CN115677923B - Pre-crosslinked gel particle plugging agent and preparation method and application thereof - Google Patents
Pre-crosslinked gel particle plugging agent and preparation method and application thereof Download PDFInfo
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- CN115677923B CN115677923B CN202211317032.5A CN202211317032A CN115677923B CN 115677923 B CN115677923 B CN 115677923B CN 202211317032 A CN202211317032 A CN 202211317032A CN 115677923 B CN115677923 B CN 115677923B
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- crosslinked gel
- plugging agent
- gel particle
- hectorite
- acrylamide
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- 239000007863 gel particle Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 53
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 claims abstract description 85
- 229910000271 hectorite Inorganic materials 0.000 claims abstract description 83
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 55
- 239000006185 dispersion Substances 0.000 claims abstract description 52
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000178 monomer Substances 0.000 claims abstract description 36
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims abstract description 31
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 30
- 125000000129 anionic group Chemical group 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 20
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 19
- -1 amino silicate Chemical compound 0.000 claims abstract description 18
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 12
- 150000000703 Cerium Chemical class 0.000 claims abstract description 11
- 230000002378 acidificating effect Effects 0.000 claims abstract description 8
- 230000001105 regulatory effect Effects 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 239000012071 phase Substances 0.000 claims description 47
- 238000003756 stirring Methods 0.000 claims description 27
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 claims description 21
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 claims description 21
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 17
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 16
- HKVFISRIUUGTIB-UHFFFAOYSA-O azanium;cerium;nitrate Chemical compound [NH4+].[Ce].[O-][N+]([O-])=O HKVFISRIUUGTIB-UHFFFAOYSA-O 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 13
- 239000008346 aqueous phase Substances 0.000 claims description 13
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims description 5
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 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
- 150000002148 esters Chemical class 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 4
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 claims description 4
- 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 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 3
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 claims description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- PGJHGXFYDZHMAV-UHFFFAOYSA-K azanium;cerium(3+);disulfate Chemical compound [NH4+].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O PGJHGXFYDZHMAV-UHFFFAOYSA-K 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 3
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- 229920000136 polysorbate Polymers 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 16
- 239000000243 solution Substances 0.000 description 39
- 239000002245 particle Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 16
- 230000032683 aging Effects 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 13
- 230000001276 controlling effect Effects 0.000 description 11
- 230000007774 longterm Effects 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 230000000903 blocking effect Effects 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 239000000839 emulsion Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 125000003368 amide group Chemical group 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 238000004945 emulsification Methods 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- 229940094522 laponite Drugs 0.000 description 4
- XCOBTUNSZUJCDH-UHFFFAOYSA-B lithium magnesium sodium silicate Chemical group [Li+].[Li+].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 XCOBTUNSZUJCDH-UHFFFAOYSA-B 0.000 description 4
- 238000012703 microemulsion polymerization Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 238000012688 inverse emulsion polymerization Methods 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 229920002401 polyacrylamide Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000008398 formation water Substances 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 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 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- IPGANOYOHAODGA-UHFFFAOYSA-N dilithium;dimagnesium;dioxido(oxo)silane Chemical compound [Li+].[Li+].[Mg+2].[Mg+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O IPGANOYOHAODGA-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical group O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- 239000012802 nanoclay Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical group O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
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- 230000000717 retained effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
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Abstract
The invention belongs to the technical field of oilfield chemistry, and particularly relates to a novel pre-crosslinked gel particle plugging agent, and a preparation method and application thereof. The preparation method of the novel pre-crosslinked gel particle plugging agent provided by the invention comprises the following steps: dissolving an emulsifier in white oil to obtain an oil phase; (2) Dissolving hectorite and 2-acrylamide-2-methylpropanesulfonic acid in water, and dropwise adding an ethanol solution of amino silicate under an acidic condition to obtain a hectorite nano-dispersion; (3) Dissolving acrylamide, N-dimethylacrylamide, an anionic monomer, N' -methylenebisacrylamide and persulfate in water, and regulating pH to be acidic to obtain a water phase; (4) Sequentially dripping the hectorite nano-dispersion liquid and the water phase into the oil phase, and introducing N after the dripping is finished 2 Removing oxygen, and adding cerium salt to obtain the novel pre-crosslinked gel particle plugging agent. The size of the pre-crosslinked gel particle type plugging agent is in the micro-nano level, so that the plugging agent can enter the deep part of a stratum, and a better profile control and water plugging effect is realized.
Description
Technical Field
The invention belongs to the technical field of oilfield chemistry, and particularly relates to a novel pre-crosslinked gel particle plugging agent, and a preparation method and application thereof.
Background
Petroleum is one of the indispensable non-renewable resources in modern society, and the exploitation and utilization of petroleum plays an important role in the development of national economy. With the continuous progress of oil exploitation, most of developed oil fields in China enter a high water content period at present. Not only does this produced water corrode the production lines, but it also occupies a large amount of construction sites (especially for offshore platforms) if not handled in time, and in addition, excessive produced water can lead to high water content in the well, ultimately significantly affecting oil production. The pre-crosslinked gel particles are one of the plugging agents which are used for improving the water absorption profile currently, and are the polymerization products with three-dimensional network structures formed by monomers under the action of the crosslinking agent. The pre-crosslinked gel contains a large number of carboxyl, amido and other water absorbing groups, can absorb water with the weight of several times or even tens times of the self weight, and has good water retention performance. The particles are expanded by water absorption to form a dispersion elastomer with certain size and strength, can be retained in a body layer, can deform under the action of pressure and the like, and migrate into stratum pores to achieve the effects of blocking a hypertonic channel, improving sweep absorption, reducing water production and the like.
However, the strength of the conventional acrylamide polymer pre-crosslinked gel is low after water absorption, shearing and crushing are easy to generate, and the plugging adjusting effect is poor; in addition, under the condition of a high-temperature high-salt extreme oil reservoir, amide groups in gel molecules are gradually hydrolyzed into carboxyl groups, a cross-linked structure is gradually destroyed, the mechanical properties of the gel molecules are further deteriorated, and even the plugging regulating function is completely lost. Therefore, the long-term stability of the pre-crosslinked gel under high temperature and high salt is improved, the application field is enlarged, and the need is felt. In order to improve the temperature resistance and salt resistance of the pre-crosslinked gel under the long-term condition, functional units such as sulfonic acid groups, pyrrolidone groups, caprolactam groups, phenyl groups, cationic groups and the like are often introduced into the molecular structure of the acrylamide polymer, so that the hydration and degradation resistance of polymer molecules under the high-temperature and high-salt condition are improved.
Chinese patent No. 112279963A discloses a temperature-resistant salt-resistant multi-component copolymerization pre-crosslinked gel particle, a preparation method and application thereof, wherein acrylamide and 2 acrylamide 2 methylpropanesulfonic acid are used as monomers, N, N dimethylacrylamide is used as a crosslinking agent, potassium persulfate ionic liquid is used as an initiator, after aqueous solution pre-polymerization, nano clay is added for reaction for 3-4 hours, then the colloid temperature is raised to 80-85 ℃ for hydrolysis for 1.5-2 hours, a polymerized sample is taken out, and the polymerized sample is dried and crushed to obtain the pre-crosslinked gel particle, so that the obtained product can be used for profile control and water shutoff as well as improvement of recovery ratio.
The Chinese patent No. 104119472A discloses an active pre-crosslinked gel particle, which is prepared by taking acrylamide, an anionic compound (acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid and the like), 3-alkyl-4-styrene fatty alcohol polyoxyethylene ether sodium sulfonate as monomers, N, N-methylene bisacrylamide as a cross-linking agent, tetramethyl ethylenediamine, persulfate, azo compound, sulfite and the like as an initiator, introducing nitrogen for 30min within the range of 21-22 ℃ to polymerize, preserving the temperature for 5h after the temperature of a reaction system is not increased any more, cutting, granulating, drying, crushing and screening gel block products to obtain the active pre-crosslinked gel particle, wherein the prepared product has certain interfacial activity and emulsifying property and can be used as a profile control agent.
The above patents all realize the promotion of the temperature resistance and the salt resistance of the pre-crosslinked gel by introducing functional units, and in the process, the following defects often exist: the preparation process of the functional monomer is complicated, and the subsequent operations such as purification and the like exist, so that the product cost is increased; compared with acrylamide monomers, the functional monomers have higher price, poorer polymerization activity and lower conversion rate, are difficult to fully utilize in the polymerization process, and have great difference in molecular structures of polymers generated in the initial stage and the end stage of the polymerization reaction; as an organic component, only through the change of the structures of the functional monomer and the cross-linking agent, the gel has bottlenecks in the aspects of temperature resistance, salt resistance, mechanical properties and the like, and cannot be broken through further.
Disclosure of Invention
The invention aims at overcoming the defects of the prior art and provides a novel pre-crosslinked gel particle plugging agent, and a preparation method and application thereof.
Specifically, the preparation method of the novel pre-crosslinked gel particle type plugging agent provided by the invention comprises the following steps:
(1) Dissolving an emulsifier in white oil to obtain an oil phase;
(2) Dissolving hectorite and 2-acrylamide-2-methylpropanesulfonic acid in water to obtain a hectorite nano-dispersion system; under an acidic condition, dripping an ethanol solution of amino silicate into the hectorite nano-dispersion system, and continuously stirring after the dripping is finished to obtain a hectorite nano-dispersion;
(3) Dissolving acrylamide, N-dimethylacrylamide, an anionic monomer, N' -methylenebisacrylamide and persulfate in water, and regulating pH to be acidic to obtain a water phase;
(4) Sequentially dripping the hectorite nano-dispersion liquid and the water phase into the oil phase, stirring while dripping, and introducing N after dripping is finished 2 Removing oxygen, adding cerium salt, reacting at 0-30 ℃ for 1-12 h, heating to 50-85 ℃ and reacting for 0.5-8 h to obtain the novel pre-crosslinked gel particle plugging agent.
The preparation method of the novel pre-crosslinked gel particle type plugging agent comprises the steps of preparing an emulsifier by using Span 80, OP 10 and Tween 85; the white oil is one of 3# white oil, 5# white oil, 7# white oil and 10# white oil.
The mass ratio of Span 80, OP 10, tween85 and white oil is 1 (0.01-0.2) (0.01-0.1) (5-80).
The mass ratio of Span 80, OP 10, tween85 and white oil is 1 (0.03-0.15) (0.01-0.07) (5-35).
In the step (2), the concentration of the ethanol solution of the amino silicate is 400-600 g/L; the mass ratio of the hectorite to the ethanol solution of the 2-acrylamide-2-methylpropanesulfonic acid and the aminosilate to the water is 1 (2-8) (0.01-1) (10-100),
the mass ratio of the hectorite, the 2-acrylamide-2-methylpropanesulfonic acid and the ethanol solution of the aminosilane ester to the water is 1 (2-4) (0.3-1) (15-70).
The preparation method of the novel pre-crosslinked gel particle plugging agent comprises the step of preparing the aminosilate from one of 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3- (2-aminoethylamino) propyl trimethoxysilane and 3- (2-aminoethylamino) propyl triethoxysilane.
The mass ratio of the acrylamide, the N, N-dimethylacrylamide, the anionic monomer, the N, N' -methylenebisacrylamide and the persulfate is 1 (0.01-0.35) (0.01-10) (0.0005-0.004) (0.0001-0.005); wherein the ratio of the total mass of the acrylamide, the N, N-dimethylacrylamide and the anionic monomer to the mass of water is 1 (0.5-6).
The mass ratio of the acrylamide, the N, N-dimethylacrylamide, the anionic monomer, the N, N' -methylenebisacrylamide and the persulfate is 1 (0.05-0.25) (0.1-5) (0.0005-0.0025) (0.0005-0.005); wherein the ratio of the total mass of the acrylamide, the N, N-dimethylacrylamide and the anionic monomer to the mass of water is 1 (0.5-4).
The preparation method of the novel pre-crosslinked gel particle plugging agent comprises the steps that the anionic monomer is one or a mixture of more than two of acrylic acid, methacrylic acid, maleic acid, itaconic acid, 2-acrylamide-2-methylpropanesulfonic acid, sodium vinylsulfonate, sodium styrenesulfonate and sodium allylsulfonate; the persulfate is one of potassium persulfate, sodium persulfate and ammonium persulfate; the cerium salt is one of ammonium cerium nitrate and ammonium cerium sulfate.
In the step (4), the mass ratio of the oil phase to the hectorite nano-dispersion to the aqueous phase solution is 1 (0.05-0.5) (0.3-2); the mass ratio of the hectorite nano-dispersion liquid and the ammonium cerium nitrate is 1 (0.001-0.02).
In the step (4), the mass ratio of the oil phase to the hectorite nano-dispersion to the aqueous phase solution is 1 (0.1-0.5) (0.5-1.5); the mass ratio of the hectorite nano-dispersion liquid and the ammonium cerium nitrate is 1 (0.001-0.012).
On the other hand, the invention also provides a novel pre-crosslinked gel particle type plugging agent, which is prepared by the preparation method of the novel pre-crosslinked gel particle type plugging agent.
In still another aspect, the invention also provides application of the novel pre-crosslinked gel particle plugging agent in offshore oilfield exploitation.
The technical scheme of the invention has the following beneficial effects:
(1) In the preparation method of the novel pre-crosslinked gel particle plugging agent, hectorite forms an inorganic-organic composite structure through the interaction between hectorite and polymer molecules, so that the long-term temperature resistance and salt resistance of polymer components are improved, and the long-term stability of gel particles under the condition of a high-temperature high-salt oil reservoir is improved;
(2) According to the preparation method of the novel pre-crosslinked gel particle type plugging agent, an amino silicate component is introduced between hectorite particles and polymer molecular chains, the interaction between the hectorite particles and the polymer can be further enhanced through the hydrogen bond and the electrostatic effect between amino groups, amide groups and sulfonic groups, in addition, in the aging process, an inorganic-organic covalent structure is formed between the amino groups and the amide groups through condensation reaction, so that the long-term stability of a system is enhanced;
(3) In the preparation method of the novel pre-crosslinked gel particle type plugging agent, the polymerization high-temperature reaction section initiates the polymerization of residual monomers by utilizing the chain transfer performance of methyl on N, N-dimethylacrylamide under the action of a peroxide type initiator, so that a novel self-crosslinked structure is generated, the thermal stability of the crosslinked structure is good, and the long-term stability of gel particles can be improved;
(4) According to the preparation method of the novel pre-crosslinked gel particle type plugging agent, the particle size of gel particles obtained through inverse emulsion polymerization has a certain particle size distribution range, and stratum with certain heterogeneity can be plugged;
(5) The novel pre-crosslinked gel particle type plugging agent provided by the invention is provided with a rigid inorganic component and a branched polymer component initiated by amino and cerium salt, so that gel particles have better mechanical properties and deformability;
(6) The novel pre-crosslinked gel particle type plugging agent has good compatibility with sandstone stratum and conventional oil displacement auxiliary agents, and in addition, the size of the novel pre-crosslinked gel particle type plugging agent is in the micro-nano level, so that the novel pre-crosslinked gel particle type plugging agent can enter the deep part of the stratum to realize better profile control and water plugging effects;
(7) The invention has the advantages of easily obtained raw materials, simple and safe process, low production cost, simple post-treatment of the product, easy realization of continuous production, convenient product storage and use, and meeting the requirements of environmental protection.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention.
FIG. 1 is an infrared spectrum of the samples of example 1 and comparative example 1;
FIG. 2 shows the results of thermogravimetric analysis of the samples of example 1 and comparative example 1;
FIG. 3 is a profile of the sample of example 1.
Detailed Description
The present invention will be described in detail with reference to the following embodiments for a full understanding of the objects, features, and effects of the present invention. The process of the present invention is carried out by methods or apparatus conventional in the art, except as described below. The following terms have the meanings commonly understood by those skilled in the art unless otherwise indicated.
The terms "the," "one," and "the" as used herein do not denote a limitation of quantity, but rather denote the presence of at least one of the referenced item. The terms "preferred," "more preferred," and the like refer to embodiments of the invention that may provide certain benefits in certain circumstances. However, other embodiments may be preferred under the same or other circumstances. Furthermore, the recitation of one or more embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
When a range of values is disclosed herein, the range is considered to be continuous and includes both the minimum and maximum values for the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range description features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to include any and all subranges subsumed therein.
The hectorite is also called magnesium lithium silicate, and English name is Laponite, is an artificially synthesized octahedral layered colloid material, has extremely strong colloid forming performance in a water system, and has excellent thixotropic property, dispersibility, suspension property and thickening property.
Hectorite is a layered hectorite clay synthesized from inorganic salt, and has good monodispersity, a thickness of about 1nm, a diameter of about 30nm, and a chemical formula of [ (Si) 8 (Mg 5.34 Li 0.66 )O 20 (OH) 4 ]Na 0.66 The hectorite particles are negatively charged. In the aqueous solution, the hectorite has a large specific surface area, and the surface contains a large amount of oxygen atoms and hydroxyl groups, so that the hectorite has good hydration capability in the aqueous solution, and in addition, the hectorite has good interaction with groups such as amide groups, carboxyl groups, sulfonic groups and the like in the acrylamide polymer molecules.
However, the dispersion properties of the hectorite nanosystems are very sensitive to changes in external conditions, when there is a small amount of salt or polymer in the solution, the hectorite nanoparticles will agglomerate and settle; research shows that after the hectorite particles adsorb 2-acrylamide-2-methylpropanesulfonic acid, the dispersibility of the hectorite particles is obviously improved, and the nano dispersion state can be maintained in polymer and ionic monomer solutions, so that the inorganic-organic compound with nano hectorite components can be prepared.
Based on the method, the 2-acrylamide-2-methylpropanesulfonic acid modified hectorite nano-particles are selected to prepare the micro-nano inorganic-organic composite pre-crosslinked gel particles. The product has good high-temperature and long-term aging resistance, better mechanical property and deformation capability, can enter the deep part of a stratum, realizes better profile control and water shutoff effects, and shows excellent shutoff effects on sandstone cores.
Specifically, the preparation method of the novel pre-crosslinked gel particle plugging agent provided by the invention comprises the following steps:
(1) Dissolving an emulsifier in white oil to obtain an oil phase;
(2) Dissolving hectorite and 2-acrylamide-2-methylpropanesulfonic acid in water to obtain a hectorite nano-dispersion system; under an acidic condition, dripping an ethanol solution of amino silicate into the hectorite nano-dispersion system, and continuously stirring after the dripping is finished to obtain a hectorite nano-dispersion;
(3) Dissolving acrylamide, N-dimethylacrylamide, an anionic monomer, N' -methylenebisacrylamide and persulfate in water, and regulating pH to be acidic to obtain a water phase;
(4) Sequentially dripping the hectorite nano-dispersion liquid and the water phase into the oil phase, stirring while dripping, and introducing N after dripping is finished 2 Removing oxygen, adding cerium salt, reacting at 0-30 ℃ for 1-12 h, heating to 50-85 ℃ and reacting for 0.5-8 h to obtain the novel pre-crosslinked gel particle plugging agent.
The preparation method of the novel pre-crosslinked gel particle plugging agent comprises the steps of selecting 2-acrylamide-2-methylpropanesulfonic acid modified hectorite nano particles to prepare a nano dispersion system which can exist stably in high polymer and salt solution, then further modifying the hectorite nano particles by utilizing amino silicate to prepare hectorite particles with a certain amount of amino groups on the surfaces, and preparing micro-nano inorganic-organic compound pre-crosslinked gel particles by using inverse emulsion polymerization on the basis of the nano dispersion system under the initiation of cerium salt and persulfate by using modified hectorite, acrylamide, N-dimethylacrylamide, anionic monomers and N, N' -methylenebisacrylamide. Through tests, the product has good high-temperature long-term aging resistance and shows good plugging effect on sandstone cores.
In some preferred embodiments, the method of preparing the novel pre-crosslinked gel particulate plugging agent of the present invention comprises:
(1) Preparation of oil phase
Emulsifying agents Span 80, OP 10 and Tween85 are dissolved in white oil to obtain an oil phase. Wherein the mass ratio of Span 80, OP 10, tween85 and white oil in the oil phase is 1 (0.01-0.2), 0.01-0.1, 5-80, preferably 1 (0.03-0.15), 0.01-0.07 and 5-35.
White oil is the most commonly used oil phase for the industrial reverse emulsion products, and has the advantages of low cost, low toxicity, nonflammability, difficult volatilization and the like. The invention selects low viscosity white oil, such as: the 3# white oil, the 5# white oil, the 7# white oil and the 10# white oil can ensure good emulsion stability, good heat dissipation in the reaction process and good temperature control.
(2) Preparation of hectorite nano dispersion liquid
Dissolving hectorite and 2-acrylamide-2-methylpropanesulfonic acid in water to obtain a hectorite nano-dispersion system; and (3) dropwise adding the ethanol solution of the aminosilate into the hectorite nano-dispersion system, stirring while dropwise adding, controlling the pH to be 1-6 (preferably 3-6), and continuously stirring for 30min after the dropwise adding is finished to obtain the hectorite nano-dispersion.
In the process of preparing the hectorite nano-dispersion liquid, the amino silicate reacts on the surface of the hectorite to form a Si-O-Si structure.
Preferably, the hectorite and the 2-acrylamide-2-methylpropanesulfonic acid are added into water and then stirred for 24 hours, so that the hectorite is fully hydrated and dispersed, and in addition, the 2-acrylamide-2-methylpropanesulfonic acid is fully adsorbed on the surfaces of the hectorite particles, so that the dispersion stability of the hectorite particles in the subsequent mixing and reaction processes is improved.
Wherein the concentration of the ethanol solution of the amino silicate is 400-600g/L, preferably 500g/L.
Wherein the mass ratio of the hectorite to the ethanol solution of the 2-acrylamide-2-methylpropanesulfonic acid and the aminosilate ester to the water is 1 (2-8) (0.01-1) (10-100). When the amount of the 2-acrylamide-2-methylpropanesulfonic acid is within the protection range of the invention, the good dispersibility of the hectorite nanoparticles in the subsequent reaction process can be ensured; when the amount of the amino silicate is within the protection range of the invention, the surface of the hectorite particles can be ensured to have enough amino groups, and then the amino groups and monomers such as acrylamide are subjected to graft polymerization to further form good crosslinking. Preferably, the mass ratio of the hectorite, the 2-acrylamide-2-methylpropanesulfonic acid and the ethanol solution of the amino silicate to the water is 1 (2-4) (0.3-1) (15-70).
Wherein the amino silicate is one of 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3- (2-aminoethylamino) propyl trimethoxysilane and 3- (2-aminoethylamino) propyl triethoxysilane.
(3) Preparation of aqueous phase
Acrylamide, N-dimethylacrylamide, anionic monomer, N' -methylenebisacrylamide and persulfate are dissolved in water, and the pH is regulated to 1-6 (preferably 3-5) to obtain a water phase.
Wherein the mass ratio of the acrylamide to the N, N-dimethylacrylamide to the anionic monomer to the N, N '-methylenebisacrylamide to the persulfate is 1 (0.01-0.35), the mass ratio of the acrylamide to the N, N' -methylenebisacrylamide to the persulfate is 0.01-10, the mass ratio of the acrylamide to the N, N-dimethylacrylamide to the persulfate is 0.0005-0.004, the mass ratio of the total mass of the acrylamide to the N, N-dimethylacrylamide to the water is 1 (0.5-6). When the amount of persulfate is within the scope of the present invention, the conversion of the monomer can be ensured, and furthermore, the reaction process is not too vigorous. When the amount of N, N' -methylene bisacrylamide is within the protection scope of the invention, a cross-linked structure can be formed, and the viscoelasticity of the gel is good; the proportion of acrylamide, N-dimethylacrylamide and anionic monomers can ensure good salt resistance and long-term aging resistance of the gel only within the scope of the invention.
Preferably, the mass ratio of the acrylamide to the N, N-dimethylacrylamide to the anionic monomer to the N, N' -methylenebisacrylamide to the persulfate is 1 (0.05-0.25): (0.1-5): (0.0005-0.0025): (0.0005-0.005); the ratio of the total mass of the acrylamide, the N, N-dimethylacrylamide and the anionic monomer to the mass of water is 1 (0.5-4).
Wherein the anionic monomer is one or more than two of acrylic acid, methacrylic acid, maleic acid, itaconic acid, 2-acrylamido-2-methylpropanesulfonic acid, sodium vinylsulfonate, sodium styrenesulfonate and sodium allylsulfonate; the persulfate is one of potassium persulfate, sodium persulfate and ammonium persulfate.
(4) Preparation of novel pre-crosslinked gel particle plugging agent
Adding the oil phase into a three-necked glass bottle provided with a stirrer, a condenser tube and a thermometer, sequentially dripping the hectorite nano-dispersion liquid and the water phase into the oil phase, and rapidly stirring while dripping to facilitate system emulsification, and introducing N under stirring after dripping 2 Removing oxygen for 30min, adding cerium salt, reacting for 1-12 h at 0-30 ℃, heating to 50-85 ℃ and reacting for 0.5-8 h to obtain the novel pre-crosslinked gel particle plugging agent.
Specifically, a polymerization reaction using cerium salt/amino group as an initiator mainly occurs at 0-30 ℃; the monomer polymerization mainly takes potassium persulfate as initiator at 50-85 ℃.
Wherein the cerium salt is one of ammonium cerium nitrate and ammonium cerium sulfate.
Wherein the mass ratio of the oil phase to the hectorite nano-dispersion to the aqueous phase solution is 1 (0.05-0.5) to 0.3-2. Through practice, when the amount of the hectorite nano-dispersion liquid is larger than the maximum value of the invention, the hectorite is easy to agglomerate, and when the content of the hectorite nano-dispersion liquid is smaller than the minimum value of the invention, the inorganic-organic gel structure cannot be achieved, and the mechanical property, the ageing resistance and the like of the gel are influenced; when the oil-water ratio is in the protection range of the invention, the stability of the emulsion system, the stable reaction process and the size of the formed gel are ensured to be in the required range. Preferably, the mass ratio of the oil phase to the hectorite nano-dispersion to the aqueous phase solution is 1 (0.1-0.5) (0.5-1.5).
Wherein the mass ratio of the hectorite nano-dispersion liquid and the ammonium cerium nitrate is 1 (0.001-0.02). Through practice, when the dosage of the ammonium cerium nitrate is smaller than the minimum value of the invention, the formed grafted structure is insufficient; when the amount of ceric ammonium nitrate is more than the maximum value of the present invention, the reaction is too severe, and the production cost is increased. Preferably, the mass ratio of the hectorite nano-dispersion liquid to the ammonium cerium nitrate is 1: (0.001-0.012).
Preferably, after cerium salt is added, the reaction system is placed at 5-20 ℃ for reaction for 1-8 hours, and then the temperature is raised to 65-80 ℃ for reaction for 0.5-5 hours, so that the novel pre-crosslinked gel particle type plugging agent is obtained.
On the other hand, the invention also provides a novel pre-crosslinked gel particle type plugging agent, which is prepared by the preparation method of the novel pre-crosslinked gel particle type plugging agent.
Through practice, the novel pre-crosslinked gel particle plugging agent disclosed by the invention has good high-temperature and long-term aging resistance, better mechanical property and deformation capacity, can enter the deep part of a stratum, realizes better profile control and water plugging effects, and shows excellent plugging effects on sandstone cores.
In still another aspect, the invention also provides application of the novel pre-crosslinked gel particle plugging agent in offshore oilfield exploitation.
The novel pre-crosslinked gel particle type plugging agent is anionic, has good compatibility with sandstone stratum and conventional oil displacement auxiliary agents, has a size of micro-nano level, can enter the deep part of stratum, and realizes better profile control and water plugging effects.
Examples
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods without specific conditions noted in the following examples follow conventional methods and conditions. The starting materials used in the following examples are all conventionally commercially available.
Example 1:
a preparation method of a pre-crosslinked gel particle type plugging agent comprises the following steps.
(1) Preparation of oil phase
12g Span 80, 1g OP 10 and 0.6g Tween85 as emulsifying agent are dissolved in 200g No. 5 white oil to obtain an oil phase;
(2) Preparation of hectorite nano dispersion liquid
Dissolving 3-aminopropyl triethoxysilane in ethanol to prepare a solution with the concentration of 500g/L, adding 10g of hectorite and 30g of 2-acrylamide-2-methylpropanesulfonic acid into 250g of water, stirring for 24 hours to prepare a hectorite nano-dispersion system, then dripping 6g of ethanol solution of 3-aminopropyl triethoxysilane into the hectorite nano-dispersion system, stirring while dripping, controlling the pH to be 3.5, and stirring for 30 minutes after dripping is finished to obtain a hectorite nano-dispersion;
(3) Preparation of aqueous solutions
100g of acrylamide, 15g of N, N-dimethylacrylamide, 85g of 2-acrylamide-2-methylpropanesulfonic acid, 0.1g of N, N' -methylenebisacrylamide and 0.15g of potassium persulfate were dissolved in 300g of water, and the pH was adjusted to 4.5 to obtain an aqueous solution;
(4) Preparation of Pre-crosslinked gel particles
Adding 100g of oil phase into a three-necked glass bottle provided with a stirrer, a condenser tube and a thermometer, sequentially dripping 30g of hectorite nano-dispersion liquid and 80g of aqueous phase solution into the oil phase slowly, rapidly stirring while dripping, facilitating system emulsification, and introducing N under stirring after dripping is completed 2 Deoxidizing for 30min, adding 0.3g of ammonium cerium nitrate, controlling the temperature at 10 ℃, reacting for 5h, increasing the temperature to 75 ℃, and reacting for 3h to obtain the pre-crosslinked gel particles.
Example 2:
as described in example 1, except that OP 10 was added in an amount of 0.6g and Tween85 was added in an amount of 0.8g in step (1).
Example 3:
as described in example 1, except that the amount of 5# white oil added in step (1) was 100g.
Example 4:
as described in example 1, except that 3# white oil was used in the step (1), the amount added was 300g.
Example 5:
as described in example 1, except that 2-acrylamido-2-methylpropanesulfonic acid was added in an amount of 20g in step (2).
Example 6:
as described in example 1, except that the water addition amount in step (2) was 350g.
Example 7:
the ethanol solution of 3-aminopropyl triethoxysilane in step (2) was added in an amount of 4.5g, as described in example 1.
Example 8:
as described in example 1, except that the aminosiloxane in step (2) was 3- (2-aminoethylamino) propyl trimethoxysilane, the ethanol solution was added in an amount of 9g.
Example 9:
as described in example 1, except that N, N-dimethylacrylamide was added in an amount of 8g in step (3).
Example 10:
as described in example 1, except that the anionic monomer in step (3) was 40g of acrylic acid and 60g of 2-acrylamido-2-methylpropanesulfonic acid.
Example 11:
as described in example 1, except that the anionic monomer in step (3) was 40g of acrylic acid, 100g of 2-acrylamido-2-methylpropanesulfonic acid and 20g of sodium styrene sulfonate.
Example 12:
as described in example 1, except that N, N' -methylenebisacrylamide was added in an amount of 0.2g and potassium persulfate was added in an amount of 0.35g in step (3).
Example 13:
as described in example 1, except that N, N' -methylenebisacrylamide was added in an amount of 0.05g and potassium persulfate was added in an amount of 0.25g in step (3).
Example 14:
as described in example 1, except that the water addition amount in step (3) was 200g.
Example 15:
the procedure is as in example 1, except that the hectorite nanodispersion in step (4) is added in an amount of 45g.
Example 16:
the aqueous phase solution in step (4) was added in an amount of 120g as described in example 1.
Example 17:
as described in example 1, except that the amount of ammonium cerium nitrate added in step (4) was 0.15g.
Example 18:
as described in example 1, except that cerium ammonium nitrate was added in the step (4), the temperature was controlled at 15℃for 3 hours, the temperature was increased to 75℃for 1.5 hours.
Comparative example 1:
(1) Preparation of oil phase
12g Span 80, 1g OP 10 and 0.6g Tween85 as emulsifying agent are dissolved in 200g No. 5 white oil to obtain an oil phase;
(2) Preparation of 3-aminopropyl triethoxysilane solution
Dissolving 3-aminopropyl triethoxysilane in ethanol to prepare a solution with the concentration of 500g/L, adding 30g of 2-acrylamide-2-methylpropanesulfonic acid and 6g of ethanol solution of 3-aminopropyl triethoxysilane into 250g of water, controlling the pH to 3.5, and stirring for 30min to obtain 3-aminopropyl triethoxysilane solution;
(3) Preparation of aqueous solutions
100g of acrylamide, 15g of N, N-dimethylacrylamide, 85g of 2-acrylamide-2-methylpropanesulfonic acid, 0.1g of N, N' -methylenebisacrylamide and 0.15g of potassium persulfate were dissolved in 300g of water, and the pH was adjusted to 4.5 to obtain an aqueous solution;
(4) Preparation of Pre-crosslinked gel particles
100g of the oil phase was introduced into a three-necked glass flask equipped with a stirrer, a condenser and a thermometer, and 30g of 3-aminopropyl triethoxysilane solution and 80g of aqueous phase solution were slowly dropped in this orderAdding into oil phase, dripping while stirring rapidly to facilitate system emulsification, and introducing N under stirring 2 Deoxidizing for 30min, adding 0.3g of ammonium cerium nitrate, controlling the temperature at 10 ℃, reacting for 5h, increasing the temperature to 75 ℃, and reacting for 3h to obtain the pre-crosslinked gel particles.
Comparative example 2:
(1) Preparation of oil phase
12g Span 80, 1g OP 10 and 0.6g Tween85 as emulsifying agent are dissolved in 200g No. 5 white oil to obtain an oil phase;
(2) Preparation of hectorite nano dispersion liquid
Adding 10g of hectorite and 30g of 2-acrylamide-2-methylpropanesulfonic acid into 250g of water, stirring for 24 hours to prepare a hectorite nano-dispersion system, controlling the pH value to be 3.5, and stirring for 30 minutes after the dripping is finished to obtain a hectorite nano-dispersion liquid;
(3) Preparation of aqueous solutions
100g of acrylamide, 15g of N, N-dimethylacrylamide, 85g of 2-acrylamide-2-methylpropanesulfonic acid, 0.1g of N, N' -methylenebisacrylamide and 0.15g of potassium persulfate were dissolved in 300g of water, and the pH was adjusted to 4.5 to obtain an aqueous solution;
(4) Preparation of Pre-crosslinked gel particles
Adding 100g of oil phase into a three-necked glass bottle provided with a stirrer, a condenser tube and a thermometer, sequentially dripping 30g of hectorite nano-dispersion liquid and 80g of aqueous phase solution into the oil phase slowly, rapidly stirring while dripping, facilitating system emulsification, and introducing N under stirring after dripping is completed 2 Deoxidizing for 30min, adding 0.3g of ammonium cerium nitrate, controlling the temperature at 10 ℃, reacting for 5h, increasing the temperature to 75 ℃, and reacting for 3h to obtain the pre-crosslinked gel particles.
Comparative example 3:
(1) Preparation of oil phase
12g Span 80, 1g OP 10 and 0.6g Tween85 as emulsifying agent are dissolved in 200g No. 5 white oil to obtain an oil phase;
(2) Preparation of 2-acrylamide-2-methylpropanesulfonic acid solution
Adding 30g of 2-acrylamide-2-methylpropanesulfonic acid into 250g of water, controlling the pH to 3.5, and stirring for 30min to obtain a 2-acrylamide-2-methylpropanesulfonic acid solution;
(3) Preparation of aqueous solutions
100g of acrylamide, 15g of N, N-dimethylacrylamide, 85g of 2-acrylamide-2-methylpropanesulfonic acid, 0.1g of N, N' -methylenebisacrylamide and 0.15g of potassium persulfate were dissolved in 300g of water, and the pH was adjusted to 4.5 to obtain an aqueous solution;
(4) Preparation of Pre-crosslinked gel particles
Adding 100g of oil phase into a three-necked glass bottle provided with a stirrer, a condenser and a thermometer, slowly dripping 30g of 2-acrylamide-2-methylpropanesulfonic acid solution and 80g of aqueous phase solution into the oil phase in sequence, rapidly stirring while dripping, facilitating emulsification of the system, and introducing N under stirring after the dripping is completed 2 Deoxidizing for 30min, adding 0.3g of ammonium cerium nitrate, controlling the temperature at 10 ℃, reacting for 5h, increasing the temperature to 75 ℃, and reacting for 3h to obtain the pre-crosslinked gel particles.
Comparative example 4:
referring to the relevant literature, a pre-crosslinked gel particle is prepared by reverse phase microemulsion polymerization, as follows.
(1) Preparation of oil phase
24.3g Span 80 and 4g OP 10 of an emulsifying agent are dissolved in 200g No. 5 white oil to obtain an oil phase;
(2) Preparation of 3-aminopropyl triethoxysilane solution
Dissolving 3-aminopropyl triethoxysilane in ethanol to prepare a solution with the concentration of 500g/L, adding 30g of 2-acrylamide-2-methylpropanesulfonic acid and 6g of ethanol solution of 3-aminopropyl triethoxysilane into 250g of water, controlling the pH to 3.5, and stirring for 30min to obtain 3-aminopropyl triethoxysilane solution;
(3) Preparation of aqueous solutions
100g of acrylamide, 15g of N, N-dimethylacrylamide, 85g of 2-acrylamide-2-methylpropanesulfonic acid, 0.1g of N, N' -methylenebisacrylamide and 0.15g of potassium persulfate were dissolved in 300g of water, and the pH was adjusted to 4.5 to obtain an aqueous solution;
(4) Preparation of Pre-crosslinked gel particles
165g of the oil phase are introduced into a three-necked flask equipped with stirrer, condenser and thermometerIn a glass bottle, 30g of 3-aminopropyl triethoxysilane solution and 80g of aqueous phase solution are slowly added into the oil phase in sequence, and the mixture is rapidly stirred while being dropwise added, so that the system is convenient to emulsify, and N is introduced under stirring after the dropwise addition is completed 2 Deoxidizing for 30min, adding 0.3g of ammonium cerium nitrate, controlling the temperature at 10 ℃, reacting for 5h, increasing the temperature to 75 ℃, and reacting for 3h to obtain the pre-crosslinked gel particles.
Structural characterization
The emulsion was added to absolute ethanol, the precipitate was collected by filtration, the precipitate was washed 1 time with ethanol/water solution (v/v=7/3), 3 times with absolute ethanol, and dried in vacuo to give a powder sample. The infrared spectrum absorption of the powder samples was tested using KBr pellet method and the results are shown in FIG. 1. At N 2 In the atmosphere, the powder sample was analyzed for thermal decomposition, and the results are shown in fig. 2.
The emulsion was diluted with white oil and placed on a glass slide, and the morphology and particle size of the sample were measured by an optical microscope, and the results are shown in fig. 3.
As can be seen from FIG. 1, example 1 was performed at 450cm -1 And 520cm -1 Absorption occurs to the left and right, whereas comparative example 1 does not absorb here, which is a characteristic absorption peak of the silicone compound, and can correspond to the structure of laponite. In addition, both samples showed significant sulfonic acid groups (1033 cm -1 Left and right) absorption, carbon-based (1730 cm) -1 Left and right) absorb and absorb hydrocarbon bond (2940 cm) -1 Left-right) absorption. It can be seen that example 1 contains a laponite component and that the copolymerization of the monomers was successful.
As can be seen from fig. 2, the thermal weight loss process of example 1 and comparative example 1 is similar, which shows that both have similar organic components, and in addition, the residual weight of comparative example 1 at 800 ℃ is smaller than that of example 1, because laponite is an inorganic component in the examples, and the thermal stability is better.
As can be seen from FIG. 3, the gel particles in example 1 were all in a regular sphere shape, but their particle diameters were largely different and existed from several hundred nanometers to several micrometers.
Evaluation of Performance
In order to examine the blocking ability before and after aging of examples 1 to 18 and comparative examples 1 to 4, the following test was conducted in simulated mineralized water, the ion concentration and the total mineralization degree thereof are shown in Table 1, and the experimental results are shown in tables 2 and 3.
Sample preparation:
at room temperature, 3g of an emulsion sample of pre-crosslinked gel particles was added to 1L of simulated mineralized water and stirred at 400rpm for 15min to form a dispersion of pre-crosslinked particles.
Sample aging:
in a glove box, the dispersion of the pre-crosslinked particles was deoxygenated using nitrogen and vacuum, and aged in an oven at 90 ℃ for 180 days.
Plugging performance test:
(1) Selecting a sand filling pipe with an inner diameter of 2.5cm and a length of 20cm, filling a sand core, vacuumizing to saturate simulated formation water, and measuring the core permeability K 1 ；
(2) Injecting a dispersion of pre-crosslinked particles at a rate of 0.5mL/min, the injection amount being 2 void volumes;
(3) Injecting simulated formation water into the sand filling pipe, and measuring the permeability K after plugging 2 。
Plugging rate= (K) 1 -K 2 )/K 1 ×100％
The results show that the embodiment has better plugging effect before aging, and the plugging rate is more than 94 percent; after aging, the plugging performance of the comparative example is remarkably reduced, while the plugging rate of the example can be maintained above 80%, and the good long-term aging stability performance is shown.
As can be seen from the evaluation results of example 1 and comparative example 1, if no hectorite component is added to the gel particles, the initial blocking performance is slightly reduced, but the blocking performance is obviously reduced after aging, so that the addition of the inorganic component has obvious effects on improving the mechanical and ageing resistance of the system.
As can be seen from the evaluation results of example 1 and comparative example 2, if no aminosilate ester component is added to the gel particles, the blocking property is significantly reduced after aging, and thus it can be seen that the addition of aminosilate ester has a significant effect of improving the aging resistance of the system.
As can be seen from the evaluation results of example 1 and comparative example 4, the blocking property of the samples prepared by the inverse microemulsion polymerization was not good, and even if the amount was increased to 2 times, the blocking property of example 1 was not achieved much, and the analysis reasons were probably that the particle size distribution of the samples prepared by example 4 was narrow, and it was not suitable for heterogeneous characteristics of the formation, and in addition, the size of the samples prepared by the inverse microemulsion polymerization was small, and it was not suitable for the medium-high permeability formation.
TABLE 1 mineralized Water composition
| Ion composition | K + +Na + | Ca 2+ | Mg 2+ | Cl - | SO 4 2- | HCO 3 - | CO 3 2- | Total mineral content |
| Content (mg/L) | 8748 | 507 | 3309 | 16585 | 2372 | 157 | 2014 | 33692 |
TABLE 2 evaluation results of Properties of samples prepared by inverse emulsion polymerization of examples 1 to 18 and comparative examples 1 to 3
TABLE 3 evaluation results of Properties of samples prepared by reverse microemulsion polymerization of comparative example 4
The present invention has been disclosed above in terms of preferred embodiments, but it will be understood by those skilled in the art that these embodiments are merely illustrative of the present invention and should not be construed as limiting the scope of the present invention. It should be noted that all changes and substitutions equivalent to those of the embodiments are considered to be covered by the scope of the claims of the present invention. The scope of the invention should, therefore, be determined with reference to the appended claims.
Claims (14)
1. The preparation method of the pre-crosslinked gel particle type plugging agent is characterized by comprising the following steps:
(1) Dissolving an emulsifier in white oil to obtain an oil phase;
(2) Dissolving hectorite and 2-acrylamide-2-methylpropanesulfonic acid in water to obtain a hectorite nano-dispersion system; under an acidic condition, dripping an ethanol solution of amino silicate into the hectorite nano-dispersion system, and continuously stirring after the dripping is finished to obtain a hectorite nano-dispersion;
(3) Dissolving acrylamide, N-dimethylacrylamide, an anionic monomer, N' -methylenebisacrylamide and persulfate in water, and regulating pH to be acidic to obtain a water phase;
(4) Sequentially dripping the hectorite nano-dispersion liquid and the water phase into the oil phase, stirring while dripping, and introducing N after dripping is finished 2 Removing oxygen, adding cerium salt, reacting for 1-12 h at 0-30 ℃, heating to 50-85 ℃ and reacting for 0.5-8 h to obtain the pre-crosslinked gel particle plugging agent.
2. The method for preparing the pre-crosslinked gel particle-type plugging agent according to claim 1, wherein the emulsifier comprises Span 80, OP 10, tween 85; the white oil is one of 3# white oil, 5# white oil, 7# white oil and 10# white oil.
3. The preparation method of the pre-crosslinked gel particle plugging agent according to claim 2, wherein the mass ratio of Span 80 to OP 10 to Tween85 to white oil is 1 (0.01-0.2): 0.01-0.1): 5-80.
4. The preparation method of the pre-crosslinked gel particle plugging agent according to claim 3, wherein the mass ratio of Span 80 to OP 10 to Tween85 to white oil is 1 (0.03 to 0.15): 0.01 to 0.07): 5 to 35.
5. The method for preparing a pre-crosslinked gel particle plugging agent according to claim 1, wherein in the step (2), the concentration of the ethanol solution of the aminosilate ester is 400-600 g/L; the mass ratio of the hectorite to the ethanol solution of the 2-acrylamide-2-methylpropanesulfonic acid and the aminosilate to the water is 1 (2-8) (0.01-1) (10-100).
6. The method for preparing the pre-crosslinked gel particle type plugging agent according to claim 1, wherein the mass ratio of hectorite, 2-acrylamide-2-methylpropanesulfonic acid, an ethanol solution of amino silicate and water is 1 (2-4): 0.3-1): 15-70.
7. The method for preparing the pre-crosslinked gel particle plugging agent according to claim 1, wherein the aminosilicates are one of 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3- (2-aminoethylamino) propyl trimethoxysilane and 3- (2-aminoethylamino) propyl triethoxysilane.
8. The preparation method of the pre-crosslinked gel particle type plugging agent according to claim 1, wherein the mass ratio of the acrylamide to the N, N-dimethylacrylamide to the anionic monomer to the N, N' -methylenebisacrylamide to the persulfate is 1 (0.01-0.35): (0.01-10): (0.0005-0.004): (0.0001-0.005); wherein the ratio of the total mass of the acrylamide, the N, N-dimethylacrylamide and the anionic monomer to the mass of water is 1 (0.5-6).
9. The method for preparing the pre-crosslinked gel particle type plugging agent according to claim 1, wherein the mass ratio of the acrylamide to the N, N-dimethylacrylamide to the anionic monomer to the N, N' -methylenebisacrylamide to the persulfate is 1 (0.05-0.25): (0.1-5): (0.0005-0.0025): (0.0005-0.005); wherein the ratio of the total mass of the acrylamide, the N, N-dimethylacrylamide and the anionic monomer to the mass of water is 1 (0.5-4).
10. The method for preparing the pre-crosslinked gel particle-type plugging agent according to claim 1, wherein the anionic monomer is one or a mixture of more than two of acrylic acid, methacrylic acid, maleic acid, itaconic acid, 2-acrylamido-2-methylpropanesulfonic acid, sodium vinylsulfonate, sodium styrenesulfonate and sodium allylsulfonate; the persulfate is one of potassium persulfate, sodium persulfate and ammonium persulfate; the cerium salt is one of ammonium cerium nitrate and ammonium cerium sulfate.
11. The preparation method of the pre-crosslinked gel particle plugging agent according to claim 1, wherein in the step (4), the mass ratio of the oil phase to the hectorite nano-dispersion to the aqueous phase solution is 1 (0.05-0.5): 0.3-2); the mass ratio of the hectorite nano-dispersion liquid and the ammonium cerium nitrate is 1 (0.001-0.02).
12. The preparation method of the pre-crosslinked gel particle plugging agent according to claim 1, wherein in the step (4), the mass ratio of the oil phase to the hectorite nano-dispersion to the aqueous phase solution is 1 (0.1-0.5) (0.5-1.5); the mass ratio of the hectorite nano-dispersion liquid and the ammonium cerium nitrate is 1 (0.001-0.012).
13. A pre-crosslinked gel particle-type plugging agent characterized by being prepared by the preparation method of the pre-crosslinked gel particle-type plugging agent according to any one of claims 1 to 12.
14. Use of the pre-crosslinked gel particulate plugging agent of any one of claims 1-13 in offshore oilfield exploitation.
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