CN118546292A - Polyacrylamide copolymer for displacement material and preparation method thereof, displacement material and application thereof - Google Patents
Polyacrylamide copolymer for displacement material and preparation method thereof, displacement material and application thereof Download PDFInfo
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- 229920002401 polyacrylamide Polymers 0.000 title claims abstract description 30
- 239000000463 material Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006073 displacement reaction Methods 0.000 title abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 17
- 238000011161 development Methods 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- 239000002332 oil field water Substances 0.000 claims abstract description 4
- 239000000178 monomer Substances 0.000 claims description 53
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 229920006322 acrylamide copolymer Polymers 0.000 claims description 34
- 239000000084 colloidal system Substances 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 22
- 239000003431 cross linking reagent Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 238000006460 hydrolysis reaction Methods 0.000 claims description 19
- 239000003999 initiator Substances 0.000 claims description 19
- 229920001577 copolymer Polymers 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 13
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 12
- 239000008139 complexing agent Substances 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical group [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 7
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 7
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 7
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 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 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 2
- 229940015043 glyoxal Drugs 0.000 claims description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 2
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical group [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 claims description 2
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical group C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims 1
- UMGDCJDMYOKAJW-UHFFFAOYSA-N aminothiocarboxamide Natural products NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 claims 1
- 230000035699 permeability Effects 0.000 abstract description 14
- 238000004945 emulsification Methods 0.000 abstract description 8
- 239000003795 chemical substances by application Substances 0.000 abstract description 7
- 238000002347 injection Methods 0.000 abstract description 7
- 239000007924 injection Substances 0.000 abstract description 7
- 150000003839 salts Chemical class 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 44
- 229920000642 polymer Polymers 0.000 description 20
- 239000003921 oil Substances 0.000 description 18
- 239000007864 aqueous solution Substances 0.000 description 17
- 239000008187 granular material Substances 0.000 description 16
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 229910001873 dinitrogen Inorganic materials 0.000 description 10
- 230000033558 biomineral tissue development Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- JCGVEGFEGJLZDW-UHFFFAOYSA-N naphthalen-2-ylthiourea Chemical group C1=CC=CC2=CC(NC(=S)N)=CC=C21 JCGVEGFEGJLZDW-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000018109 developmental process Effects 0.000 description 6
- 230000033116 oxidation-reduction process Effects 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000010779 crude oil Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000008398 formation water Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- KCOYHFNCTWXETP-UHFFFAOYSA-N (carbamothioylamino)thiourea Chemical compound NC(=S)NNC(N)=S KCOYHFNCTWXETP-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 229940099427 potassium bisulfite Drugs 0.000 description 1
- ZLMJMSJWJFRBEC-AKLPVKDBSA-N potassium-42 Chemical compound [42K] ZLMJMSJWJFRBEC-AKLPVKDBSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000009671 shengli Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000005406 washing 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/12—Hydrolysis
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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
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
本发明涉及油田注水开发中调剖堵水领域，公开了一种调驱材料用聚丙烯酰胺共聚物及其制备方法、调驱材料和应用。该聚丙烯酰胺共聚物含有结构单元一、结构单元二和结构单元三，其中，所述结构单元一具有式Ⅰ所示的结构，所述结构单元二具有式Ⅱ所示的结构，所述结构单元三具有式Ⅲ所示的结构；其中，R为C5‑C15的烷基，n为1‑6的整数，M为金属元素。该可动型凝胶调驱材料可以进入到油藏深部，并且在高温、高盐条件下具有较高的粘度，还能够降低油水表界面张力，具有较好的乳化性能，具有较高的封堵率，适于在高渗透油藏(渗透率高于2000mD)中作为调驱剂和调堵剂应用。The present invention relates to the field of profile control and water plugging in oilfield water injection development, and discloses a polyacrylamide copolymer for profile control and displacement material, a preparation method thereof, a profile control and displacement material and application thereof. The polyacrylamide copolymer contains a structural unit 1, a structural unit 2 and a structural unit 3, wherein the structural unit 1 has a structure shown in formula I, the structural unit 2 has a structure shown in formula II, and the structural unit 3 has a structure shown in formula III; Wherein, R is a C5-C15 alkyl group, n is an integer of 1-6, and M is a metal element. The movable gel flooding material can enter deep into the reservoir, and has a high viscosity under high temperature and high salt conditions, can also reduce the interfacial tension of the oil-water surface, has good emulsification performance, has a high plugging rate, and is suitable for use as a flooding agent and a plugging agent in high permeability reservoirs (permeability higher than 2000mD).
Description
技术领域Technical Field
本发明涉及油田注水开发中调剖堵水领域，具体地，涉及一种调驱材料用聚丙烯酰胺共聚物及其制备方法、调驱材料和应用。The invention relates to the field of profile control and water plugging in oil field water injection development, and in particular to a polyacrylamide copolymer for profile control and displacement material, a preparation method thereof, a profile control and displacement material and application thereof.
背景技术Background Art
近些年来，聚合物驱油技术已经在大庆、胜利等常规油田条件取得了良好的应用效果和经济效益，主要聚合物为部分水解聚丙烯酰胺。但是由于部分水解聚丙烯酰胺的耐温耐盐性差、稳定性差等缺点，使其在高温高盐油藏中的应用受到了严重的限制。近十几年来，国内外开展了大量聚丙烯酰胺聚合物的改性工作，其目的在于改进传统聚合物固有的缺点，以使其能够更好地适用于高温高盐等苛刻条件油藏。In recent years, polymer flooding technology has achieved good application results and economic benefits in conventional oilfield conditions such as Daqing and Shengli, and the main polymer is partially hydrolyzed polyacrylamide. However, due to the shortcomings of partially hydrolyzed polyacrylamide, such as poor temperature and salt resistance and poor stability, its application in high-temperature and high-salinity reservoirs is severely limited. In the past decade, a large number of polyacrylamide polymer modification works have been carried out at home and abroad, with the aim of improving the inherent shortcomings of traditional polymers so that they can be better applied to reservoirs with harsh conditions such as high temperature and high salt.
近年来，随着我国油田注水开发程度地不断提高，致使油藏含水率进一步升高，含水率达到95％以上，由此提出了在油藏深部调整吸水剖面，迫使液流转向，改善注水开发效果，实现提高原油采收率的目的。随科研人员对地层注水开发的不断深入认识和技术的发展，逐渐形成了深部调驱技术研究的新热点，在稳油控水等额方面发挥重要的作用，相应地研制了强凝胶、弱凝胶、颗粒凝胶等新型化学剂。凝胶是指一定浓度的聚合物与交联剂反应后，在一定条件下形成具有三维空间网络结构的粘弹体，交联主要方式为分子间交联。冻胶是目前使用最为广泛的堵剂，但其高分子链仍为聚丙烯酰胺，故其性能受外界物理化学条件影响大，导致耐温抗盐性差。在油田现场应用时应充分考虑其与地层水、地层温度、矿化度等的配伍性，优选新型改性聚合物与交联剂，以提高在高温高盐下的适应性，并解决无法到达油藏深部调驱的目的。In recent years, with the continuous improvement of the degree of water injection development in my country's oil fields, the water content of the reservoir has further increased, and the water content has reached more than 95%. Therefore, it is proposed to adjust the water absorption profile in the deep reservoir, force the liquid flow to turn, improve the effect of water injection development, and achieve the purpose of increasing crude oil recovery. With the continuous deepening of scientific researchers' understanding of formation water injection development and the development of technology, a new hotspot in the research of deep displacement technology has gradually formed, playing an important role in stabilizing oil and controlling water. Accordingly, new chemical agents such as strong gel, weak gel, and granular gel have been developed. Gel refers to a viscoelastic body with a three-dimensional spatial network structure formed under certain conditions after a certain concentration of polymer reacts with a cross-linking agent, and the main cross-linking method is intermolecular cross-linking. Gel is the most widely used plugging agent at present, but its polymer chain is still polyacrylamide, so its performance is greatly affected by external physical and chemical conditions, resulting in poor temperature resistance and salt resistance. When applied on-site in oil fields, full consideration should be given to its compatibility with formation water, formation temperature, mineralization, etc., and new modified polymers and cross-linking agents should be selected to improve adaptability under high temperature and high salinity conditions and to solve the problem of being unable to reach deep reservoirs for flooding.
发明内容Summary of the invention
本发明的目的是为了克服现有技术的存在的上述问题，提供一种调驱材料用聚丙烯酰胺共聚物及其制备方法、调驱材料和应用，该丙烯酰胺共聚物形成的可动型凝胶调驱材料可以进入到油藏深部，并且在高温、高盐条件下具有较高的粘度，还能够降低油水表界面张力，具有较好的乳化性能，适于在高渗透油藏(渗透率高于2000mD)中作为调驱剂和调堵剂应用，具有较高的封堵率。The purpose of the present invention is to overcome the above-mentioned problems existing in the prior art and to provide a polyacrylamide copolymer for a flooding material and a preparation method thereof, a flooding material and an application thereof. The movable gel flooding material formed by the acrylamide copolymer can enter the deep part of the oil reservoir and has a high viscosity under high temperature and high salt conditions. It can also reduce the interfacial tension between the oil and water surfaces and has good emulsification properties. It is suitable for use as a flooding agent and a plugging agent in high permeability oil reservoirs (permeability higher than 2000mD) and has a high plugging rate.
本发明的第一个方面是提供一种调驱材料用聚丙烯酰胺共聚物，所述聚丙烯酰胺共聚物含有结构单元一、结构单元二和结构单元三，其中，所述结构单元一具有式Ⅰ所示的结构，所述结构单元二具有式Ⅱ所示的结构，所述结构单元三具有式Ⅲ所示的结构；The first aspect of the present invention is to provide a polyacrylamide copolymer for a displacement material, wherein the polyacrylamide copolymer comprises a structural unit 1, a structural unit 2 and a structural unit 3, wherein the structural unit 1 has a structure shown in formula I, the structural unit 2 has a structure shown in formula II, and the structural unit 3 has a structure shown in formula III;
其中，R为C5-C15的烷基，n为1-6的整数，M为金属元素。Wherein, R is a C5-C15 alkyl group, n is an integer of 1-6, and M is a metal element.
在本发明中，各结构单元的含量具有较宽的选择范围，在本发明一种优选的实施方式中，以所述丙烯酰胺共聚物的总重量为100％计，所述结构单元一的含量为85-97.5重量％，所述结构单元二的含量为2-12重量％，所述结构单元三的含量为0.5-3重量％。In the present invention, the content of each structural unit has a wide selection range. In a preferred embodiment of the present invention, based on the total weight of the acrylamide copolymer as 100%, the content of the structural unit 1 is 85-97.5% by weight, the content of the structural unit 2 is 2-12% by weight, and the content of the structural unit 3 is 0.5-3% by weight.
更优选地，以所述丙烯酰胺共聚物的总重量为100％计，所述结构单元一的含量为88-94重量％，所述结构单元二的含量为5-10重量％，所述结构单元三的含量为1-2重量％。More preferably, based on 100% of the total weight of the acrylamide copolymer, the content of the structural unit 1 is 88-94% by weight, the content of the structural unit 2 is 5-10% by weight, and the content of the structural unit 3 is 1-2% by weight.
本发明中，聚合物中的结构单元的含量可以通过本领域的检测得到。后文的实施例中通过单体的投料量进行计算。In the present invention, the content of the structural unit in the polymer can be obtained by detection in the art. In the following examples, it is calculated by the feeding amount of the monomer.
在本发明中，一种优选的实施方式中，R为C5-C15的直链烷基，优选为C7-C12的直链烷基。In the present invention, in a preferred embodiment, R is a C5-C15 straight-chain alkyl group, preferably a C7-C12 straight-chain alkyl group.
在本发明中，n具有较宽的选择范围，在本发明一种优选的实施方式中，n为3-5的整数。In the present invention, n has a wide selection range. In a preferred embodiment of the present invention, n is an integer of 3-5.
在本发明中，M具有较宽的选择范围，在本发明一种优选的实施方式中，M为碱金属元素，优选为钾或钠。In the present invention, M has a wide selection range. In a preferred embodiment of the present invention, M is an alkali metal element, preferably potassium or sodium.
本发明的第二个方面是提供一种第一个方面所述的聚丙烯酰胺共聚物的制备方法，包括在引发剂存在下，将单体混合物在溶剂中进行聚合反应，得到共聚物胶体；再将共聚物胶体进行水解反应；The second aspect of the present invention is to provide a method for preparing the polyacrylamide copolymer described in the first aspect, comprising subjecting a monomer mixture to a polymerization reaction in a solvent in the presence of an initiator to obtain a copolymer colloid; and then subjecting the copolymer colloid to a hydrolysis reaction;
其中，所述单体混合物含有丙烯酰胺、单体二和单体三，所述单体二具有式Ⅳ所示结构、所述单体三具有式Ⅴ所示结构；Wherein, the monomer mixture contains acrylamide, monomer 2 and monomer 3, the monomer 2 has a structure shown in formula IV, and the monomer 3 has a structure shown in formula V;
其中，式Ⅳ中R为C5-C15的烷基，n为1-6的整数，M为金属元素。Wherein, in formula IV, R is a C5-C15 alkyl group, n is an integer of 1-6, and M is a metal element.
在本发明中，各单体的用量具有较宽的选择范围，在本发明一种优选的实施方式中，各单体的用量使得：以所述丙烯酰胺共聚物的总重量为100％计，所述结构单元一的含量为85-97.5重量％，所述结构单元二的含量为2-12重量％，所述结构单元三的含量为0.5-3重量％。In the present invention, the amount of each monomer has a wide selection range. In a preferred embodiment of the present invention, the amount of each monomer is such that: based on the total weight of the acrylamide copolymer as 100%, the content of the structural unit 1 is 85-97.5% by weight, the content of the structural unit 2 is 2-12% by weight, and the content of the structural unit 3 is 0.5-3% by weight.
更优选地，各单体的用量使得：以所述丙烯酰胺共聚物的总重量为100％计，所述结构单元一的含量为88-94重量％，所述结构单元二的含量为5-10重量％，所述结构单元三的含量为1-2重量％。More preferably, the amount of each monomer is such that: based on the total weight of the acrylamide copolymer being 100%, the content of the structural unit 1 is 88-94% by weight, the content of the structural unit 2 is 5-10% by weight, and the content of the structural unit 3 is 1-2% by weight.
在本发明中，一种优选的实施方式中，式Ⅳ中R为C5-C15的直链烷基，优选为C7-C12的直链烷基。In the present invention, in a preferred embodiment, R in formula IV is a C5-C15 straight-chain alkyl group, preferably a C7-C12 straight-chain alkyl group.
在本发明中，式Ⅳ中n具有较宽的选择范围，在本发明一种优选的实施方式中，n为3-5的整数。In the present invention, n in Formula IV has a wide selection range. In a preferred embodiment of the present invention, n is an integer of 3-5.
在本发明中，M具有较宽的选择范围，在本发明一种优选的实施方式中，M为碱金属元素，优选为钾或钠。In the present invention, M has a wide selection range. In a preferred embodiment of the present invention, M is an alkali metal element, preferably potassium or sodium.
在本发明一种优选的实施方式中，该制备方法包括以下步骤：In a preferred embodiment of the present invention, the preparation method comprises the following steps:
1)在引发剂存在下，将单体混合物在水中进行溶液聚合反应，得到共聚物胶体；1) In the presence of an initiator, the monomer mixture is subjected to solution polymerization in water to obtain a copolymer colloid;
2)将所述共聚物胶体进行水解反应。2) subjecting the copolymer colloid to a hydrolysis reaction.
在本发明中，所述溶液聚合反应的条件具有较宽的选择范围，在本发明一种优选的实施方式中，所述溶液聚合反应的条件还包括：在络合剂和/或促进剂存在下进行。In the present invention, the conditions for the solution polymerization reaction have a wide range of selection. In a preferred embodiment of the present invention, the conditions for the solution polymerization reaction further include: carrying out the reaction in the presence of a complexing agent and/or a promoter.
对于络合剂的用量，选择范围较宽，优选地，相对于100重量份的所述单体混合物，所述络合剂的用量为0.01-0.1重量份。The amount of the complexing agent used has a wide selection range. Preferably, the amount of the complexing agent used is 0.01-0.1 parts by weight relative to 100 parts by weight of the monomer mixture.
对于促进剂的用量，在本发明中选择范围较宽，在本发明一种优选的实施方式中，所述促进剂的用量为0.05-0.2重量份。The amount of the accelerator used has a wide range of selection in the present invention. In a preferred embodiment of the present invention, the amount of the accelerator used is 0.05-0.2 parts by weight.
本发明中，所述络合剂可以有多种选择，优选为乙二胺四乙酸二钠。In the present invention, the complexing agent can be selected from a variety of options, preferably disodium ethylenediaminetetraacetate.
在本发明中，促进剂可以有多种选择，在本发明一种优选的实施方式中，所述促进剂为2-萘基硫脲。In the present invention, there are many options for the accelerator. In a preferred embodiment of the present invention, the accelerator is 2-naphthylthiourea.
在本发明一种更优选的实施方式中，所述溶液聚合反应的条件还包括：在络合剂和促进剂存在下进行。在溶液聚合反应过程中加入促进剂能够进一步提高制备得到的丙烯酰胺共聚物的增粘性和乳化性能。优选地，相对于100重量份的所述单体混合物，所述氧化-还原体系引发剂为0.015-0.15重量份，所述络合剂为0.01-0.1重量份，所述促进剂0.05-0.2重量份。In a more preferred embodiment of the present invention, the solution polymerization reaction further comprises: being carried out in the presence of a complexing agent and a promoter. Adding a promoter during the solution polymerization reaction can further improve the viscosity and emulsification properties of the prepared acrylamide copolymer. Preferably, relative to 100 parts by weight of the monomer mixture, the oxidation-reduction system initiator is 0.015-0.15 parts by weight, the complexing agent is 0.01-0.1 parts by weight, and the promoter is 0.05-0.2 parts by weight.
在本发明中，所述溶液聚合反应的条件具有较宽的选择范围，在本发明一种优选的实施方式中，所述溶液聚合反应的条件包括：所述溶液聚合反应在惰性气氛下进行；和/或，聚合反应温度为30-40℃；和/或，时间为8-10h；和/或pH值为6-8。In the present invention, the conditions of the solution polymerization reaction have a wide range of selection. In a preferred embodiment of the present invention, the conditions of the solution polymerization reaction include: the solution polymerization reaction is carried out under an inert atmosphere; and/or the polymerization reaction temperature is 30-40°C; and/or the time is 8-10h; and/or the pH value is 6-8.
在本发明一种更加优选的实施方式中，所述溶液聚合反应的条件包括：所述溶液聚合反应在惰性气氛下进行，所述引发剂为氧化-还原体系引发剂，温度为30-40℃，时间为8-10h，pH值为6-8。所述惰性气氛可以由氮气提供。pH值的调节可以采用现有技术中常用的手段进行，例如通过加入氢氧化钠等碱性物质。In a more preferred embodiment of the present invention, the conditions of the solution polymerization reaction include: the solution polymerization reaction is carried out under an inert atmosphere, the initiator is an oxidation-reduction system initiator, the temperature is 30-40° C., the time is 8-10 hours, and the pH value is 6-8. The inert atmosphere can be provided by nitrogen. The pH value can be adjusted by means commonly used in the prior art, such as by adding alkaline substances such as sodium hydroxide.
在本发明中，所述引发剂可以选择本领域常规的引发剂，在本发明一种优选的实施方式中，所述引发剂为氧化-还原体系引发剂。In the present invention, the initiator can be selected from conventional initiators in the art. In a preferred embodiment of the present invention, the initiator is an oxidation-reduction system initiator.
对于引发剂的用量，本领域技术人员也可以在较宽的范围调整，在本发明一种优选的实施方式中，相对于100重量份的所述单体混合物，所述氧化-还原体系引发剂的用量为0.015-0.15重量份；优选地，所述氧化-还原体系引发剂选自过硫酸盐和亚硫酸盐；更优选地，所述过硫酸盐选自过硫酸钾、过硫酸钠和过硫酸铵中的至少一种；和/或，所述亚硫酸盐选自亚硫酸氢钾和/或亚硫酸氢钠。Regarding the amount of the initiator, those skilled in the art can also adjust it within a wider range. In a preferred embodiment of the present invention, the amount of the oxidation-reduction system initiator is 0.015-0.15 parts by weight relative to 100 parts by weight of the monomer mixture; preferably, the oxidation-reduction system initiator is selected from persulfates and sulfites; more preferably, the persulfate is selected from at least one of potassium persulfate, sodium persulfate and ammonium persulfate; and/or the sulfite is selected from potassium bisulfite and/or sodium bisulfite.
在本发明一种更加优选的实施方式中，相对于100重量份的所述单体混合物，所述过硫酸盐的用量为0.01-0.1重量份；所述亚硫酸盐的用量为0.005-0.05重量份。In a more preferred embodiment of the present invention, relative to 100 parts by weight of the monomer mixture, the amount of the persulfate is 0.01-0.1 parts by weight; the amount of the sulfite is 0.005-0.05 parts by weight.
在本发明中，所述水解反应的条件具有较宽的选择范围，在本发明一种优选的实施方式中，所述水解反应在碱性条件下进行，优选通过将共聚物胶体与固体碱性物质混合，进一步优选所述固体碱性物质选自氢氧化钠和/或氢氧化钾。In the present invention, the conditions of the hydrolysis reaction have a wide range of selection. In a preferred embodiment of the present invention, the hydrolysis reaction is carried out under alkaline conditions, preferably by mixing the copolymer colloid with a solid alkaline substance. It is further preferred that the solid alkaline substance is selected from sodium hydroxide and/or potassium hydroxide.
对于固体碱性物质的用量，本领域技术人员也可以灵活调整，在本发明一种优选的实施方式中，所述固体碱性物质与共聚物胶体的质量比为1：(15-44)；The amount of the solid alkaline substance can also be flexibly adjusted by those skilled in the art. In a preferred embodiment of the present invention, the mass ratio of the solid alkaline substance to the copolymer colloid is 1:(15-44);
优选地，所述水解反应的条件包括：温度为80-90℃，和/或，时间为2-3h。Preferably, the conditions of the hydrolysis reaction include: a temperature of 80-90° C., and/or a time of 2-3 h.
在本发明中，所述水解反应可以在碱性条件下进行，碱性条件可以通过加入氢氧化钠粒碱等物质实现，对碱性物质的加入量没有特别限定，本领域技术人员可以根据反应的需要进行调整。优选地，所述水解反应的条件包括：温度为80-90℃，时间为2-3h。In the present invention, the hydrolysis reaction can be carried out under alkaline conditions, and the alkaline conditions can be achieved by adding sodium hydroxide granules and other substances. There is no particular limitation on the amount of alkaline substance added, and those skilled in the art can adjust it according to the needs of the reaction. Preferably, the conditions of the hydrolysis reaction include: a temperature of 80-90°C and a time of 2-3h.
优选地，在进行水解反应之后，对反应产物进行造粒、干燥、粉碎、筛分得到丙烯酰胺共聚物。Preferably, after the hydrolysis reaction, the reaction product is granulated, dried, crushed and sieved to obtain the acrylamide copolymer.
根据本发明提供的一种优选的具体实施方式中，制备丙烯酰胺共聚物的方法包括：According to a preferred embodiment provided by the present invention, the method for preparing acrylamide copolymer comprises:
1)将丙烯酰胺加入到反应器中配成水溶液，然后加入单体二、单体三、络合物水溶液和促进剂，调节pH值，充分搅拌使其成为稳定的溶液；1) adding acrylamide into a reactor to prepare an aqueous solution, then adding monomer 2, monomer 3, complex aqueous solution and accelerator, adjusting the pH value, and stirring sufficiently to make it a stable solution;
2)加入氧化-还原体系引发剂，鼓入惰性气体使其混合均匀后，密封后聚合得到聚合物胶体；2) adding an oxidation-reduction system initiator, blowing in an inert gas to mix evenly, sealing and polymerizing to obtain a polymer colloid;
3)取出胶体，经造粒后加入碱性物质，使其糅合均匀后进行水解反应；3) Taking out the colloid, adding alkaline substances after granulation, mixing it evenly and then carrying out hydrolysis reaction;
4)将水解反应产物进行造粒、干燥、粉碎、筛分后得到丙烯酰胺共聚物。4) Granulating, drying, crushing and screening the hydrolysis reaction product to obtain an acrylamide copolymer.
本发明的第三个方面是提供一种调驱材料，含有第一个方面所述的聚丙烯酰胺共聚物或者第二个方面所述的制备方法制备得到的聚丙烯酰胺共聚物，以及交联剂和水。The third aspect of the present invention is to provide a displacement material, comprising the polyacrylamide copolymer described in the first aspect or the polyacrylamide copolymer prepared by the preparation method described in the second aspect, a cross-linking agent and water.
本发明提供了本发明第一方面所述的丙烯酰胺共聚物和由本发明第二方面所述方法制备得到的丙烯酰胺采用现场水配制后，加入交联剂，在油藏地层下2-5天后形成可动型凝胶，这种可动型凝胶在高渗透油藏(渗透率高于2000mD)中作为调驱剂和调堵剂应用。The present invention provides an acrylamide copolymer as described in the first aspect of the present invention and an acrylamide prepared by the method as described in the second aspect of the present invention, which is prepared with on-site water and then a cross-linking agent is added to form a movable gel under the oil reservoir formation after 2-5 days. The movable gel is used as a displacement agent and a plugging agent in a high permeability oil reservoir (permeability higher than 2000mD).
在本发明中，调驱材料中聚丙烯酰胺共聚物、交联剂的含量具有较宽的选择范围，在本发明一种优选的实施方式中，相对于100重量份的水，所述聚丙烯酰胺共聚物的含量为0.2-0.6重量份，优选为0.3-0.6重量份，所述交联剂的含量为0.004-0.01重量份，优选为0.005-0.009重量份。In the present invention, the content of polyacrylamide copolymer and cross-linking agent in the displacement material has a wide selection range. In a preferred embodiment of the present invention, relative to 100 parts by weight of water, the content of the polyacrylamide copolymer is 0.2-0.6 parts by weight, preferably 0.3-0.6 parts by weight, and the content of the cross-linking agent is 0.004-0.01 parts by weight, preferably 0.005-0.009 parts by weight.
在本发明中，交联剂具有较宽的选择范围，在本发明一种优选的实施方式中，所述交联剂选自甲醛、乙二醛和六次甲基四胺中的至少一种。In the present invention, the cross-linking agent has a wide selection range. In a preferred embodiment of the present invention, the cross-linking agent is selected from at least one of formaldehyde, glyoxal and hexamethylenetetramine.
在本发明中，“和/或”意味着可以为两者中的任一种情况，也可以两种情况并存。In the present invention, "and/or" means that it can be either one of the two situations, or both situations can exist.
本发明的第四个方面是提供一种第一个方面所述的聚丙烯酰胺共聚物或者第二个方面所述的制备方法制备得到的聚丙烯酰胺共聚物或者第三个方面所述的调驱材料在油田注水开发调剖堵水中的应用。The fourth aspect of the present invention provides an application of the polyacrylamide copolymer described in the first aspect or the polyacrylamide copolymer prepared by the preparation method described in the second aspect or the displacement material described in the third aspect in profile control and water plugging in oilfield water injection development.
本发明通过在聚丙烯酰胺的大分子链中同时引入单体二和单体三，制备得到的聚丙烯酰胺共聚物在高温(150℃)、高矿化度(150000mg/L)条件下具有较高的粘度，与交联剂混合后注入地层，可以进入到油藏深部，在2-5天后形成可动型凝胶实现有效封堵，尤其适应于高渗透油藏(渗透率高于2000mD)，并且能够降低油水表界面张力，具有较好的乳化性能。通过验证以看出，本发明提供的丙烯酰胺共聚物在温度为95℃，矿化度为150000mg/L的条件下具有更高的表观粘度和良好的表面活性，在地层温度150℃下可形成可动型凝胶，具有优异的封堵效果，可应用于高渗透油藏(高于2000mD)，对提高原油采收率具有重要意义。The present invention introduces monomer two and monomer three into the macromolecular chain of polyacrylamide at the same time, and the prepared polyacrylamide copolymer has a higher viscosity under high temperature (150°C) and high mineralization (150000mg/L) conditions, and after being mixed with a cross-linking agent and injected into the formation, it can enter the deep part of the oil reservoir, and after 2-5 days, a movable gel is formed to achieve effective plugging, which is particularly suitable for high permeability reservoirs (permeability higher than 2000mD), and can reduce the interfacial tension of the oil-water surface, and has good emulsification performance. Through verification, it can be seen that the acrylamide copolymer provided by the present invention has a higher apparent viscosity and good surface activity under the conditions of a temperature of 95°C and a mineralization of 150000mg/L, and can form a movable gel at a formation temperature of 150°C, has an excellent plugging effect, can be applied to high permeability reservoirs (higher than 2000mD), and is of great significance to improving crude oil recovery.
本发明所述的丙烯酰胺共聚物及其制备方法，与现有技术相比，发明人通过研究验证，发现本发明在分子设计合成和性能上具有以下优点和效果：Compared with the prior art, the acrylamide copolymer and the preparation method thereof of the present invention have the following advantages and effects in terms of molecular design, synthesis and performance, as verified by the inventors through research:
本发明是在聚丙烯酰胺的大分子链上同时引入功能单体二和功能单体三，大幅度提高了共聚物的耐温抗盐性和表界面活性，与交联剂混合后可有效进入高温高盐油藏深部，达到深部调驱的目的，同时在2-5天后可形成可动型凝胶，对油藏地层中高渗层形成有效封堵。功能单体二含有超亲水基团和亲油基团，具有良好的乳化效果，在聚合体系中发挥自乳化作用，形成的共聚物具有良好的乳化携油作用。功能单体三在促进剂的作用下，其聚合活性得到显著提升，可使三种共聚单体的结构单元无规地分布在高分子链中，进而使其具有优异的增粘性和乳化洗油能力。The present invention simultaneously introduces functional monomers 2 and 3 into the macromolecular chain of polyacrylamide, which greatly improves the temperature resistance and salt resistance and the surface activity of the copolymer. After mixing with a cross-linking agent, it can effectively enter the deep part of the high-temperature and high-salt oil reservoir to achieve the purpose of deep adjustment and displacement. At the same time, it can form a movable gel after 2-5 days to effectively block the high-permeability layer in the oil reservoir formation. Functional monomer 2 contains superhydrophilic groups and lipophilic groups, has a good emulsification effect, plays a self-emulsification role in the polymerization system, and the formed copolymer has a good emulsification and oil-carrying effect. Under the action of the promoter, the polymerization activity of functional monomer 3 is significantly improved, and the structural units of the three copolymer monomers can be randomly distributed in the polymer chain, thereby making it have excellent viscosity increasing and emulsification and oil washing capabilities.
本发明的丙烯酰胺共聚物采用油田现场水配制成溶液与交联剂混合后一并注入油藏地层，具有很好的流动性，可以顺利进入油藏深部，达到深部调驱和调堵的效果，而且在关井2-5天后形成可动型凝胶，增强对油藏地层中高渗层形成有效封堵，可大幅度提高原油采收率，尤其适应于高渗透油藏(渗透率高于2000mD)，对油田增产增效具有重要的意义。The acrylamide copolymer of the invention is prepared into a solution by using on-site water of the oil field and mixed with a cross-linking agent and then injected into the oil reservoir stratum. The acrylamide copolymer has good fluidity and can smoothly enter the deep part of the oil reservoir to achieve the effect of deep displacement and plugging. Moreover, the copolymer forms a movable gel after shutting in the well for 2-5 days, which enhances the effective plugging of the high permeability layer in the oil reservoir stratum and can greatly improve the crude oil recovery rate. The copolymer is particularly suitable for high permeability oil reservoirs (permeability is higher than 2000mD) and has important significance for increasing the production and efficiency of oil fields.
具体实施方式DETAILED DESCRIPTION
下面结合具体实施例对本发明进行具体的描述，有必要在此指出的是以下实施例只用于对本发明的进一步说明，不能理解为对本发明保护范围的限制，本领域技术人员根据本发明内容对本发明做出的一些非本质的改进和调整仍属本发明的保护范围。The present invention is described in detail below in conjunction with specific embodiments. It is necessary to point out that the following embodiments are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made to the present invention by those skilled in the art based on the contents of the present invention still fall within the scope of protection of the present invention.
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。The endpoints and any values of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoint values of each range, the endpoint values of each range and the individual point values, and the individual point values can be combined with each other to obtain one or more new numerical ranges, which should be regarded as specifically disclosed in this article.
以下将通过实施例对本发明进行详细描述。以下实施例中，The present invention will be described in detail below by way of examples. In the following examples,
除特殊说明外，所有原料均来自商购。其中，丙烯酰胺购于东营宝莫环境工程有限公司，功能单体二的结构式如式Ⅳ所示，M为Na，n、R分别见对应的实施例，均购于广州科的化工有限公司，功能单体三如式Ⅴ所示，购于天津希恩思生化科技有限公司。Unless otherwise specified, all raw materials are purchased from commercial sources. Among them, acrylamide was purchased from Dongying Baomo Environmental Engineering Co., Ltd., the structural formula of functional monomer II is shown in Formula IV, M is Na, n and R are shown in the corresponding embodiments, and they are all purchased from Guangzhou Kedi Chemical Co., Ltd., and functional monomer III is shown in Formula V, and was purchased from Tianjin Xiens Biochemical Technology Co., Ltd.
所述丙烯酰胺共聚物采用现场水(矿化度150000mg/L)配制后测试其表观粘度和表面张力，与交联剂混合后注入岩心后，在150℃下稳定保持90天，然后测定封堵率。The acrylamide copolymer was prepared with on-site water (mineralization 150,000 mg/L) and its apparent viscosity and surface tension were tested. After being mixed with a cross-linking agent and injected into the core, it was stably maintained at 150° C. for 90 days and then the plugging rate was measured.
封堵率通过实验室岩心物模试验测定。具体地：The plugging rate is determined by laboratory core simulation test. Specifically:
封堵率的测定：将人造岩心装入岩心夹持器，先用水饱和后水驱测量渗透率(K1)，注入0.5PV丙烯酰胺聚合物和交联剂的混合溶液，在150℃下养护48h后，最后再水驱测定封堵后的渗透率(K2)，(1-K2/K1)×100％，即为封堵率。Determination of plugging rate: The artificial core is placed in the core holder, saturated with water and then water-flooded to measure the permeability (K1), a mixed solution of 0.5PV acrylamide polymer and cross-linking agent is injected, and after curing at 150°C for 48 hours, water-flooded to measure the permeability after plugging ( K2 ), (1- K2 / K1 )×100% is the plugging rate.
通过Brookfield粘度计62号转子进行测定丙烯酰胺共聚物溶液的表观粘度，测试温度为95℃；通过DCAT-21表面张力仪进行测定丙烯酰胺共聚物溶液的表面张力，测试温度为25℃。The apparent viscosity of the acrylamide copolymer solution was measured by a Brookfield viscometer with a No. 62 rotor at a test temperature of 95°C; the surface tension of the acrylamide copolymer solution was measured by a DCAT-21 surface tension meter at a test temperature of 25°C.
实施例1Example 1
1)将714g丙烯酰胺加入到保温聚合反应瓶中，加入去离子水3360g溶解配成水溶液，依次加入功能单体二(其中R为C5的直链烷基，n＝1)100.8g，功能单体三25.2g，EDTA-2Na0.09g，2-萘基硫脲1.68g，再加入氢氧化钠调节溶液pH至6.0，充分搅拌成为稳定的溶液；1) 714 g of acrylamide was added to a heat-insulating polymerization reaction bottle, 3360 g of deionized water was added to dissolve and prepare an aqueous solution, 100.8 g of functional monomer II (wherein R is a C5 straight-chain alkyl group, n=1), 25.2 g of functional monomer III, 0.09 g of EDTA-2Na, and 1.68 g of 2-naphthylthiourea were added in sequence, and sodium hydroxide was added to adjust the solution pH to 6.0, and the solution was fully stirred to form a stable solution;
2)在40℃下，向上述溶液中通高纯氮气除氧30分钟后，再加入1重量％的过硫酸钾水溶液84g和1重量％的亚硫酸氢钠水溶液42g，引发反应，继续通氮气五分钟后停止，密封后聚合反应8小时得到聚合物胶体；2) After passing high-purity nitrogen gas through the above solution at 40° C. for 30 minutes to deoxygenate, 84 g of a 1 wt % aqueous solution of potassium persulfate and 42 g of a 1 wt % aqueous solution of sodium bisulfite were added to initiate the reaction, and the nitrogen gas was continued to pass for five minutes before stopping. After sealing, the solution was polymerized for 8 hours to obtain a polymer colloid;
3)取出胶体，造粒后加入94.6g氢氧化钠粒碱混合均匀后，在85℃下进行水解反应3小时；3) Take out the colloid, granulate it, add 94.6g of sodium hydroxide granules, mix well, and then carry out hydrolysis reaction at 85°C for 3 hours;
4)取出胶粒再进行造粒、60℃下干燥至恒重、粉碎、过筛得到白色颗粒状丙烯酰胺共聚物NJD1。4) The granules were taken out and granulated, dried at 60° C. to constant weight, crushed, and sieved to obtain white granular acrylamide copolymer NJD1.
取现场水(矿化度150000mg/L)1000g，加入丙烯酰胺共聚物NJD1样品2.2g，搅拌后形成溶液，分别测试其表观粘度和表面张力，在上述溶液中加入0.043g交联剂甲醛混合均匀后注入岩心，在150℃下稳定保持90天，然后测定封堵率。Take 1000g of on-site water (mineralization 150000mg/L), add 2.2g of acrylamide copolymer NJD1 sample, stir to form a solution, test its apparent viscosity and surface tension respectively, add 0.043g of cross-linking agent formaldehyde to the above solution, mix well and inject into the core, keep it stable at 150℃ for 90 days, and then measure the plugging rate.
实施例2Example 2
1)将739.2g丙烯酰胺加入到保温聚合反应瓶中，加入去离子水3360g溶解配成水溶液，依次加入功能单体二(其中R为C7的直链烷基，n＝3)84.0g，功能单体三16.8g，EDTA-2Na 0.44，2-萘基硫脲0.62g，再加入氢氧化钠调节溶液pH至6.8，充分搅拌成为稳定的溶液；1) 739.2 g of acrylamide was added to a heat-insulated polymerization reaction bottle, 3360 g of deionized water was added to dissolve and prepare an aqueous solution, 84.0 g of functional monomer II (wherein R is a C7 straight-chain alkyl group, n=3), 16.8 g of functional monomer III, 0.44 of EDTA-2Na, and 0.62 g of 2-naphthylthiourea were added in sequence, and sodium hydroxide was added to adjust the pH of the solution to 6.8, and the solution was fully stirred to form a stable solution;
2)在35℃下，向上述溶液中通高纯氮气除氧30分钟后，再加入1重量％的过硫酸钾水溶液12.4g和1重量％的亚硫酸氢钠水溶液6.2g，引发反应，继续通氮气五分钟后停止，密封后聚合反应10小时得到聚合物胶体；2) After passing high-purity nitrogen gas through the above solution at 35° C. to deoxygenate for 30 minutes, 12.4 g of a 1 wt % aqueous solution of potassium persulfate and 6.2 g of a 1 wt % aqueous solution of sodium bisulfite were added to initiate the reaction, and the nitrogen gas was continued to pass for five minutes before stopping. After sealing, the solution was polymerized for 10 hours to obtain a polymer colloid;
3)取出胶体，造粒后加入104.1g氢氧化钠粒碱混合均匀后，在90℃下进行水解反应2小时；3) Take out the colloid, granulate it, add 104.1g of sodium hydroxide granules, mix well, and perform hydrolysis reaction at 90°C for 2 hours;
4)取出胶粒再进行造粒、60℃下干燥至恒重、粉碎、过筛得到白色颗粒状丙烯酰胺共聚物NJD2。4) The granules were taken out and granulated, dried at 60° C. to constant weight, crushed, and sieved to obtain white granular acrylamide copolymer NJD2.
取现场水(矿化度150000mg/L)1000g，加入丙烯酰胺共聚物NJD2样品4.2g，搅拌后形成溶液，分别测试其表观粘度和表面张力，在上述溶液中加入0.064g交联剂甲醛混合均匀后注入岩心，在150℃下稳定保持90天，然后测定封堵率。结果见表1。Take 1000g of on-site water (mineralization 150000mg/L), add 4.2g of acrylamide copolymer NJD2 sample, stir to form a solution, test its apparent viscosity and surface tension respectively, add 0.064g of cross-linking agent formaldehyde to the above solution, mix well and inject into the core, keep it stable at 150℃ for 90 days, and then measure the plugging rate. The results are shown in Table 1.
实施例3Example 3
1)将772.8g丙烯酰胺加入到保温聚合反应瓶中，加入去离子水3360g溶解配成水溶液，依次加入功能单体二(其中R为C9的直链烷基，n＝5)58.8g，功能单体三8.4g，EDTA-2Na 0.62，2-萘基硫脲0.88g，再加入氢氧化钠调节溶液pH至7.1，充分搅拌成为稳定的溶液；1) 772.8 g of acrylamide was added to a heat-insulating polymerization reaction bottle, 3360 g of deionized water was added to dissolve and prepare an aqueous solution, 58.8 g of functional monomer II (wherein R is a C9 straight-chain alkyl group, n=5), 8.4 g of functional monomer III, 0.62 g of EDTA-2Na, and 0.88 g of 2-naphthylthiourea were added in sequence, and sodium hydroxide was added to adjust the pH of the solution to 7.1, and the solution was fully stirred to form a stable solution;
2)在35℃下，向上述溶液中通高纯氮气除氧30分钟后，再加入1重量％的过硫酸钾水溶液40.8g和1重量％的亚硫酸氢钠水溶液20.4g，引发反应，继续通氮气五分钟后停止，密封后聚合反应9小时得到聚合物胶体；2) After passing high-purity nitrogen gas through the above solution at 35° C. to deoxygenate for 30 minutes, 40.8 g of a 1 wt % aqueous solution of potassium persulfate and 20.4 g of a 1 wt % aqueous solution of sodium bisulfite were added to initiate the reaction, and the nitrogen gas was continued to pass for five minutes before stopping. After sealing, the solution was polymerized for 9 hours to obtain a polymer colloid;
3)取出胶体，造粒后加入118.3g氢氧化钠粒碱混合均匀后，在90℃下进行水解反应2.5小时；3) Take out the colloid, granulate it, add 118.3g of sodium hydroxide granules, mix well, and perform hydrolysis reaction at 90°C for 2.5 hours;
4)取出胶粒再进行造粒、60℃下干燥至恒重、粉碎、过筛得到白色颗粒状丙烯酰胺共聚物NJD3。4) The granules were taken out and granulated, dried at 60° C. to constant weight, crushed, and sieved to obtain white granular acrylamide copolymer NJD3.
取现场水(矿化度150000mg/L)1000g，加入丙烯酰胺共聚物NJD3样品6.0g，搅拌后形成溶液，分别测试其表观粘度和表面张力，在上述溶液中加入0.082g交联剂甲醛混合均匀后注入岩心，在150℃下稳定保持90天，然后测定封堵率。结果见表1。1000g of on-site water (mineralization 150000mg/L) was taken, 6.0g of acrylamide copolymer NJD3 sample was added, and the solution was stirred to form a solution. The apparent viscosity and surface tension were tested respectively. 0.082g of cross-linking agent formaldehyde was added to the above solution and mixed evenly. After injection into the core, the solution was kept stable at 150°C for 90 days, and then the plugging rate was measured. The results are shown in Table 1.
实施例4Example 4
1)将785.4g丙烯酰胺加入到保温聚合反应瓶中，加入去离子水3360g溶解配成水溶液，依次加入功能单体二(其中R为C12的直链烷基，n＝4)42.0g，功能单体三12.6g，EDTA-2Na 0.78g，2-萘基硫脲1.25g，再加入氢氧化钠调节溶液pH至6.9，充分搅拌成为稳定的溶液；1) 785.4 g of acrylamide was added to a heat-insulating polymerization reaction bottle, 3360 g of deionized water was added to dissolve and prepare an aqueous solution, 42.0 g of functional monomer II (wherein R is a C12 straight-chain alkyl group, n=4), 12.6 g of functional monomer III, 0.78 g of EDTA-2Na, and 1.25 g of 2-naphthylthiourea were added in sequence, and sodium hydroxide was added to adjust the pH of the solution to 6.9, and the solution was fully stirred to form a stable solution;
2)在30℃下，向上述溶液中通高纯氮气除氧30分钟后，再加入1重量％的过硫酸钾水溶液64.4g和1重量％的亚硫酸氢钠水溶液32.2g，引发反应，继续通氮气五分钟后停止，密封后聚合反应10小时得到聚合物胶体；2) After passing high-purity nitrogen gas through the above solution at 30° C. to deoxygenate for 30 minutes, 64.4 g of a 1 wt % aqueous solution of potassium persulfate and 32.2 g of a 1 wt % aqueous solution of sodium bisulfite were added to initiate the reaction, and the nitrogen gas was continued to pass for five minutes before stopping. After sealing, the solution was polymerized for 10 hours to obtain a polymer colloid;
3)取出胶体，造粒后加入123.0g氢氧化钠粒碱混合均匀后，在85℃下进行水解反应3小时；3) Take out the colloid, granulate it, add 123.0g of sodium hydroxide granules, mix well, and then carry out hydrolysis reaction at 85°C for 3 hours;
4)取出胶粒再进行造粒、60℃下干燥至恒重、粉碎、过筛得到白色颗粒状丙烯酰胺共聚物NJD4。4) The granules were taken out and granulated, dried at 60° C. to constant weight, crushed, and sieved to obtain white granular acrylamide copolymer NJD4.
取现场水(矿化度150000mg/L)1000g，加入丙烯酰胺共聚物NJD4样品3.5g，搅拌后形成溶液，分别测试其表观粘度和表面张力，在上述溶液中加入0.058g交联剂甲醛混合均匀后注入岩心，在150℃下稳定保持90天，然后测定封堵率。结果见表1。Take 1000g of on-site water (mineralization 150000mg/L), add 3.5g of acrylamide copolymer NJD4 sample, stir to form a solution, test its apparent viscosity and surface tension respectively, add 0.058g of cross-linking agent formaldehyde to the above solution, mix well and inject into the core, keep it stable at 150℃ for 90 days, and then measure the plugging rate. The results are shown in Table 1.
实施例5Example 5
1)将819.0g丙烯酰胺加入到保温聚合反应瓶中，加入去离子水3360g溶解配成水溶液，依次加入功能单体二(其中R为C15的直链烷基，n＝6)16.8g，功能单体三4.2g，EDTA-2Na 0.84g，2-萘基硫脲1.04g，再加入氢氧化钠调节溶液pH至8.0，充分搅拌成为稳定的溶液；1) 819.0 g of acrylamide was added to a heat-insulating polymerization reaction bottle, 3360 g of deionized water was added to dissolve and prepare an aqueous solution, 16.8 g of functional monomer II (wherein R is a C15 straight-chain alkyl group, n=6), 4.2 g of functional monomer III, 0.84 g of EDTA-2Na, and 1.04 g of 2-naphthylthiourea were added in sequence, and sodium hydroxide was added to adjust the solution pH to 8.0, and the solution was fully stirred to form a stable solution;
2)在40℃下，向上述溶液中通高纯氮气除氧30分钟后，再加入1重量％的过硫酸钾水溶液31.2g和1重量％的亚硫酸氢钠水溶液15.6g，引发反应，继续通氮气五分钟后停止，密封后聚合反应8.5小时得到聚合物胶体；2) After passing high-purity nitrogen gas through the above solution at 40° C. to deoxygenate for 30 minutes, 31.2 g of a 1 wt % aqueous solution of potassium persulfate and 15.6 g of a 1 wt % aqueous solution of sodium bisulfite were added to initiate the reaction, and the nitrogen gas was continued to pass for five minutes before stopping. After sealing, the solution was polymerized for 8.5 hours to obtain a polymer colloid;
3)取出胶体，造粒后加入118.5g氢氧化钠粒碱混合均匀后，在80℃下进行水解反应3小时；3) Take out the colloid, granulate it, add 118.5g of sodium hydroxide granules, mix well, and then carry out hydrolysis reaction at 80°C for 3 hours;
4)取出胶粒再进行造粒、60℃下干燥至恒重、粉碎、过筛得到白色颗粒状丙烯酰胺共聚物NJD5。4) The granules were taken out and granulated, dried at 60° C. to constant weight, crushed, and sieved to obtain white granular acrylamide copolymer NJD5.
取现场水(矿化度150000mg/L)1000g，加入丙烯酰胺共聚物NJD5样品2.5g，搅拌后形成溶液，分别测试其表观粘度和表面张力，在上述溶液中加入0.059g交联剂甲醛混合均匀后注入岩心，在150℃下稳定保持90天，然后测定封堵率。结果见表1。Take 1000g of on-site water (mineralization 150000mg/L), add 2.5g of acrylamide copolymer NJD5 sample, stir to form a solution, test its apparent viscosity and surface tension respectively, add 0.059g of cross-linking agent formaldehyde to the above solution, mix well and inject into the core, keep it stable at 150℃ for 90 days, and then measure the plugging rate. The results are shown in Table 1.
实施例6Example 6
按照实施例3的方法制备聚合物以及可动性凝胶，不同的是，单体的配比不同，其中丙烯酰胺的用量为814.8g，功能单体二的用量为16.8g，功能单体三的用量为8.4g，即丙烯酰胺质量比为97％，功能单体二质量比为2％，功能单体三质量比为1％，得到丙烯酰胺共聚物NJD6。结果见表1。The polymer and the movable gel were prepared according to the method of Example 3, except that the ratio of the monomers was different, wherein the amount of acrylamide was 814.8 g, the amount of functional monomer II was 16.8 g, and the amount of functional monomer III was 8.4 g, that is, the mass ratio of acrylamide was 97%, the mass ratio of functional monomer II was 2%, and the mass ratio of functional monomer III was 1%, to obtain acrylamide copolymer NJD6. The results are shown in Table 1.
实施例7Example 7
按照实施例3的方法制备聚合物以及可动性凝胶，不同的是，功能单体二中R为C9的直链烷基替换为C14的直链烷基，得到丙烯酰胺共聚物NJD7。结果见表1。The polymer and the movable gel were prepared according to the method of Example 3, except that the linear alkyl group R of C9 in the functional monomer 2 was replaced by a linear alkyl group of C14, to obtain acrylamide copolymer NJD7. The results are shown in Table 1.
实施例8Example 8
按照实施例3的方法制备聚合物，不同的是，以2,5-二硫代联二脲为促进剂替代实施例3中的2-萘基硫脲，得到丙烯酰胺共聚物NJD8。结果见表1。The polymer was prepared according to the method of Example 3, except that 2,5-dithiodiurea was used as the accelerator to replace the 2-naphthylthiourea in Example 3, to obtain acrylamide copolymer NJD8. The results are shown in Table 1.
对比例1Comparative Example 1
按照实施例3的方法制备聚合物，不同的是，以N-苯基马来酰亚胺替代实施例2中的功能单体三，得到丙烯酰胺共聚物D1。结果见表1。The polymer was prepared according to the method of Example 3, except that N-phenylmaleimide was used to replace the functional monomer three in Example 2, to obtain acrylamide copolymer D1. The results are shown in Table 1.
对比例2Comparative Example 2
按照实施例3的方法制备聚合物，不同的是，不加入功能单体三，得到丙烯酰胺共聚物D2。结果见表1。The polymer was prepared according to the method of Example 3, except that the functional monomer 3 was not added, to obtain acrylamide copolymer D2. The results are shown in Table 1.
表1Table 1
应当注意的是，以上所述的实施例仅用于解释本发明，并不构成对本发明的任何限制。通过参照典型实施例对本发明进行了描述，但应当理解为其中所用的词语为描述性和解释性词汇，而不是限定性词汇。可以按规定在本发明权利要求的范围内对本发明作出修改，以及在不背离本发明的范围和精神内对本发明进行修订。尽管其中描述的本发明涉及特定的方法、材料和实施例，但是并不意味着本发明限于其中公开的特定例，相反，本发明可扩展至其他所有具有相同功能的方法和应用。It should be noted that the embodiments described above are only used to explain the present invention and do not constitute any limitation to the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory words, rather than restrictive words. The present invention may be modified as specified within the scope of the claims of the present invention, and the present invention may be revised without departing from the scope and spirit of the present invention. Although the present invention described therein relates to specific methods, materials and embodiments, it does not mean that the present invention is limited to the specific examples disclosed therein, on the contrary, the present invention can be extended to all other methods and applications with the same functions.
本说明书提到的所有出版物、专利申请、专利和其它参考文献全都通过引用并入本文。除非另有定义，本说明书所用的所有技术和科学术语都具有本领域技术人员常规理解的含义。在有冲突的情况下，以本说明书的定义为准。All publications, patent applications, patents and other references mentioned in this specification are incorporated herein by reference. Unless otherwise defined, all technical and scientific terms used in this specification have the meanings conventionally understood by those skilled in the art. In the event of a conflict, the definition in this specification shall prevail.
当本说明书以词头“本领域技术人员公知”、“现有技术”或其类似用语来导出材料、物质、方法、步骤、装置或部件等时，该词头导出的对象涵盖本申请提出时本领域常规使用的那些，但也包括目前还不常用，却将变成本领域公认为适用于类似目的的那些。When this specification uses the prefix "well-known to those skilled in the art", "prior art" or similar terms to introduce materials, substances, methods, steps, devices or components, etc., the objects introduced by the prefix cover those commonly used in the art when this application is filed, but also include those that are not commonly used at present but will become recognized in the art as being suitable for similar purposes.
在本申请文件中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。在下文中，各个技术方案之间原则上可以相互组合而得到新的技术方案，这也应被视为在本文中具体公开。The endpoints and any values of the scope disclosed in the present application document are not limited to the precise scope or value, and these scopes or values should be understood to include values close to these scopes or values. For numerical ranges, between the endpoint values of each scope, between the endpoint values of each scope and a separate point value, and between separate point values, one or more new numerical ranges can be combined with each other, and these numerical ranges should be considered as specifically disclosed in this article. Hereinafter, in principle, each technical solution can be combined with each other to obtain a new technical solution, which should also be considered as specifically disclosed in this article.
在本说明书的上下文中，除了明确说明的内容之外，未提到的任何事宜或事项均直接适用本领域已知的那些而无需进行任何改变。In the context of the present specification, any matters or items not mentioned are directly applicable to those known in the art without any changes except those explicitly stated.
而且，本文描述的任何实施方式均可以与本文描述的一种或多种其他实施方式自由结合，由此而形成的技术方案或技术思想均视为本发明原始公开或原始记载的一部分，而不应被视为是本文未曾披露或预期过的新内容，除非本领域技术人员认为该结合是明显不合理的。Moreover, any embodiment described in this document may be freely combined with one or more other embodiments described in this document, and the technical solutions or technical ideas formed thereby are deemed to be part of the original disclosure or original record of the present invention, and should not be regarded as new content that has not been disclosed or anticipated in this document, unless a person skilled in the art considers that the combination is obviously unreasonable.
Claims (12)
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| Application Number | Priority Date | Filing Date | Title |
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| CN202310195031.6A CN118546292A (en) | 2023-02-27 | 2023-02-27 | Polyacrylamide copolymer for displacement material and preparation method thereof, displacement material and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202310195031.6A CN118546292A (en) | 2023-02-27 | 2023-02-27 | Polyacrylamide copolymer for displacement material and preparation method thereof, displacement material and application thereof |
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| CN (1) | CN118546292A (en) |
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