂缝、微孔隙和层理发育地层的封堵需求。并且,在常温和高温条件下均可大幅度封堵实验岩心,具有更好的封堵效果。
以上仅为本发明的优选实施例而已,并不用于限制本发明,对于本领域的技术人员来说,本发明可以有各种更改和变化。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (7)
1.一种改性纤维材料,其特征在于,所述改性纤维材料包括基体纤维以及通过物理包覆和/或化学键连接在其表面的丙烯酸类单体、酰胺类单体、丙烯酸酯类单体、阳离子单体及抗温单体的共聚物;其中,所述基体纤维为改性胶粘纤维、废纸浆纤维和弹性纤维中的一种或多种;所述基体纤维和所述丙烯酸酯类单体的重量比为(4:3)~(1:1),所述丙烯酸类单体、所述酰胺类单体、所述丙烯酸酯类单体和所述阳离子单体与的重量比为(10~15):(10~15):(15~20):(3~4);
所述丙烯酸类单体为丙烯酸和/或甲基丙烯酸;所述酰胺类单体选自己内酰胺、丙烯酰胺、二甲基二丙烯酰胺基丙磺酸、N-羟甲基丙烯酰胺中的一种或多种;所述丙烯酸酯类单体选自丙烯酸丁酯、丙烯酸十二酯、丙烯酸十八酯、甲基丙烯酸甲酯中的一种或多种;所述阳离子单体选自二甲基二烯丙基氯化铵和/或2-(甲基丙烯酰氧基)乙基三甲基氯化铵;所述抗温单体选自N-乙烯基吡咯烷酮、苯乙烯、苯乙烯磺酸钠、4-羟基苯磺酸钠中的一种或多种;
所述改性纤维材料的制备方法包括以下步骤;
S1,将所述丙烯酸类单体、所述酰胺类单体、所述丙烯酸酯类单体、所述阳离子单体、所述抗温单体、水及乳化剂混合,得到预乳液;
S2,依次向所述预乳液中加入基体纤维、引发剂及交联剂进行乳液聚合反应,得到所述改性纤维材料。
2.根据权利要求1所述的改性纤维材料,其特征在于,所述基体纤维的长度为2~4mm,直径为10~20μm。
3.根据权利要求1所述的改性纤维材料,其特征在于,所述抗温单体和所述纤维材料的重量比为(1:4)~(2:5)。
4.一种权利要求1至3中任一项所述的改性纤维材料的制备方法,其特征在于,所述制备方法包括以下步骤;
S1,将丙烯酸类单体、酰胺类单体、丙烯酸酯类单体、阳离子单体、抗温单体、水及乳化剂混合,得到预乳液;
S2,依次向所述预乳液中加入基体纤维、引发剂及交联剂进行乳液聚合反应,得到所述改性纤维材料。
5.根据权利要求4所述的改性纤维材料的制备方法,其特征在于,所述步骤S1包括:
将所述丙烯酸类单体、所述酰胺类单体、所述阳离子单体、所述水及pH调节剂混合,得到混合液,其中,所述混合液pH为6.0~8.0;所述pH调节剂为氢氧化钠或其水溶液;
将所述混合液与所述丙烯酸酯类单体、所述抗温单体及所述乳化剂混合,通过剪切乳化机乳化得到所述预乳液;
所述乳化剂选自MS-1、OP-10、Span20中的一种。
6.根据权利要求4所述的改性纤维材料的制备方法,其特征在于,所述步骤S2中,所述乳液聚合反应温度为70~80℃,时间为3.5~4.5h;
所述引发剂选自过硫酸铵、过硫酸钾、过氧化氢、过氧化二苯甲酰、偶氮二异丁腈中的一种;
所述交联剂为N,N-亚甲基双丙烯酰胺、4-乙烯基吡啶、2-乙烯苯中的一种。
7.一种油基钻井液用封堵剂,其特征在于,所述油基钻井液用封堵剂为权利要求1至3中任一项所述的改性纤维材料,或权利要求4至6中任一项所述的改性纤维材料的制备方法制备得到的所述改性纤维材料。
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