CN112424312A - 用于油田工业中延迟酸化的单氯乙酸的盐和螯合剂 - Google Patents
用于油田工业中延迟酸化的单氯乙酸的盐和螯合剂 Download PDFInfo
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- CN112424312A CN112424312A CN201980047131.6A CN201980047131A CN112424312A CN 112424312 A CN112424312 A CN 112424312A CN 201980047131 A CN201980047131 A CN 201980047131A CN 112424312 A CN112424312 A CN 112424312A
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- China
- Prior art keywords
- acid
- salt
- monovalent
- chelating agent
- monochloroacetic acid
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- 150000003839 salts Chemical class 0.000 title claims abstract description 54
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000002738 chelating agent Substances 0.000 title claims abstract description 43
- 230000020477 pH reduction Effects 0.000 title description 6
- 230000003111 delayed effect Effects 0.000 title description 4
- 238000000034 method Methods 0.000 claims abstract description 35
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 34
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 22
- 150000001768 cations Chemical class 0.000 claims abstract description 19
- 239000011734 sodium Substances 0.000 claims abstract description 16
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- 239000012530 fluid Substances 0.000 claims description 56
- 239000002253 acid Substances 0.000 claims description 19
- 239000013522 chelant Substances 0.000 claims description 16
- 239000003112 inhibitor Substances 0.000 claims description 15
- 230000007797 corrosion Effects 0.000 claims description 13
- 238000005260 corrosion Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000000654 additive Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 10
- 239000003349 gelling agent Substances 0.000 claims description 9
- -1 galacturonic acid Chemical class 0.000 claims description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- 239000003623 enhancer Substances 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 230000035699 permeability Effects 0.000 claims description 6
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Chemical class OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 5
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical class OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 5
- 150000007513 acids Chemical class 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000006254 rheological additive Substances 0.000 claims description 4
- 239000000080 wetting agent Substances 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- DSLZVSRJTYRBFB-LLEIAEIESA-N D-glucaric acid Chemical class OC(=O)[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O DSLZVSRJTYRBFB-LLEIAEIESA-N 0.000 claims description 3
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 3
- 229940123973 Oxygen scavenger Drugs 0.000 claims description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 3
- 230000000844 anti-bacterial effect Effects 0.000 claims description 3
- 239000003899 bactericide agent Substances 0.000 claims description 3
- 239000003139 biocide Substances 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- 230000001804 emulsifying effect Effects 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 239000004088 foaming agent Substances 0.000 claims description 3
- 239000000174 gluconic acid Chemical class 0.000 claims description 3
- 235000012208 gluconic acid Nutrition 0.000 claims description 3
- 239000003607 modifier Substances 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 claims description 3
- WSHYKIAQCMIPTB-UHFFFAOYSA-M potassium;2-oxo-3-(3-oxo-1-phenylbutyl)chromen-4-olate Chemical class [K+].[O-]C=1C2=CC=CC=C2OC(=O)C=1C(CC(=O)C)C1=CC=CC=C1 WSHYKIAQCMIPTB-UHFFFAOYSA-M 0.000 claims description 3
- 239000011435 rock Substances 0.000 claims description 3
- 239000002455 scale inhibitor Substances 0.000 claims description 3
- 239000003381 stabilizer Substances 0.000 claims description 3
- 238000009736 wetting Methods 0.000 claims description 3
- IAJILQKETJEXLJ-UHFFFAOYSA-N Galacturonsaeure Natural products O=CC(O)C(O)C(O)C(O)C(O)=O IAJILQKETJEXLJ-UHFFFAOYSA-N 0.000 claims description 2
- IAJILQKETJEXLJ-RSJOWCBRSA-N aldehydo-D-galacturonic acid Chemical compound O=C[C@H](O)[C@@H](O)[C@@H](O)[C@H](O)C(O)=O IAJILQKETJEXLJ-RSJOWCBRSA-N 0.000 claims description 2
- 239000004971 Cross linker Substances 0.000 claims 1
- 239000013618 particulate matter Substances 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 43
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 33
- 238000005755 formation reaction Methods 0.000 description 26
- 229910000019 calcium carbonate Inorganic materials 0.000 description 24
- 239000000243 solution Substances 0.000 description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 20
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- FOCAUTSVDIKZOP-UHFFFAOYSA-M chloroacetate Chemical compound [O-]C(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-M 0.000 description 12
- 239000000523 sample Substances 0.000 description 12
- 238000004090 dissolution Methods 0.000 description 11
- 239000002244 precipitate Substances 0.000 description 9
- 239000003921 oil Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- CHRHZFQUDFAQEQ-UHFFFAOYSA-L calcium;2-hydroxyacetate Chemical compound [Ca+2].OCC([O-])=O.OCC([O-])=O CHRHZFQUDFAQEQ-UHFFFAOYSA-L 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 239000000176 sodium gluconate Substances 0.000 description 6
- 235000012207 sodium gluconate Nutrition 0.000 description 6
- 229940005574 sodium gluconate Drugs 0.000 description 6
- 239000012267 brine Substances 0.000 description 5
- 238000006073 displacement reaction Methods 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 5
- QGJDXUIYIUGQGO-UHFFFAOYSA-N 1-[2-[(2-methylpropan-2-yl)oxycarbonylamino]propanoyl]pyrrolidine-2-carboxylic acid Chemical compound CC(C)(C)OC(=O)NC(C)C(=O)N1CCCC1C(O)=O QGJDXUIYIUGQGO-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 150000003464 sulfur compounds Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
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- 238000010438 heat treatment Methods 0.000 description 3
- 239000006028 limestone Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000001509 sodium citrate Substances 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 3
- 229940038773 trisodium citrate Drugs 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 2
- KWMLJOLKUYYJFJ-UHFFFAOYSA-N 2,3,4,5,6,7-Hexahydroxyheptanoic acid Chemical compound OCC(O)C(O)C(O)C(O)C(O)C(O)=O KWMLJOLKUYYJFJ-UHFFFAOYSA-N 0.000 description 2
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 2
- IEZDTNCUMWPRTD-UHFFFAOYSA-N 346704-04-9 Chemical compound [O-][N+](=O)C1=CC=C(N2CCNCC2)C=C1N1CCCCC1 IEZDTNCUMWPRTD-UHFFFAOYSA-N 0.000 description 2
- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OS(O)(=O)=O)[C@@H](O)[C@H]1O IRLPACMLTUPBCL-KQYNXXCUSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
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- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- FLVIGYVXZHLUHP-UHFFFAOYSA-N N,N'-diethylthiourea Chemical compound CCNC(=S)NCC FLVIGYVXZHLUHP-UHFFFAOYSA-N 0.000 description 2
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- 150000001298 alcohols Chemical class 0.000 description 2
- 239000002519 antifouling agent Substances 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
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- PBZROIMXDZTJDF-UHFFFAOYSA-N hepta-1,6-dien-4-one Chemical compound C=CCC(=O)CC=C PBZROIMXDZTJDF-UHFFFAOYSA-N 0.000 description 2
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- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
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- UPMFZISCCZSDND-UHFFFAOYSA-M sodium;2,3,4,5,6-pentahydroxyhexanoate Chemical compound [Na+].OCC(O)C(O)C(O)C(O)C([O-])=O UPMFZISCCZSDND-UHFFFAOYSA-M 0.000 description 2
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- IOQLZVQKTDKIOZ-UHFFFAOYSA-N 2,3,4,5,6,7-hexahydroxyheptanoic acid;sodium;hydrate Chemical compound O.[Na].OCC(O)C(O)C(O)C(O)C(O)C(O)=O IOQLZVQKTDKIOZ-UHFFFAOYSA-N 0.000 description 1
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
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Abstract
本公开内容涉及一种通过在螯合剂存在下将单氯乙酸的一价盐引入地下地层中来处理所述地下地层的方法,所述螯合剂包含至少一个具有一价抗衡离子的羧酸根,且还包含带有至少5个羟基的碳链。优选地,单氯乙酸的一价盐的阳离子为钠。
Description
领域
本发明涉及一种处理地下地层的方法和用于该方法的含水酸化处理液。
背景
酸化液通常用于石油工业中以产生蚓孔并将井筒与地层连接。通常,盐酸(HCl)已经使用了几十年。然而,HCl具有与其与石灰石储层中存在的碳酸钙(CaCO3)的高反应性有关的主要缺点。HCl的反应性受储层中温度的高度影响。温度越高,HCl反应越快,从而形成具有不稳定结构的蚓孔,该蚓孔随后可能坍塌并堵塞通向地层的通道。由于上述原因,当在较高温度下使用含HCl的酸化液时,需要采取特定的措施。这明显增加了成本并限制了应用自由度。另一个缺点是高腐蚀性,这使得酸化处理昂贵。根据经验,在高达200°F(93℃)下,可以用HCl和腐蚀抑制剂进行处理,但是在高于200°F(93℃)下,还需要腐蚀抑制剂增强剂。使用腐蚀抑制剂增强剂增加了酸化液的成本。它们可高达总处理成本的60%。
需要进入更深的井,因为最近发现的许多储层被分类为高压高温(HPHT)。在这种意义上,发现HCl的替代选项是有意义的,其在暴露于高温时不反应,并且提供可以以受控方式释放的酸化特征。
已经公开了试图解决这些问题的若干公开文献:
US 2014/0296113公开了一种维护地下地层中的井筒的方法,其包括制备包含氨基多羧酸螯合剂、pH调节化合物和含水基础液的修井液,并使修井液与在与井筒和/或地下地层流体连通的表面上的污垢沉积物接触。
GB 2519388公开了一种处理地下地层中的地层损害的方法,其包括使用含环糊精的处理液,该处理液还可包含酸、有机酸前体、螯合剂和螯合剂前体。
WO 2015/030801涉及一种用于地下应用的酸化液,更特别地,涉及用于包含碳酸盐的地下地层的络合-酸化自转向处理液及其相关方法。
US 2009/0042748涉及对穿透地下地层的井的增产。更特别地,其涉及砂岩的基岩酸化;最特别地,其涉及在不使用酸前置液的情况下将包含聚合物添加剂的基岩酸化液注入砂岩地层中的方法。
US 2016/0115376涉及一种通过将组合物引入地层中来处理地下地层的方法,所述组合物包含基于组合物总重量为1-40重量%的螯合剂,所述螯合剂选自谷氨酸N,N-二乙酸或其盐(GLDA)、天冬氨酸N,N-二乙酸或其盐(ASDA)和甲基甘氨酸N,N-二乙酸或其盐(MGDA),其中所述方法包括浸泡步骤。
US 3885630涉及一种方法,其中通过接触水溶性弱酸和水溶性弱酸盐如乙酸和乙酸钠而酸化钻孔或井中或周围的酸反应性物质。
US 4122896涉及一种方法,其中通过将基本上不含酸的氯代羧酸盐如单或二氯乙酸盐或2-氯丙酸盐的水溶液注入到地下储层中,从而酸化该储层。
后两篇公开文献描述了利用氯代羧酸盐的水解的延迟酸化。在水解过程中形成乙醇酸和HCl。然而,发现形成的乙醇酸可与石灰石储层中存在的碳酸钙反应,从而形成乙醇酸钙。如果形成足够量的沉淀物,则乙醇酸钙可能导致管道堵塞。乙醇酸钙具有低溶解度,且容易沉淀。在油井中酸化过程中乙醇酸钙的沉淀(也称为结垢)是不希望的。进一步发现,以溶液形式具有乙醇酸钙的溶液在冷却至室温时形成凝胶。该凝胶化可能导致管道堵塞。
本公开内容的目的是找到上述问题的解决方案。
本公开内容的概述
本公开内容涉及一种通过在螯合剂存在下将单氯乙酸的一价盐引入地下地层中来处理所述地下地层的方法,所述螯合剂包含至少一个具有一价抗衡离子的羧酸根,且还包含带有至少5个羟基的碳链。
在本发明中,仅使用单氯乙酸的一价盐。“单氯乙酸的一价盐”意指单氯乙酸盐中的阳离子具有一价的化合价。优选地,单氯乙酸盐的阳离子(也称为一价抗衡离子)选自锂、钾、钠和铵。单氯乙酸盐的阳离子最优选为钠(单氯乙酸的钠盐在下文中也称为SMCA)。
螯合剂的羧酸根的数量(n)介于1和5之间(或者换言之,螯合剂包含1、2、3、4或5个羧酸根)。优选的螯合剂选自葡糖二酸的一价盐、葡糖酸的一价盐、葡庚糖酸的一价盐,以及2,3,4,5,6-五羟基己酸和2,3,4,5,6,7-六羟基庚酸的其他立体异构体(其中“一价盐”意指螯合剂的羧酸根具有一价阳离子)。具体实例为葡糖酸钠、葡庚糖酸钠、2,3,4,5,6-五羟基己酸钠和2,3,4,5,6,7-六羟基庚酸钠的其他立体异构体。
通常存在大于2重量%的螯合剂,且单氯乙酸盐(例如单氯乙酸钠)与螯合剂的摩尔比为1:0.5/n至1:10/n,其中n为螯合剂的羧酸根的数量。
在本公开内容的方法中,可将单氯乙酸的一价盐和螯合剂以包含该单氯乙酸盐和螯合剂的含水酸化处理液的形式引入地下地层中。
在本公开内容的方法中,其中引入本发明的单氯乙酸盐和螯合剂的地层的温度可为80-200℃,优选为85-180℃,更优选为90-160℃。
本公开内容涉及一种含水酸化处理液,其包含:
(i)单氯乙酸的一价盐,和
(ii)螯合剂,其包含至少一个具有一价抗衡离子的羧酸根,且还包含带有至少5个羟基的碳链。
本公开内容进一步涉及一种含水酸化处理液,其中本发明的单氯乙酸盐以至少3重量%,优选至少5重量%,最优选至少10重量%的量存在(基于所述含水酸化处理液的总量)。所述含水酸化处理液优选包含至多20重量%的单氯乙酸盐,优选至多18重量%的单氯乙酸盐,最优选至多14重量%的单氯乙酸盐(基于所述含水酸化处理液的总量)。通常,单氯乙酸盐以3-20重量%,优选4-18重量%,最优选5-14重量%的量存在,基于所述含水酸化处理液的总重量。单氯乙酸盐的浓度可调节至所述处理液的所需溶解能力。本领域技术人员清楚的是,总配制剂的溶解度还取决于处理液的使用温度。
通常,所述含水酸化处理液中的本发明的单氯乙酸的一价盐(优选单氯乙酸钠)与螯合剂的摩尔比为1:0.5/n至1:10/n,优选为1:0.5/n至1:5/n,最优选为1:0.8/n至1:2/n,其中n为螯合剂中的羧酸根的数量(1、2、3、4或5)。
本公开内容的含水酸化处理液可进一步包含一种或多种常规添加剂,其选自互溶剂、抗淤积剂、(水润湿或乳化)表面活性剂、腐蚀抑制剂、腐蚀抑制剂增强剂、起泡剂、增粘剂、润湿剂、转向剂、氧清除剂、载液、降滤失添加剂、降阻剂、稳定剂、流变改性剂、胶凝剂、阻垢剂、破乳剂、盐、盐水、pH调节添加剂如其他酸和/或碱、杀菌剂/生物杀伤剂、颗粒物、交联剂、盐替代物(例如四甲基氯化铵)、相对渗透率改性剂、硫化物清除剂、纤维、纳米颗粒、其组合等。
详细描述
下文将进一步阐述本发明的各个方面。
如上所述,本发明涉及一种通过在螯合剂存在下将单氯乙酸的一价盐引入地下地层中而处理所述地下地层的方法,所述螯合剂包含至少一个具有一价抗衡离子的羧酸根,且还包含带有至少5个羟基的碳链。
在本发明中,仅使用单氯乙酸的一价盐。“单氯乙酸的一价盐”意指单氯乙酸盐中的阳离子具有一价的化合价。优选地,单氯乙酸盐的阳离子(也称为一价抗衡离子)选自锂、钾、钠和铵。单氯乙酸盐的阳离子最优选为钠(单氯乙酸的钠盐在下文中也称为SMCA)。
单氯乙酸的一价盐可水解成乙醇酸(GA)和盐酸(HCl)。水解速率取决于温度、浓度和pH。使用单氯乙酸的盐,可以建立良好控制的延迟酸化。
发现通过加入螯合剂,抑制了乙醇酸钙的形成,从而可避免结垢和堵塞,所述螯合剂包含至少一个具有一价抗衡离子的羧酸根,且还包含带有至少5个羟基的碳链。
此外,利用本公开内容的方法,可以完全抑制或避免在注入位置处的面溶解,从而产生良好形成的蚓孔,确保地层的稳定性并且有效地使用酸化处理液。
所述螯合剂包含至少一个具有一价抗衡离子的羧酸根。“一价抗衡离子”是指化合价为一价的阳离子。合适的阳离子的实例为钠、铵、锂和钾。
取决于待处理的岩石类型,可以选择最优选的阳离子。在碳酸盐基岩石的情况下,单氯乙酸盐的阳离子优选为钠、钾和/或锂。在砂岩的情况下,铵是优选的阳离子。
所述螯合剂的羧酸根的数量n为1-5,其中n优选为1。优选的螯合剂选自葡糖二酸的一价盐、葡糖酸的一价盐、葡庚糖酸的一价盐、糖醛酸如半乳糖醛酸、醛糖酸,以及2,3,4,5,6,7-六羟基己酸和2,3,4,5,6,7-六羟基庚酸的其他立体异构体(其中“一价盐”意指螯合剂的羧酸根具有一价阳离子)。具体实例为葡糖酸钠、葡庚糖酸钠、2,3,4,5,6-五羟基己酸钠和2,3,4,5,6,7-六羟基庚酸钠的其他立体异构体。
在本公开内容的方法中,将单氯乙酸的一价盐和螯合剂以包含单氯乙酸的一价盐和螯合剂的含水酸化处理液的形式引入地下地层中。
通常使用大于2重量%的螯合剂(基于处理液的总重量),且单氯乙酸盐与螯合剂的摩尔比为1:0.5/n至1:10/n,其中n为螯合剂的羧酸根的数量。
在本公开内容的方法中,其中引入单氯乙酸盐和螯合剂的地层的温度优选为85-180℃,更优选为90-160℃。
本公开内容涉及一种含水酸化处理液,其包含:
(i)单氯乙酸的一价盐,和
(ii)螯合剂,其包含至少一个具有一价抗衡离子的羧酸根,且还包含带有至少5个羟基的碳链。
如实施例中所示,浓度高于4重量%的单氯乙酸盐混合物会与碳酸钙形成沉淀。然而,通过添加本公开内容的螯合剂,可以避免该沉淀,并且单氯乙酸盐可以以高于8重量%或者甚至更高(例如10重量%)的浓度使用。从实验数据可以清楚地看出,这种效果不能用其他常规的多羧酸盐螯合剂如EDTA和柠檬酸三钠达到。
因此,本公开内容进一步涉及一种含水酸化处理液,其中本发明的单氯乙酸盐以至少3重量%,优选至少5重量%,最优选至少10重量%的量存在,基于处理液的总量。所述含水酸化处理液优选包含至多20重量%的单氯乙酸盐,优选至多18重量%的单氯乙酸盐,最优选至多14重量%的单氯乙酸盐(基于所述含水酸化处理液的总量)。单氯乙酸盐的浓度可以调节至处理液的所需溶解能力。本领域技术人员清楚的是,总配制剂的溶解度还取决于处理液的使用温度。
通常,本发明的单氯乙酸盐以3-20重量%,优选4-18重量%,最优选5-14重量%的量存在,基于所述含水酸化处理液的总重量。
通常,含水酸化处理液的本发明单氯乙酸盐与螯合剂的摩尔比为1:0.5/n至1:10/n,优选为1:0.5/n至1:5/n,最优选为1:0.8/n至1:2/n,其中n为螯合剂中的羧酸根的数量。
本公开内容的含水酸化处理液包含水作为其他成分的溶剂,其中水可例如为淡水、采出水或海水。也可加入其他溶剂,例如以产生乳液。合适的其他溶剂为酮、醇或酯。
本公开内容的含水酸化处理液可进一步包含一种或多种常规添加剂,其选自互溶剂、抗淤积剂、(水润湿或乳化)表面活性剂、腐蚀抑制剂、腐蚀抑制剂增强剂、起泡剂、增粘剂、润湿剂、转向剂、氧清除剂、载液、降滤失添加剂、降阻剂、稳定剂、流变改性剂、胶凝剂、阻垢剂、破乳剂、盐、盐水、pH调节添加剂如其他酸和/或碱、杀菌剂/生物杀伤剂、颗粒物、交联剂、盐替代物(例如四甲基氯化铵)、相对渗透率改性剂、硫化物清除剂、纤维、纳米颗粒、其组合等。
互溶剂是可溶于油、水、酸(通常基于HCl)和其他井处理液的化学添加剂。互溶剂通常用于一系列应用中,在处理之前、期间和/或之后调节接触表面的润湿性,并防止或破坏乳液。合适的互溶剂为酮、醇或酯。
表面活性剂可为本领域技术人员已知的用于油气井的任何表面活性剂。优选地,表面活性剂为非离子表面活性剂或阳离子表面活性剂,甚至更优选为阳离子表面活性剂。
抗淤积剂稳定酸-油乳液,并且包括烷基酚、脂肪酸和阴离子表面活性剂。经常用作表面活性剂的是磺酸衍生物和分散表面活性剂在溶剂中的混合物。该混合物通常具有十二烷基苯磺酸(DDBSA)或其盐作为主要分散剂,即抗淤积组分。
腐蚀抑制剂可选自胺和季铵化合物以及硫化合物。实例为二乙基硫脲(DETU,其适合最高185°F(约85℃)),烷基吡啶鎓或喹啉鎓盐如十二烷基吡啶鎓溴化物(DDPB),和硫化合物如硫脲或硫氰酸铵(其适合203-302°F(约95-150℃)),苯并三唑(BZT),苯并咪唑(BZI),二丁基硫脲,称为TIA的专有抑制剂和烷基吡啶。
可加入一种或多种腐蚀抑制剂增强剂,例如甲酸、碘化钾、氯化锑或碘化铜。
通常,用于有机酸和螯合剂的最成功的抑制剂配制剂包含胺、还原性硫化合物,或氮化合物(胺、季铵或多官能化合物)和硫化合物的组合。腐蚀抑制剂的量优选为总液体的0.1-5.0体积%,更优选0.1-2.0体积%。
可使用一种或多种盐作为流变改性剂以改变处理液的流变性能(例如,粘度和弹性性能)。这些盐可为有机或无机的。当加入盐时,应当注意不要对pH产生有害影响,从而对水解速率产生有害影响。
可适用于本发明的润湿剂包括粗妥尔油、氧化的粗妥尔油、表面活性剂、有机磷酸酯、改性的咪唑啉和酰胺基胺、烷基芳族硫酸盐和磺酸盐等,以及这些化合物和本领域技术人员应当熟知的类似此类化合物的组合或衍生物。
在优选的实施方案中,胶凝剂为聚合物胶凝剂。通常使用的聚合物胶凝剂的实例包括但不限于生物聚合物、多糖如瓜尔胶及其衍生物、纤维素衍生物、合成聚合物如聚丙烯酰胺和粘弹性表面活性剂等。这些胶凝剂在水合时和在足够的浓度下能够形成粘性溶液。
当用于制备水基处理液时,将胶凝剂与水性流体组合,并且胶凝剂的可溶性部分溶解在水性流体中,从而增加流体的粘度。
增粘剂可包括天然聚合物和衍生物,例如黄原胶和羟乙基纤维素(HEC)或合成聚合物和低聚物,例如聚乙二醇[PEG]、聚二烯丙基胺、聚丙烯酰胺、聚氨甲基丙基磺酸酯[AMPS聚合物]、聚丙烯腈、聚乙酸乙烯酯、聚乙烯醇、聚乙烯基胺、聚乙烯基磺酸盐、聚苯乙烯基磺酸盐、聚丙烯酸酯、聚丙烯酸甲酯、聚甲基丙烯酸酯、聚甲基丙烯酸甲酯、聚乙烯基吡咯烷酮、聚乙烯基内酰胺,以及下列(共)单体的二元、三元和四元共聚物:乙烯、丁二烯、异戊二烯、苯乙烯、二乙烯基苯、二乙烯基胺、1,4-戊二烯-3-酮(二乙烯基酮)、1,6-庚二烯-4-酮(二烯丙基酮)、二烯丙胺、乙二醇、丙烯酰胺、AMPS、丙烯腈、乙酸乙烯酯、乙烯醇、乙烯基胺、乙烯基磺酸盐、苯乙烯基磺酸盐、丙烯酸酯、丙烯酸甲酯、甲基丙烯酸酯、甲基丙烯酸甲酯、乙烯基吡咯烷酮和乙烯基内酰胺。其他增粘剂还包括粘土基增粘剂,尤其是合成锂皂石和其他小纤维状粘土如坡缕石(绿坡缕石和海泡石)。当使用含聚合物的增粘剂时,增粘剂的用量可为流体的至多5重量%。
盐水的使用是本领域所已知的,此处不需要进一步说明。
任何选择的盐水应该与地层相容,并且应该具有足够的密度以提供适当程度的井控。
可将其他盐加入水源中,例如以提供盐水和所得处理液,以便具有所需的密度。加入的盐的量应该是地层相容性所必需的量,例如粘土矿物的稳定性所必需的量,其中要考虑盐水的结晶温度,例如当温度下降时盐从盐水中沉淀的温度。优选的合适盐水可包括海水和/或地层盐水。
应指出的是,本发明的各种要素,包括但不限于各种参数的优选范围,可以组合,除非它们是相互排斥的。
本发明将通过以下实施例来阐明,但并不限于此或受其限制。
实施例
实施例1:CaCO3在SMCA存在下的溶解
为了研究沉淀的形成,将750g 10重量%SMCA(pH约8-9)溶液加入到搅拌的1L反应器中。通过漏斗向混合物中加入32.2g碳酸钙粉末。闭合反应器,在顶部空间中充入3巴(表压)氮气。温度探针连续测量溶液的温度。然后,将该溶液用油浴加热至120℃约5小时。使用汲取管从反应器中取出第一样品,并通过使用硝酸银的滴定测定氯离子浓度来检测SMCA是否完全与酸反应。在5小时后,停止加热,在环境压力下将反应混合物的温度降低至80℃。从反应器中排出25mL的第二样品,并转移到玻璃小瓶中。将该样品在油浴中保持在40℃的恒温下。在24小时后,注意到样品已经完全变成固体(参见图2a)。使用不同的SMCA水溶液重复该实验,其中SMCA水溶液的浓度在2-8重量%之间变化。还将碳酸钙等摩尔加入到这些溶液中。从表1可以看出,仅含2重量%SMCA的混合物在反应后得到澄清溶液。
表1:加入碳酸钙的不同浓度SMCA溶液的结果
实施例2:CaCO3在SMCA和葡糖酸钠存在下的溶解
重复实施例1,但现在在葡糖酸钠存在下使用10重量%的SMCA。使用与实施例1中所用的相同条件进行实验。仅在该实验中,将750g包含75g(10重量%)SMCA和142.5g(19重量%)D-葡糖酸钠盐(纯度99%,获自Sigma Aldrich)的水溶液装入反应器中。还通过漏斗向反应器中加入32.2g碳酸钙。随后闭合反应器,在顶部空间中充入3巴(表压)氮气。温度探针连续测量溶液的温度。然后,将该溶液用油浴加热至120℃约5小时。使用汲取管从反应器中取出第一样品,并通过滴定测量氯离子浓度以检查SMCA是否完全转化为酸。在5小时后,停止加热,在环境压力下将反应混合物的温度降低至80℃。从反应器中排出25mL样品并转移到玻璃小瓶中。将该样品在油浴中保持在40℃的恒温下。在24小时后,注意到样品仍然完全澄清,并且不含任何沉淀(参见图2b)。因此,通过加入本公开内容的螯合剂,可以使用大量的SMCA而不形成沉淀。
实施例3:在150℃下用10重量%SMCA溶液和18重量%葡糖酸钠进行岩心驱替测试
图1显示了岩心驱替装置的示意图。对于岩心驱替测试,使用具有1.5英寸(3.81cm)直径和6英寸(15.24cm)长度的新岩心块。将岩心放置在岩心夹持器中,并使用可收缩密封件来防止夹持器和岩心之间的任何泄漏。将岩心夹持器放置在炉中。加热的岩心的温度由Binder ED400系列控制,波动为±0.3℃。在岩心夹持器的入口和出口中,安装Pt-100以控制注入流体的温度。
使用Isco注射双活塞泵将盐水或测试流体泵送通过岩心,并使用Enerpac手动液压泵来施加所需的上覆压力。施加1,000psi(6.9MPa)的背压以将CO2保持在溶液中。将盐水溶液保持在烘箱内的储存收集器中。将测试流体置于烘箱外部的第二收集器中,并与岩心夹持器一起连接到预热管线。
背压由Mity-Mite背压调节器型号S91W-EQ控制,并保持恒定在比上覆压力小300-400psi(2.1-2.8MPa)下。用一套Jumo dTrans p02差压传感器测量跨岩心的压降,并通过实验室观察软件监测。分别安装两个范围为0-800psi(0-5.5MPa)和0-1500psi(0-10.3MPa)的压力计。
在进行岩心驱替测试之前,首先将岩心在160°F(71℃)的烘箱中干燥并称重。随后在室温下在真空下用水饱和该岩心。由干燥和饱和岩心的重量差计算孔体积。
处理前后的岩心渗透率使用牛顿流体在多孔介质中的层流、线性流和稳态流的Darcy方程由压降计算:
K=(122.81qμL)/(ΔpD2)
其中K为岩心渗透率(以md计),q为流速(以cm3/分钟计),μ为流体粘度(以cP计),L为岩心长度(以英寸计),Δp为跨岩心的压降(以psi计),D为岩心直径(以英寸计)。
在岩心驱替测试之前,将岩心用盐水以0.01cm3/分钟的低注入速率预热至所需的测试温度至少12小时。
该程序用于证明通过将pH=7.5的10重量%SMCA与19重量%(D)葡糖酸钠和0.25重量%腐蚀抑制剂的混合物以1.5cm3/分钟的流速注入渗透率为12mD印度石灰石岩芯中来产生蚓孔的理念。
在通过CT扫描检查岩芯时,表明利用根据本公开内容的方法,在没有面溶解的情况下形成良好形成的蚓孔。
实施例4:CaCO3在10重量%SMCA和各种螯合剂存在下的溶解
为了研究各种螯合剂的性能,将结晶EDTA-Na4四水合物(也称为产品DissolvineNa-X,获自AkzoNobel)、柠檬酸三钠二水合物(纯度为99%,获自J.T.Baker)和α-D-葡庚糖酸钠盐(纯度为99%,获自Sigma Aldrich)分别与750g 10重量%SMCA水溶液等摩尔混合。对每种混合物应用与实施例1中解释的相同程序。因此,在向反应器中加入SMCA溶液和相应的螯合剂后,向每个反应器中加入32.2g碳酸钙。在120℃下反应5小时后,从反应混合物中取出样品以检查酸的完全释放,并分别取出25mL样品并在40℃下调节24小时。
表2 实施例4中使用的螯合剂的概述
螯合剂 | 量(g) | |
1 | EDTA-Na<sub>4</sub>四水合物 | 72.8 |
2 | 柠檬酸三钠二水合物 | 93.0 |
3 | α-D-葡庚糖酸钠盐 | 159.8 |
当比较SMCA分别与Na4-EDTA、柠檬酸三钠和葡庚糖酸钠的混合物的反应产物时,很明显,只有从SMCA和葡庚糖酸钠起始的样品仍然是完全澄清的(参见图2d)并且不含任何沉淀。分别从SMCA与Na4-EDTA以及SMCA与柠檬酸三钠起始的反应混合物中充满沉淀(分别参见图2c和图2e)。
本实施例证明,通过使用本公开内容的螯合物可以防止由SMCA和碳酸钙反应形成沉淀。
实施例5:SMCA和MCA的CaCO3溶解速率
在本实施例中比较了用SMCA和MCA溶解给定量的CaCO3所需的时间。该方法的反应速率可以通过温度控制。用水水解SMCA并通过加热成为乙醇酸和氯化钠。乙醇酸与CaCO3反应非常快。通过测定氯离子浓度来跟踪该反应的程度。将750g 10重量%SMCA(pH约8-9)溶液加入到搅拌的1L反应器中。通过漏斗向混合物中加入32.2g碳酸钙粉末。闭合反应器,在顶部空间中充入3巴(表压)氮气。温度探针连续测量溶液的温度。然后,将该溶液用油浴加热至100℃。使用汲取管和加压样品系统取样。分析这些样品的氯离子以计算水解速率。使用硝酸银滴定测量氯离子。然后,将该氯离子浓度与所有SMCA转化成乙醇酸和氯化钠时氯离子的理论量进行比较。当达到完全水解时,认为CaCO3完全溶解。在140和160℃的温度下重复该程序。表3中描述了在各种温度下测量用SMCA完全溶解CaCO3的时间。对于10重量%MCA,使用不同的程序。由于其高反应性,实验在室温和大气压下进行。将750g 10重量%MCA溶液和39.7g碳酸钙粉末加入玻璃容器中。肉眼监测MCA完全溶解CaCO3的时间,结果示于表3中。这些结果证实,SMCA溶解CaCO3的速率比MCA溶解CaCO3的速率慢得多,这有利于进入更深的井。
表3 SMCA和MCA的CaCO3溶解速率
Claims (17)
1.一种通过在螯合剂存在下将单氯乙酸的一价盐引入地下地层中而处理所述地下地层的方法,所述螯合剂包含至少一个具有一价抗衡离子的羧酸根,且还包含带有至少5个羟基的碳链。
2.根据权利要求1的方法,其中所述地下地层包括碳酸盐基岩石。
3.根据权利要求2的方法,其中单氯乙酸盐的阳离子为钠、钾和/或锂。
4.根据权利要求1的方法,其中所述地下地层包括砂岩。
5.根据权利要求4的方法,其中单氯乙酸盐的阳离子为铵和/或钾。
6.根据权利要求1-4中任一项的方法,其中单氯乙酸盐的阳离子为钠。
7.根据前述权利要求中任一项的方法,其中螯合剂中的羧酸根的数量n为1-5。
8.根据前述权利要求中任一项所述的方法,其中所述螯合剂选自葡糖二酸的一价盐、葡糖酸的一价盐、葡庚糖酸的一价盐、糖醛酸如半乳糖醛酸、醛糖酸以及2,3,4,5,6-五羟基己酸和2,3,4,5,6,7-六羟基庚酸的其他立体异构体的一价盐。
9.根据前述权利要求中任一项的方法,其中将单氯乙酸的一价盐和螯合剂以包含单氯乙酸的一价盐和螯合剂的含水酸化处理液的形式引入地下地层中。
10.根据权利要求9的方法,其中所述含水酸化处理液中存在大于2重量%的螯合剂(基于所述含水酸化处理液的总重量),并且单氯乙酸的一价盐与螯合剂的摩尔比为1:0.5/n至1:10/n,其中n为螯合剂的羧酸根的数量。
11.根据前述权利要求中任一项的方法,其中引入单氯乙酸的一价盐和螯合剂的地层温度为80-200℃,优选为85-180℃,更优选为90-160℃。
12.一种含水酸化处理液,其包含:
(i)单氯乙酸的一价盐,和
(ii)螯合剂,其包含至少一个具有一价抗衡离子的羧酸根,且还包含带有至少5个羟基的碳链。
13.根据权利要求12的含水酸化处理液,其中单氯乙酸的一价盐以至少3重量%,优选至少5重量%,更优选至少10重量%,最优选至少14重量%的量存在,基于所述含水酸化处理液的总重量。
14.根据权利要求12或13的含水酸化处理液,其中单氯乙酸的一价盐与螯合剂的摩尔比为1:0.5/n至1:10/n,其中n为螯合剂中的羧酸根的数量。
15.根据权利要求12-14中任一项的含水酸化处理液,其中单氯乙酸的一价盐的阳离子选自钠、钾、锂和铵。
16.根据权利要求12-15中任一项的含水酸化处理液,其中单氯乙酸的一价盐的阳离子为钠。
17.根据权利要求12-16中任一项的含水酸化处理液,其进一步包含一种或多种选自互溶剂、抗淤积剂、(水润湿或乳化)表面活性剂、腐蚀抑制剂、腐蚀抑制剂增强剂、起泡剂、增粘剂、润湿剂、转向剂、氧清除剂、载液、降滤失添加剂、降阻剂、稳定剂、流变改性剂、胶凝剂、阻垢剂、破乳剂、盐、盐水、pH调节添加剂如其他酸和/或碱、杀菌剂/生物杀伤剂、颗粒物、交联剂、盐替代物(例如四甲基氯化铵)、相对渗透率改性剂、硫化物清除剂、纤维、纳米颗粒、其组合等的化合物。
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PCT/EP2019/065805 WO2020002011A1 (en) | 2018-06-26 | 2019-06-17 | Salt of monochloroacetic acid with chelating agent for delayed acidification in the oil field industry |
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US11649399B1 (en) | 2021-11-09 | 2023-05-16 | Halliburton Energy Services, Inc. | Acid precursor treatment fluid generating and/or releasing acid for use downhole in a subterranean formation |
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