CN116284751B - 聚天冬氨酸衍生物及其制备方法与作为润滑剂的应用、水基钻井液及其应用 - Google Patents
聚天冬氨酸衍生物及其制备方法与作为润滑剂的应用、水基钻井液及其应用 Download PDFInfo
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- CN116284751B CN116284751B CN202211101124.XA CN202211101124A CN116284751B CN 116284751 B CN116284751 B CN 116284751B CN 202211101124 A CN202211101124 A CN 202211101124A CN 116284751 B CN116284751 B CN 116284751B
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- Prior art keywords
- water
- polyaspartic acid
- drilling fluid
- acid derivative
- lubricant
- Prior art date
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- 238000005553 drilling Methods 0.000 title claims abstract description 87
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000012530 fluid Substances 0.000 title claims abstract description 74
- 239000000314 lubricant Substances 0.000 title claims abstract description 61
- 229920000805 Polyaspartic acid Polymers 0.000 title claims abstract description 51
- 108010064470 polyaspartate Proteins 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000006073 displacement reaction Methods 0.000 claims abstract description 17
- 239000003638 chemical reducing agent Substances 0.000 claims description 33
- 239000000706 filtrate Substances 0.000 claims description 33
- 239000003795 chemical substances by application Substances 0.000 claims description 27
- 229920000642 polymer Polymers 0.000 claims description 22
- 229920001285 xanthan gum Polymers 0.000 claims description 15
- 150000001412 amines Chemical class 0.000 claims description 14
- 239000000230 xanthan gum Substances 0.000 claims description 13
- 235000010493 xanthan gum Nutrition 0.000 claims description 13
- 229940082509 xanthan gum Drugs 0.000 claims description 13
- 229920002401 polyacrylamide Polymers 0.000 claims description 12
- 159000000000 sodium salts Chemical class 0.000 claims description 10
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 229920002472 Starch Polymers 0.000 claims description 8
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000008107 starch Substances 0.000 claims description 8
- 235000019698 starch Nutrition 0.000 claims description 8
- -1 sulfomethyl phenolic resin Chemical compound 0.000 claims description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 6
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 6
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- 229920002907 Guar gum Polymers 0.000 claims description 3
- 229920002752 Konjac Polymers 0.000 claims description 3
- 240000004584 Tamarindus indica Species 0.000 claims description 3
- 235000004298 Tamarindus indica Nutrition 0.000 claims description 3
- 239000000665 guar gum Substances 0.000 claims description 3
- 235000010417 guar gum Nutrition 0.000 claims description 3
- 229960002154 guar gum Drugs 0.000 claims description 3
- 239000001341 hydroxy propyl starch Substances 0.000 claims description 3
- 235000013828 hydroxypropyl starch Nutrition 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000003607 modifier Substances 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000000252 konjac Substances 0.000 claims description 2
- 235000019823 konjac gum Nutrition 0.000 claims description 2
- 239000003077 lignite Substances 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920000447 polyanionic polymer Polymers 0.000 claims 1
- 230000001050 lubricating effect Effects 0.000 abstract description 21
- 230000005764 inhibitory process Effects 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000003208 petroleum Substances 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 13
- 239000007789 gas Substances 0.000 description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 description 10
- 239000013505 freshwater Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 7
- 235000003704 aspartic acid Nutrition 0.000 description 7
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 7
- 230000000903 blocking effect Effects 0.000 description 4
- 239000013535 sea water Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical group [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 3
- 239000010428 baryte Substances 0.000 description 3
- 229910052601 baryte Inorganic materials 0.000 description 3
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- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000005098 hot rolling Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
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- 230000007613 environmental effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- DHKIVCMLYUCALN-UHFFFAOYSA-N (2-hydroxyphenyl)methanesulfonic acid Chemical compound OC1=CC=CC=C1CS(O)(=O)=O DHKIVCMLYUCALN-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical class [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 241001247197 Cephalocarida Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- ONCZQWJXONKSMM-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4].[Si+4].[Si+4].[Si+4] ONCZQWJXONKSMM-UHFFFAOYSA-N 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- MQRJBSHKWOFOGF-UHFFFAOYSA-L disodium;carbonate;hydrate Chemical compound O.[Na+].[Na+].[O-]C([O-])=O MQRJBSHKWOFOGF-UHFFFAOYSA-L 0.000 description 1
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 235000010485 konjac Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 1
- 229940073769 methyl oleate Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940080314 sodium bentonite Drugs 0.000 description 1
- 229910000280 sodium bentonite Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/341—Dicarboxylic acids, esters of polycarboxylic acids containing two carboxylic acid groups
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M173/00—Lubricating compositions containing more than 10% water
- C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON 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
- C09K8/02—Well-drilling compositions
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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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- C09K8/04—Aqueous well-drilling compositions
- C09K8/06—Clay-free compositions
- C09K8/12—Clay-free compositions containing synthetic organic macromolecular compounds or their precursors
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- C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
- C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M145/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
- C10M145/16—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate polycarboxylic
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- C10M149/12—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M149/14—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds a condensation reaction being involved
- C10M149/18—Polyamides
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- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/34—Lubricant additives
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- C10M2201/062—Oxides; Hydroxides; Carbonates or bicarbonates
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- C10M2217/024—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amido or imido group
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10N2030/02—Pour-point; Viscosity index
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Abstract
本发明提供了聚天冬氨酸衍生物及其制备方法与作为润滑剂的应用、水基钻井液及其应用,属于涉及石油钻井工程油田化学技术领域。本发明提供的聚天冬氨酸衍生物不含有磺化基团,环境友好;将其作为润滑剂用于水基钻井液,具有良好的润滑性能,同时还具有良好的抑制性能、封堵性能以及稳定性,适合用于大位移井钻采中。
Description
技术领域
本发明涉及石油钻井工程油田化学技术领域,具体涉及聚天冬氨酸衍生物及其制备方法与作为润滑剂的应用、水基钻井液及其应用。
背景技术
随着能源消耗的日益增加和浅层油气资源的衰竭,为了提高油气产量来满足能源消费需求,油气田开采过程中,油气藏的开采模式从常规的油气井开采转向水平井和大位移井开采。尤其对于深海、浅海、海滩、潮汐带等海上油气藏,由于单独开发建造平台成本高、经济效益低,而大位移井作为非常规钻井技术之一,具有高效、低成本的优点,使其在海上油气藏的开发比例逐年提高。利用开发大位移井的方式串联油气藏,扩大油层渗流面积,提高单井油气产能。虽然大位移井优点较为明显,但其最大的技术难题在于摩阻扭矩大和井壁失稳问题,长水平段钻井与套管或岩石井壁之间的高摩阻问题一直制约着大位移井的最大延伸范围。
对于以上技术难题,钻井过程中大多数首选油基钻井液,但该钻井液存在成本高、钻屑处理难、污染环境等问题。而水基钻井液在摩阻扭矩与井壁稳定方面所面临的问题尤为突出。基于此,为了解决大位移井水平段存在高摩阻和井壁失稳问题,需要开发一种具有优异润滑性能的环保处理剂,且同时兼顾抑制性能和封堵性能,以克服大位移井水基钻井液存在的问题。
中国专利CN105038732B(申请号201510362976.8)公开了一种钻井液用润滑封堵剂,可有效降低淡水基浆、盐水基浆的润滑系数以及滤失量,具有良好的封堵、润滑性能,但该润滑封堵剂分子中含有磺化基团,具有一定的生物毒性,废弃时难以处理。
发明内容
本发明的目的在于提供一种聚天冬氨酸衍生物及其制备方法与作为润滑剂的应用、水基钻井液及其应用,本发明提供的聚天冬氨酸衍生物不含有磺化基团,环境友好;将其作为润滑剂用于水基钻井液,具有优异润滑性能且兼具稳定井壁作用,适合用于大位移井钻采中。
为了实现上述发明目的,本发明提供以下技术方案:
本发明提供了一种聚天冬氨酸衍生物,具有式I所示结构:
所述式I中,R1选自-CH2-CH2-CH2-、-CH2-CH2-CH2-CH2-或-CH2-CH2-CH2-CH2-CH2-CH2-;
R2选自-OH、-N-(CH2-CH2-OH)2、-O-CH2-CH2-NH-CH2-CH2-OH、-NH-CH2-CH2-OH或-O-CH2-CH2-NH2;
n与m独立地为8~17。
优选地,所述式I中R1为-CH2-CH2-CH2-、R2为-OH,且n与m为12~17;
或者所述式I中R1为-CH2-CH2-CH2-CH2-、R2为-O-CH2-CH2-NH2,且n与m为8~12;
或者所述式I中R1为-CH2-CH2-CH2-CH2-CH2-CH2-、R2为-O-CH2-CH2-NH-CH2-CH2-OH,且n与m为10~15。
本发明提供了上述技术方案所述聚天冬氨酸衍生物的制备方法,包括以下步骤:
将天冬氨酸与水溶性有机胺混合,进行聚合反应,得到聚天冬氨酸衍生物;所述水溶性有机胺为丙二胺、丁二胺、己二胺、单乙醇胺和二乙醇胺中的一种或几种。
优选地,所述天冬氨酸与水溶性有机胺的质量比为(7~9):(1~3)。
优选地,所述聚合反应的温度为150~180℃,时间为8~12h。
本发明提供了上述技术方案所述聚天冬氨酸衍生物或上述技术方案所述制备方法制备得到的聚天冬氨酸衍生物作为润滑剂的应用。
本发明提供了一种水基钻井液,包括水、pH调节剂、聚合物增粘降滤失剂、降滤失剂、流型调节剂、润滑剂和加重剂,所述润滑剂为上述技术方案所述聚天冬氨酸衍生物或上述技术方案所述制备方法制备得到的聚天冬氨酸衍生物。
优选地,以占水的质量百分比计,所述pH调节剂的含量为0.4~0.8%,聚合物增粘降滤失剂的含量为0.5~1.5%,降滤失剂的含量为2.0~4.0%,流型调节剂的含量为0.2~0.7%,润滑剂的含量为10.0~30.0%,加重剂的含量为45.0~60.0%。
优选地,所述流型调节剂包括黄原胶、罗望子胶、魔芋胶、温伦胶和瓜尔豆胶中的一种或几种。
本发明提供了上述技术方案所述水基钻井液在大位移井钻采中的应用。
本发明提供了一种聚天冬氨酸衍生物,本发明提供的聚天冬氨酸衍生物不含有磺化基团,环境友好;将其作为润滑剂用于水基钻井液,具有良好的润滑性能,同时还具有良好的抑制性能、封堵性能以及稳定性,适合用于大位移井钻采中。
本发明提供了所述聚天冬氨酸衍生物的制备方法。本发明以聚天冬氨酸和水溶性有机胺为原料,二者均属于环境友好型化学品,通过水溶性有机胺改性聚天冬氨酸形成聚天冬氨酸衍生物,其是一种多功能环保型润滑剂;同时,本发明提供的聚天冬氨酸衍生物的制备方法操作简单,无需有机溶剂,环境友好。
具体实施方式
本发明提供了一种聚天冬氨酸衍生物,具有式I所示结构:
所述式I中,R1选自-CH2-CH2-CH2-、-CH2-CH2-CH2-CH2-或-CH2-CH2-CH2-CH2-CH2-CH2-;
R2选自-OH、-N-(CH2-CH2-OH)2、-O-CH2-CH2-NH-CH2-CH2-OH、-NH-CH2-CH2-OH或-O-CH2-CH2-NH2;
n与m独立地为8~17。
在本发明中,所述式I中n与m独立地为8~17,聚天冬氨酸衍生物对应的分子量为2000~4000;具体的,所述n=m,所述n优选为8~12、10~15或12~17。
在本发明的实施例中,所述式I中R1为-CH2-CH2-CH2-、R2为-OH,且n=m=12~17;或者所述式I中R1为-CH2-CH2-CH2-CH2-、R2为-O-CH2-CH2-NH2,且n=m=8~12;或者所述式I中R1为-CH2-CH2-CH2-CH2-CH2-CH2-、R2为-O-CH2-CH2-NH-CH2-CH2-OH,且n=m=10~15。
本发明提供了上述技术方案所述聚天冬氨酸衍生物的制备方法,包括以下步骤:
将天冬氨酸与水溶性有机胺混合,进行聚合反应,得到聚天冬氨酸衍生物;所述水溶性有机胺为丙二胺、丁二胺、己二胺、单乙醇胺和二乙醇胺中的一种或几种。
在本发明中,若无特殊说明,所涉及的原料均为本领域技术人员熟知的市售商品。
在本发明中,所述水溶性有机胺为丙二胺、丁二胺、己二胺、单乙醇胺和二乙醇胺中的一种或几种,优选为丙二胺、丁二胺-单乙醇胺混合物或己二胺-二乙醇胺混合物;所述丁二胺-单乙醇胺混合物中丁二胺与单乙醇胺的质量比优选为(5~8):(2~5),更优选为7:3;所述己二胺-二乙醇胺混合物中己二胺与二乙醇胺的质量比优选为(3~5):(5~7),更优选为4:6。
在本发明中,所述天冬氨酸与水溶性有机胺的质量比优选为(7~9):(1~3),具体可以为7:3、8:2或9:1。在本发明中,所述聚合反应的温度优选为150~180℃,具体可以为150℃、160℃或180℃;所述聚合反应的时间优选为8~12h,具体可以为8h、10h或12h;所述聚合反应优选在搅拌条件下进行。在本发明中,所述聚合反应后无需进行任何后处理即得到具有式I所示结构的聚天冬氨酸衍生物,为棕色物质。
本发明通过水溶性有机胺改性聚天冬氨酸,可提高其水溶性以及增大其分子量,提高其与钻井液的配伍性;所得聚天冬氨酸衍生物中含有大量的酰胺基团、酯基、羧基和胺基,其中的N、O原子含有孤对电子以及胺基在钻井液中遇水质子化,使聚天冬氨酸衍生物牢固吸附在黏土和金属表面,形成非极性油膜,起到润滑作用,且提高钻井液体系的抑制性能。另外,聚天冬氨酸衍生物分子链能够在水中伸展,形成空间网状结构,并在分子间作用力以及静电作用下吸附黏土表面,形成致密吸附膜,阻止地层压力传递,起到封堵作用。
本发明提供了上述技术方案所述聚天冬氨酸衍生物或上述技术方案所述制备方法制备得到的聚天冬氨酸衍生物作为润滑剂的应用。
本发明提供了一种水基钻井液,包括水、pH调节剂、聚合物增粘降滤失剂、降滤失剂、流型调节剂、润滑剂和加重剂,所述润滑剂为上述技术方案所述聚天冬氨酸衍生物或上述技术方案所述制备方法制备得到的聚天冬氨酸衍生物。在本发明中,以占水的质量百分比计,所述pH调节剂的含量优选为0.4~0.8%,聚合物增粘降滤失剂的含量优选为0.5~1.5%,降滤失剂的含量优选为2.0~4.0%,流型调节剂的含量优选为0.2~0.7%,润滑剂的含量优选为10.0~30.0%,加重剂的含量优选为45.0~60.0%。下面进行具体说明。
在本发明中,所述水优选为淡水或海水。
在本发明中,所述pH调节剂的质量优选为水质量的0.4~0.8%,具体可以为0.4%、0.6%或0.8%。在本发明中,所述pH调节剂优选为氢氧化钠、碳酸钠和氢氧化钾的一种或几种,更优选为氢氧化钠-碳酸钠混合物,所述氢氧化钠-碳酸钠混合物中氢氧化钠与碳酸钠的质量比优选为(2~4):(6~8),具体可以为2:8、3:7或4:6。本发明优选将pH调节剂的用量限定在上述范围,所得水基钻井液的pH值优选为9~11,具体可以为9、10或11。
在本发明中,所述聚合物增粘降滤失剂的质量优选为水质量的0.5~1.5%,具体可以为0.5%、1.0%或1.5%。在本发明中,所述聚合物增粘降滤失剂优选为聚丙烯酰胺钾盐、聚丙烯酰胺钠盐和聚阴离子纤维素中的一种或几种,更优选为聚丙烯酰胺钠盐,所述聚丙烯酰胺钠盐的相对分子质量优选为100~120万。本发明优选采用聚丙烯酰胺钠盐作为聚合物增粘降滤失剂,聚丙烯酰胺钠盐具有良好的抗温抗盐性能,与其他处理剂具有良好的配伍性能。
在本发明中,所述降滤失剂的质量优选为水质量的2.0~4.0%,具体可以为2.0%、3.0%或4.0%。在本发明中,所述降滤失剂优选为磺甲基酚醛树脂(SMP-II)、磺甲基褐煤树脂(SPNH)、羟丙基淀粉(HPS)和羧甲基淀粉(CMS)中的一种或几种,更优选为羧甲基淀粉(CMS)。本发明优选采用羧甲基淀粉作为降滤失剂,环境好友,且制备工艺成熟,容易获得。
在本发明中,所述流型调节剂的质量优选为水质量的0.2~0.7%,具体可以为0.2%、0.3%、0.5%或0.7%。在本发明中,所述流型调节剂包括黄原胶、罗望子胶、魔芋胶、温伦胶和瓜尔豆胶中的一种或几种,更优选为黄原胶-温伦胶混合物,所述黄原胶-温伦胶混合物中黄原胶与温伦胶的质量比优选为(3~5):(5~7),具体可以为3:7、4:6或5:5。在本发明中,所述温伦胶具有良好的抗温性能,与黄原胶复配具有协同作用,可提高所述流型调节剂的抗温性能。
在本发明中,所述润滑剂的质量优选为水质量的10.0~30.0%,具体可以为10.0%、20.0%或30.0%。将本发明提供的聚天冬氨酸衍生物作为润滑剂用于水基钻井液,具有良好的润滑性能,同时还具有良好的抑制性能、封堵性能以及稳定性,适合用于大位移井钻采中,且环境友好。
在本发明中,所述加重剂优选为水质量的45.0~60.0%。在本发明中,所述加重剂优选为重晶石。本发明优选将加重剂的用量限定在上述范围,所得水基钻井液的密度优选为1.3~1.4g/cm3。
本发明提供了上述技术方案所述水基钻井液在大位移井钻采中的应用。在本发明中,所述大位移井具体是指水垂比不小于2且测量深度大于3000m的井,或水平位移大于3000m的井。
下面将结合本发明中的实施例,对本发明中的技术方案进行清楚、完整地描述。显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1
组建配有搅拌器、回流冷凝器以及温度计的三口圆底烧瓶,按质量份计,将80份天冬氨酸和20份丙二胺加入到所述三口圆底烧瓶中,在搅拌条件下加热至160℃,保温反应10h,得到润滑剂(记为RH-1,其中,R1为-CH2-CH2-CH2-、R2为-OH,且n=m=12~17)。
为了进行后续性能测试以评价淡水中润滑剂的润滑性能,按质量份计,将90份淡水与10份润滑剂(RH-1)混合,得到水基钻井液。
实施例2
组建配有搅拌器、回流冷凝器以及温度计的三口圆底烧瓶,按质量份计,将90份天冬氨酸和10份水溶性有机胺(具体为丁二胺与单乙醇胺,所述丁二胺与单乙醇胺的质量比为7:3)加入到所述三口圆底烧瓶中,在搅拌条件下加热至150℃,保温反应12h,得到润滑剂(记为RH-2,其中,R1为-CH2-CH2-CH2-CH2-、R2为-O-CH2-CH2-NH2,且n=m=8~12)。
为了进行后续性能测试以评价淡水中润滑剂的润滑性能,按质量份计,将80份淡水与20份润滑剂(RH-2)混合,得到水基钻井液。
实施例3
组建配有搅拌器、回流冷凝器以及温度计的三口圆底烧瓶,按质量份计,将70份天冬氨酸和30份水溶性有机胺(具体为己二胺与二乙醇胺,所述己二胺与二乙醇胺的质量比为4:6)加入到所述三口圆底烧瓶中,在搅拌条件下加热至180℃,保温反应8h,得到润滑剂(记为RH-3,其中,R1为-CH2-CH2-CH2-CH2-CH2-CH2-、R2为-O-CH2-CH2-NH-CH2-CH2-OH,且n=m=10~15)。
为了进行后续性能测试以评价淡水中润滑剂的润滑性能,按质量份计,将70份淡水与30份润滑剂(RH-3)混合,得到水基钻井液。
实施例4
本实施例中水基钻井液的组成为水、pH调节剂、聚合物增粘降滤失剂、降滤失剂、流型调节剂、润滑剂和加重剂;
以占水的质量百分比计,所述pH调节剂的含量为0.8%,聚合物增粘降滤失剂的含量为1.5%,降滤失剂的含量为3.0%,流型调节剂的含量为0.5%,润滑剂的含量为10.0%,加重剂的含量为45.0%;
其中,所述水为淡水;所述pH调节剂为氢氧化钠与碳酸钠,所述氢氧化钠与碳酸钠的质量比为2:8;所述聚合物增粘降滤失剂为聚丙烯酰胺钠盐,相对分子质量为100~120万;所述降滤失剂为羧甲基淀粉(CMS);所述流型调节剂为黄原胶与温伦胶,所述黄原胶与温伦胶的质量比为3:7;所述润滑剂为实施例1制备的RH-1;所述加重剂为重晶石(市售商品);
本实施例中水基钻井液的密度为1.3g/cm3,pH值为11。
实施例5
本实施例中水基钻井液的组成为水、pH调节剂、聚合物增粘降滤失剂、降滤失剂、流型调节剂、润滑剂和加重剂;
以占水的质量百分比计,所述pH调节剂的含量为0.6%,聚合物增粘降滤失剂的含量为1.0%,降滤失剂的含量为2.0%,流型调节剂的含量为0.2%,润滑剂的含量为20.0%,加重剂的含量为45.0%;
其中,所述水为海水;所述pH调节剂为氢氧化钠与碳酸钠,所述氢氧化钠与碳酸钠的质量比为4:6;所述聚合物增粘降滤失剂为聚丙烯酰胺钠盐,相对分子质量为100~120万;所述降滤失剂为羧甲基淀粉(CMS);所述流型调节剂为黄原胶与温伦胶,所述黄原胶与温伦胶的质量比为5:5;所述润滑剂为实施例2制备的RH-2;所述加重剂为重晶石(市售商品);
本实施例中水基钻井液的密度为1.3g/cm3,pH值为10。
实施例6
本实施例中水基钻井液的组成为水、pH调节剂、聚合物增粘降滤失剂、降滤失剂、流型调节剂、润滑剂和加重剂;
以占水的质量百分比计,所述pH调节剂的含量为0.4%,聚合物增粘降滤失剂的含量为0.5%,降滤失剂的含量为4.0%,流型调节剂的含量为0.3%,润滑剂的含量为30.0%,加重剂的含量为45.0%;
其中,所述水为海水;所述pH调节剂为氢氧化钠与碳酸钠,所述氢氧化钠与碳酸钠的质量比为3:7;所述聚合物增粘降滤失剂为聚丙烯酰胺钠盐,相对分子质量为100~120万;所述降滤失剂为羧甲基淀粉(CMS);所述流型调节剂为黄原胶与温伦胶,所述黄原胶与温伦胶的质量比为4:6;所述润滑剂为实施例3制备的RH-3;所述加重剂为重晶石(市售商品);
本实施例中水基钻井液的密度为1.3g/cm3,pH值为9。
实施例7
本实施例中水基钻井液的组成为水、pH调节剂、聚合物增粘降滤失剂、降滤失剂、流型调节剂、润滑剂和加重剂;
以占水的质量百分比计,所述pH调节剂的含量为0.6%,聚合物增粘降滤失剂的含量为1.0%,降滤失剂的含量为2.0%,流型调节剂的含量为0.7%,润滑剂的含量为30.0%,加重剂的含量为60.0%;
其中,所述水为淡水;所述pH调节剂为氢氧化钠与碳酸钠,所述氢氧化钠与碳酸钠的质量比为4:6;所述聚合物增粘降滤失剂为聚丙烯酰胺钠盐,相对分子质量为100~120万;所述降滤失剂为羧甲基淀粉(CMS);所述流型调节剂为黄原胶与温伦胶,所述黄原胶与温伦胶的质量比为5:5;所述润滑剂为实施例3制备的RH-3;所述加重剂为重晶石(市售商品);
本实施例中水基钻井液的密度为1.4g/cm3,pH值为10。
对比例1
100质量份白油。
对比例2
100质量份聚合醇。
对比例3
按质量份计,将100份海水、2.5份钠基膨润土、0.25份NaOH、0.25份Na2CO3、3份磺甲基酚醛树脂、3份腐殖酸钾、5.0份KCl、2.0份NaCl、2.0份聚胺抑制剂、2.0份润滑剂(油酸甲酯)以及重晶石充分混合,得到密度为1.4g/cm3的水基钻井液。
对比例4
按质量份计,将85份0#柴油、15份饱和氯化钙水溶液、2.5份有机土、4.0份主乳化剂、1.0份辅乳化剂、0.5份提切剂、2.0份碱度调节剂、2.5份降滤失剂、2.5份封堵剂以及100份重晶石充分混合,得到密度为1.4g/cm3的油基钻井液。
测试例1
按GB/T 18420.2-2009(海洋石油勘探开发污染物生物毒性检验方法)检测润滑剂的生物毒性,按SY/T 6788-2020(水溶性油田化学剂环境保护技术评价方法)分析润滑剂的降解性能,具体结果如表1所示。
表1润滑剂的环保性能评价结果
备注:润滑剂添加量为20%;LC50为卤虫半数死亡浓度(mg/L);CODCr为化学需氧量(mg/L);BOD5为生化需氧量(mg/L)。
由表1可知,本发明实施例中制备的润滑剂的LC50均大于30000mg/L,BOD5/CODCr值均大于25%,表明润滑剂环境友好。
测试例2
分别对实施例1~7和对比例1~4中钻井液的润滑性能和抗磨性能进行测试,其中,采用EP极压润滑仪在150PSI的压力下测定钻井液的润滑系数(具体参考SY/T 6094-1994《钻井液用润滑剂评价程序》中润滑系数降低率的评价方法计算润滑系数),使用KMY201-1A抗磨试验机测定钻井液的抗磨性能;具体结果如表2所示。
表2钻井液的润滑性能和抗磨性能测试结果
钻井液来源 | M | KM |
实施例1 | 0.086 | 8 |
实施例2 | 0.048 | 10 |
实施例3 | 0.031 | 10 |
实施例4 | 0.091 | 9 |
实施例5 | 0.087 | 10 |
实施例6 | 0.063 | 10 |
实施例7 | 0.068 | 10 |
对比例1 | 0.036 | 5 |
对比例2 | 0.035 | 7 |
对比例3 | 0.120 | 8 |
对比例4 | 0.073 | 9 |
备注:M为钻井液润滑系数(无量纲);KM为钻井液抗磨性能(块)。
由表2可知,随着本发明实施例制备的润滑剂含量增加,钻井液的钻井液润滑系数显著下降,抗磨性能提高,含30%润滑剂的钻井液的润滑性能以及抗磨性能优于100%白油和100%聚合醇;另外,由本发明实施例制备的润滑剂配制的水基钻井液的润滑性能以及抗磨性能远优于常规水基钻井液,且与油基钻井液的润滑性能以及抗磨性能相近,表明本发明提供的润滑剂具有优异的润滑性能。
测试例3
按照标准GB/T 16783.1-2014(石油天然气工业钻井液现场测试第1部分:水基钻井液)对实施例4~7以及对比例3中钻井液热滚后的流变性能、封堵性能等进行评价,按照标准GB/T 16783.2-2012(石油天然气工业钻井液现场测试第2部分:油基钻井液)测试对比例4中钻井液热滚后的流变性能、封堵性能等,具体结果见表3。
表3钻井液的性能测试评价结果
钻井液来源 | PV | YP | Φ3 | PPT | G |
实施例4 | 28 | 10 | 9 | 6.4 | 90.20 |
实施例5 | 34 | 11 | 11 | 4.2 | 93.19 |
实施例6 | 38 | 13 | 12 | 3.0 | 94.23 |
实施例7 | 40 | 14 | 13 | 3.2 | 95.78 |
对比例3 | 36 | 10 | 10 | 5.8 | 84.12 |
对比例4 | 33 | 8 | 7 | 4.7 | 93.86 |
备注:热滚条件为120℃×16h;PV为钻井液塑性粘度(mPa·s);YP为钻井液动切力(Pa);Φ3为六速旋转粘度计3转读数(无量纲);PPT为封堵滤失量(mL),具体是指使用沙盘代替滤纸,在3.5MPa、120℃以及30min条件下的失水体积;G为露头土在钻井液的滚动回收率(%)。
由表3可知,本发明提供的水基钻井液在120℃热滚16h后均表现出良好的流变性能、抑制性能以及低滤失性能,所述水基钻井液中润滑剂含量增加,有助于提高水基钻井液的封堵性能以及抑制性能,说明本发明提供的聚天冬氨酸衍生物作为润滑剂对水基钻井液的抑制性能以及封堵性能有一定的改善作用。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (10)
1.一种聚天冬氨酸衍生物,具有式I所示结构:
所述式I中,R1选自-CH2-CH2-CH2-、-CH2-CH2-CH2-CH2-或-CH2-CH2-CH2-CH2-CH2-CH2-;
R2选自-OH、-N-(CH2-CH2-OH)2、-O-CH2-CH2-NH-CH2-CH2-OH、-NH-CH2-CH2-OH或-O-CH2-CH2-NH2;
n与m独立地为8~17。
2.根据权利要求1所述的聚天冬氨酸衍生物,其特征在于,所述式I中R1为-CH2-CH2-CH2-、R2为-OH,且n与m为12~17;
或者所述式I中R1为-CH2-CH2-CH2-CH2-、R2为-O-CH2-CH2-NH2,且n与m为8~12;
或者所述式I中R1为-CH2-CH2-CH2-CH2-CH2-CH2-、R2为-O-CH2-CH2-NH-CH2-CH2-OH,且n与m为10~15。
3.权利要求1~2任一项所述聚天冬氨酸衍生物的制备方法,包括以下步骤:
将聚天冬氨酸与水溶性有机胺混合,进行聚合反应,得到聚天冬氨酸衍生物;所述水溶性有机胺选自丙二胺、丁二胺、己二胺、单乙醇胺和二乙醇胺。
4.根据权利要求3所述的制备方法,其特征在于,所述聚天冬氨酸与水溶性有机胺的质量比为(7~9):(1~3)。
5.根据权利要求3所述的制备方法,其特征在于,所述聚合反应的温度为150~180℃,时间为8~12h。
6.权利要求1~2任一项所述聚天冬氨酸衍生物或权利要求3~5任一项所述制备方法制备得到的聚天冬氨酸衍生物作为润滑剂的应用。
7.一种水基钻井液,包括水、pH调节剂、聚合物增粘降滤失剂、降滤失剂、流型调节剂、润滑剂和加重剂,所述润滑剂为权利要求1~2任一项所述聚天冬氨酸衍生物或权利要求3~5任一项所述制备方法制备得到的聚天冬氨酸衍生物,所述聚合物增粘降滤失剂为聚丙烯酰胺钾盐、聚丙烯酰胺钠盐和聚阴离子纤维素中的一种或几种,所述降滤失剂为磺甲基酚醛树脂、磺甲基褐煤树脂、羟丙基淀粉和羧甲基淀粉中的一种或几种。
8.根据权利要求7所述的水基钻井液,其特征在于,以占水的质量百分比计,所述pH调节剂的含量为0.4~0.8%,聚合物增粘降滤失剂的含量为0.5~1.5%,降滤失剂的含量为2.0~4.0%,流型调节剂的含量为0.2~0.7%,润滑剂的含量为10.0~30.0%,加重剂的含量为45.0~60.0%。
9.根据权利要求7或8所述的水基钻井液,其特征在于,所述流型调节剂包括黄原胶、罗望子胶、魔芋胶、温伦胶和瓜尔豆胶中的一种或几种。
10.权利要求7~9任一项所述水基钻井液在大位移井钻采中的应用。
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