CN116948095A - Polymer, ultra-high temperature oil well cement retarder, preparation method and application thereof, and cement slurry - Google Patents
Polymer, ultra-high temperature oil well cement retarder, preparation method and application thereof, and cement slurry Download PDFInfo
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- CN116948095A CN116948095A CN202210390299.0A CN202210390299A CN116948095A CN 116948095 A CN116948095 A CN 116948095A CN 202210390299 A CN202210390299 A CN 202210390299A CN 116948095 A CN116948095 A CN 116948095A
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- Prior art keywords
- ultra
- high temperature
- oil well
- retarder
- polymer
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- 239000004568 cement Substances 0.000 title claims abstract description 171
- 239000003129 oil well Substances 0.000 title claims abstract description 98
- 229920000642 polymer Polymers 0.000 title claims abstract description 73
- 239000002002 slurry Substances 0.000 title claims description 34
- 238000002360 preparation method Methods 0.000 title abstract description 32
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 31
- 239000000178 monomer Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 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 16
- 239000007788 liquid Substances 0.000 claims description 16
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 16
- 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 description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 12
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 12
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims description 11
- 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 11
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 9
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 8
- 239000012986 chain transfer agent Substances 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- UURKSQXMUNUXSI-UHFFFAOYSA-N 1-(diethoxyphosphorylmethyl)-4-ethenylbenzene Chemical compound CCOP(=O)(OCC)CC1=CC=C(C=C)C=C1 UURKSQXMUNUXSI-UHFFFAOYSA-N 0.000 claims description 7
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 7
- -1 4-vinylbenzylamino Chemical group 0.000 claims description 7
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 235000010265 sodium sulphite Nutrition 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical compound CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 claims description 4
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 3
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 3
- 238000005553 drilling Methods 0.000 claims description 3
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 3
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 claims description 3
- 235000019252 potassium sulphite Nutrition 0.000 claims description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 3
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 3
- XQBHAZDVLGNSOJ-UHFFFAOYSA-N 1-(4-ethenylphenyl)-n,n-dimethylmethanamine Chemical compound CN(C)CC1=CC=C(C=C)C=C1 XQBHAZDVLGNSOJ-UHFFFAOYSA-N 0.000 claims description 2
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 claims description 2
- XFOZBWSTIQRFQW-UHFFFAOYSA-M benzyl-dimethyl-prop-2-enylazanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC1=CC=CC=C1 XFOZBWSTIQRFQW-UHFFFAOYSA-M 0.000 claims description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 2
- 229940079827 sodium hydrogen sulfite Drugs 0.000 claims 1
- 230000008719 thickening Effects 0.000 abstract description 39
- 239000004575 stone Substances 0.000 abstract description 8
- 239000000654 additive Substances 0.000 abstract description 7
- 238000004378 air conditioning Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 69
- 230000000052 comparative effect Effects 0.000 description 18
- 239000000047 product Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 239000003921 oil Substances 0.000 description 10
- 238000001179 sorption measurement Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 230000002159 abnormal effect Effects 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000001879 gelation Methods 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Chemical group C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Natural products OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000012264 purified product Substances 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 238000009777 vacuum freeze-drying Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- QISOBCMNUJQOJU-UHFFFAOYSA-N 4-bromo-1h-pyrazole-5-carboxylic acid Chemical compound OC(=O)C=1NN=CC=1Br QISOBCMNUJQOJU-UHFFFAOYSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 2
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910021487 silica fume Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000008876 conformational transition Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 1
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000009044 synergistic interaction Effects 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
- C08F220/585—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS]
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/003—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/20—Retarders
- C04B2103/22—Set retarders
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The application provides a polymer, an ultra-high temperature oil well cement retarder, and a preparation method and application thereofThe molecular structural formula of the polymer of the cement paste is shown as the formula (1):in the formula (1), a, b and c are all mole numbers, and the ratio of the three is 40-85:10-40:5-20; r is R 1 is-H, -CH 3 -CH 2 One of COOH; r is R 2 One selected from the following compounds: a kind of electronic device with high-pressure air-conditioning systemThe ultra-high temperature oil well cement retarder provided by the application has the advantages that the temperature resistance can reach 240 ℃, the cement paste thickening time is linearly adjustable within 200-500min within the temperature range of 110-240 ℃, the cement paste thickening time has good linear relation with temperature and addition amount, the compatibility with other additives is good, the influence on the mechanical properties of cement stones is small, the safety of ultra-high temperature well cementation operation can be ensured, and the complex and difficult well cementation technical requirements can be met.
Description
Technical Field
The application relates to a polymer, an ultrahigh-temperature oil well cement retarder, a preparation method and application thereof and cement slurry, and belongs to the technical field of oil-gas well cementing additives.
Background
The 39% of residual petroleum and 57% of residual natural gas resources on the land of China are distributed in the deep layer, the deep layer ultra-deep layer becomes an important field of oil and gas storage and up-production, has important significance for improving the level of energy guarantee of China, and is one of powerful measures for relieving the external dependence pressure of Chinese energy. The ultra-deep oil gas resource safe and efficient exploration and development faces a series of important engineering technical problems of deeper well (more than 8000 m), higher temperature (more than 240 ℃ C.), more complex well condition and the like, wherein well cementation is a key engineering technology for guaranteeing oil gas safe and efficient exploration and development, quality improvement and efficiency improvement, and is directly related to oil gas recovery ratio, well service life and long-term safe production, so that ultra-high temperature and other complex working conditions provide extremely high requirements for a well cementation cement slurry system and key materials. At ultrahigh temperature, how to effectively control the thickening time of a well cementation cement slurry system is a key for guaranteeing the safety of well cementation operation, wherein a retarder is one of main agents for prolonging the thickening time of the cement slurry, improving the rheological property of the system and guaranteeing the comprehensive performance of the system, is a key material for guaranteeing the safety of the well cementation operation of a deep well and an ultra-deep well, and directly determines the success or failure of the well cementation operation.
The oil well cement retarder has various types, wherein 2-acrylamide-2-methylpropanesulfonic Acid (AMPS) polymers become hot spots for research and application due to the characteristics of strong temperature resistance and salt resistance, diversity of molecular structure design, controllable production and the like. For example, chinese patent CN 102040987a discloses a retarder for oil well cement with a temperature resistance of 230 ℃, which is prepared from AMPS and propylene tricarboxylic acid by a free radical aqueous solution polymerization method, and the thickening time of cement paste with a doping amount of 3% is 330min, but the technology evaluates that the cement paste system is simpler, and no superfine materials, stabilizers and other substances which ensure the stability of the system are present, and the poor stability of the cement paste system may have a larger influence on the thickening time of the system. Chinese patent CN 104403056B discloses an ultra-high temperature retarder formed by copolymerizing AMPS, DMDAAC (diallyldimethylammonium chloride), MAH (maleic anhydride) or IA (itaconic acid) or FA (fumaric acid), AA (acrylic acid) or methacrylic acid four polymeric monomers, wherein the mixing amount of the ultra-high temperature retarder is 6.0% and the cement paste thickening time at 230 ℃ can reach 289min, but the mixing amount of the product is large and the coagulation performance is not related to the cement paste thickening performance above 230 ℃, so that the ultra-high temperature cementing technical requirement of ultra-deep wells with the bottom temperature above 230 ℃ cannot be met. US5536311 uses one of AMPS, sodium methallylsulfonate, SSS (sodium styrenesulfonate), VS (vinylsulfonic acid), NNDMA (N, N-dimethylacrylamide), AM (acrylamide), NVP (N-vinylpyrrolidone), acrylonitrile, etc. as a first monomer, one of IA, MA (maleic acid), MAH, FA, mesaconic acid, citric acid, TA, etc. as a second monomer, and one of AA, MA as a third monomer, various multipolymer high temperature retarders were developed, wherein the AMPS/IA/MAH terpolymer retarder resists temperatures up to 260 ℃, but in this patent the cement paste evaluation formulation is too simple (wherein the formulation contains H-grade cement, 35% silica powder, 4% retarder and 38% water), the sedimentation stability of the system cannot be guaranteed, and the retarder has strong high temperature dispersibility, possibly resulting in a longer cement paste thickening time at 260 ℃ due to poor system stability.
Therefore, although the oil well cement retarder in China represented by the patent is improved in the aspect of temperature resistance and salt resistance, the ultra-high temperature technical bottleneck of 232 ℃ is still not broken through, at present, the ultra-high temperature well cementation retarder product mainly depends on import, and the existing retarder in China in the international environment with complicated complexity can not completely meet the ultra-high temperature well cementation operation requirements under the new situation of exploration and development.
Therefore, providing a novel ultra-high temperature oil well cement retarder, a preparation method and application thereof and cement slurry have become technical problems to be solved in the field.
Disclosure of Invention
In order to solve the above-described drawbacks and disadvantages, an object of the present application is to provide a polymer.
Another object of the present application is to provide an ultra-high temperature oil well cement retarder.
The application also aims to provide a preparation method of the ultra-high temperature oil well cement retarder.
It is still another object of the present application to provide the use of the above-described polymer or the ultra-high temperature oil well cement retarder in complex job well cementing operations.
It is also a final object of the present application to provide a cement slurry comprising the above-described polymer or the above-described ultra-high temperature oil well cement retarder. The ultra-high temperature oil well cement retarder provided by the application has the advantages that the temperature resistance can reach 240 ℃, the cement paste thickening time is linearly adjustable within a temperature range of 110-240 ℃ and has good linear relation with temperature and addition, the compatibility with other additives is good, the influence on the mechanical properties of cement stones is small, the safety of ultra-high temperature well cementation operation can be ensured, and the complex well cementation technical requirements of deep wells, ultra-deep wells, vanmilch exploratory wells, high-temperature high-pressure gas wells, unconventional oil gas wells, gas storage wells and the like can be met.
In order to achieve the above object, in one aspect, the present application provides a polymer, wherein the molecular structural formula of the polymer is shown as formula (1):
in the formula (1), a, b and c are all mole numbers, and the ratio of the three is 40-85:10-40:5-20;
R 1 is-H, -CH 3 -CH 2 One of COOH;
R 2 one selected from the following compounds:
is->
On the other hand, the application also provides an ultra-high temperature oil well cement retarder, wherein the ultra-high temperature oil well cement retarder comprises the polymer and water, and the total weight of the ultra-high temperature oil well cement retarder is 100%, the content of the polymer is 20-40%, and the content of the water is 60-80%.
In still another aspect, the present application further provides a method for preparing the ultra-high temperature oil well cement retarder, where the method comprises:
(1) Dissolving 2-acrylamido-2-methylpropanesulfonic acid monomer, unsaturated carboxylic acid monomer and rigid unsaturated monomer in deionized water, and adding alkaline substances into the obtained solution to adjust the pH value of the solution to 3-5; wherein the weight ratio of the 2-acrylamide-2-methylpropanesulfonic acid monomer, the unsaturated carboxylic acid monomer and the rigid unsaturated monomer is 45-92:4-32:4-30;
(2) Adding a chain transfer agent into the system obtained in the step (1), heating, adding an initiator, and continuously heating to perform polymerization reaction;
(3) And (3) adding a reducing inorganic salt into the solution obtained after the reaction in the step (2) to carry out aftertreatment, and obtaining a viscous liquid polymer solution after the aftertreatment is finished, namely the ultra-high temperature oil well cement retarder.
As a specific embodiment of the preparation method of the present application, in the step (1), the weight ratio of the 2-acrylamido-2-methylpropanesulfonic acid monomer, the unsaturated carboxylic acid monomer, the rigid unsaturated monomer and the deionized water is in the range of 45-92:4-32:4-30:150-300.
As a specific embodiment of the above preparation method of the present application, in the step (1), the unsaturated carboxylic acid monomer includes one or a combination of several of itaconic acid, methacrylic acid, acrylic acid and crotonic acid.
As a specific embodiment of the above preparation method of the present application, in the step (1), the rigid unsaturated monomer comprises one or a combination of several of diethyl 4-vinylbenzylphosphonate, 2' - (4-vinylbenzylamino) diacetic acid, vinylbenzyltrimethylammonium chloride (N-trimethyl- (4-vinylbenzyl) ammonium chloride) and N- (4-vinylbenzyl) -N, N-dimethylamine.
As a specific embodiment of the above-mentioned preparation method of the present application, wherein in the step (1), the alkaline substance comprises sodium hydroxide in an amount of 10 to 20 parts by weight.
As a specific embodiment of the above preparation method of the present application, in the step (2), the chain transfer agent is used in an amount of 0.05 to 1.0% by mass based on the total mass of the monomers.
As a specific embodiment of the above preparation method of the present application, in the step (2), the chain transfer agent comprises one or more of 3-mercaptopropionic acid, 3-mercaptoacetic acid, mercaptoethanol, n-butylmercaptan, n-dodecylmercaptan and isopropanol.
As a specific embodiment of the preparation method of the present application, in the step (2), the initiator is used in an amount of 0.5 to 2.5% of the total mass of the monomers.
As a specific embodiment of the preparation method of the present application, in the step (2), the initiator comprises one or more of ammonium persulfate, potassium persulfate and azo diiso Ding Mi hydrochloride.
As a specific embodiment of the preparation method of the application, in the step (2), the chain transfer agent is added into the system obtained in the step (1), and then the temperature is raised to 50-65 ℃ and kept for 10-30min.
As a specific embodiment of the above preparation method of the present application, in the step (2), the continuously heating to perform the polymerization reaction includes: heating to 70-90 ℃ and reacting for 2-5h at constant temperature.
As a specific embodiment of the preparation method of the present application, in the step (2), the heating rate of the heating is 0.5-2 ℃/min.
As a specific embodiment of the preparation method of the present application, in the step (3), the amount of the reducing inorganic salt is 0.2-1.0% of the total mass of the solution obtained after the reaction in the step (2).
As a specific embodiment of the above preparation method of the present application, in the step (3), the reducing inorganic salt comprises one or more of sodium sulfite, sodium bisulfite, ammonium sulfite, potassium sulfite and potassium hydrogen sulfite.
As a specific embodiment of the preparation method of the present application, in the step (3), the post-treatment time is 30-60min.
As a specific embodiment of the above preparation method of the present application, step (3) further includes: and after finishing the post-treatment, naturally cooling the system to room temperature to obtain a viscous liquid polymer solution, namely the ultra-high temperature oil well cement retarder.
In the application, after the ultra-high temperature oil well cement retarder is prepared, acetone can be adopted to wash the prepared ultra-high temperature oil well cement retarder, and then vacuum freeze drying is carried out to obtain a purified product, namely the polymer. The times of washing the acetone, the temperature, the time and the like of the vacuum freeze drying can be reasonably adjusted according to the actual operation requirement, so long as the aim of the application can be realized.
In still another aspect, the application also provides the use of the polymer described above or the ultra-high temperature oil well cement retarder described above in complex work condition well cementing operations.
As a specific embodiment of the above application of the present application, the complex working well includes a deep well, an ultra-deep well, a myriad of meters scientific drilling well, a high temperature and high pressure gas well, an unconventional oil gas well, or a gas storage well.
In a final aspect, the application also provides a cement slurry, wherein the cement slurry comprises the polymer or the ultra-high temperature oil well cement retarder.
As a concrete embodiment of the cement paste, the addition amount of the ultra-high temperature oil well cement retarder is 1.5-6.5% based on 100% of the total weight of the cement contained in the cement paste.
The application improves the ultrahigh temperature resistance and the coagulation regulating performance of the polymer retarder by means of optimal design of a molecular structure, effective intervention of a temperature-resistant and salt-resistant rigid group, synergistic effect of a plurality of adsorption groups, efficient treatment of a reducing inorganic salt and the like. Specifically, firstly, the introduction of high temperature resistant and salt resistant rigid groups such as high temperature resistant vinyl benzyl increases the rigidity of a polymer molecular chain and the stability of an ultra-high temperature structure of the polymer molecular chain, and endows the polymer retarder with ultra-high temperature resistant capability; secondly, a plurality of adsorption groups such as carboxylic acid, dicarboxylic acid, phosphonic acid and the like are introduced into a polymer molecular structure to carry out synergistic interaction, so that the adsorption capacity and the chelation capacity of the polymer retarder on the surface of cement particles under the ultra-high temperature condition are greatly improved, and the ultra-high Wen Diaoning performance and the environment adaptability of the polymer retarder product are synergistically improved; thirdly, the molecular weight of the polymer can be reasonably regulated and controlled to reduce the linear length of the polymer molecular chain, so that the problem of abnormal gelation of a cement slurry system caused by the conformational transition of the polymer under the action of high-temperature strong adsorption can be avoided; finally, the product obtained after the polymerization reaction is subjected to post-treatment by using the reducing inorganic salt, so that the molecular conformation can be reformed, and the oxidation initiator in the system is annihilated, so that the quality stability of the polymer product is ensured, and the cement paste high-temperature abnormal gelation caused by the polycarboxylic acid retarder can be further improved and relieved. In a word, reasonable molecular structure, functional group and other technical means endow the cement retarder for the ultra-high temperature oil well with good ultra-high Wen Diaoning performance, so that the cement retarder can meet the well cementation operation requirements of complex working condition wells such as high-temperature and high-pressure gas wells, unconventional oil and gas wells, gas storage wells, deep wells, ultra-deep wells, universal meter scientific drilling wells and the like.
Compared with the prior art, the application has the following beneficial effects:
(1) The application improves the ultra-high temperature resistance and stable setting performance of the polymer retarder through the measures of optimal design of molecular structure, effective intervention of heat-resistant and salt-resistant rigid groups, synergistic effect of multiple adsorption groups, efficient treatment of reducing inorganic salt and the like. In addition, the introduction of functional groups such as phosphonic acid groups, amino groups, quaternary ammonium salts, imidazole and the like can further improve the charge density of the polymer corrosion inhibitor and promote the ultra-high temperature adsorption stability of the polymer corrosion inhibitor, so that the thickening time of an ultra-high temperature cement slurry system can be effectively regulated and controlled.
(2) The ultra-high temperature oil well cement retarder provided by the application has the advantages of wide application temperature range (70-240 ℃), linearly adjustable cement paste thickening time within 200-500min in a temperature range of 110-240 ℃, good linear relation with temperature and addition, good compatibility with other additives and small influence on the mechanical properties (development of mechanical strength of cement stones) of cement stones.
(3) The ultra-high temperature oil well cement retarder provided by the application has strong adaptability, is suitable for various cement slurry systems with conventional density, low density, high strength toughness, latex and the like, can effectively ensure the well cementation construction safety, reduces the well cementation operation risk, and meets the well cementation technical requirements of complex and difficult wells such as deep wells, ultra-deep wells, wanmidae exploratory wells, high-temperature high-pressure gas wells, unconventional oil gas wells, gas storage wells and the like.
(4) The preparation method of the ultra-high temperature oil well cement retarder provided by the application is simple, green, safe and environment-friendly, has the advantages of easily available raw materials and low production cost, and can realize industrial production and large-scale popularization and application.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings required for the description of the embodiments will be briefly described, and it is obvious that the drawings in the following description are some embodiments of the present application, and other drawings may be obtained according to the drawings without inventive effort for a person skilled in the art.
Fig. 1 is an infrared spectrum of the purified product of the ultra-high temperature oil well cement retarder S1 provided in example 1 of the present application.
FIG. 2 is a thickening graph of cement slurry at 110 ℃ x 70MPa, with an ultra-high temperature oil well cement retarder addition of 1.5% provided in example 1 of the present application.
FIG. 3 is a graph showing the thickening of cement slurry at 240 ℃ by 120MPa, wherein the cement retarder for ultra-high temperature oil well is 5% in addition, provided in example 1 of the present application.
FIG. 4 is a graph of the thickening of cement slurries at 240 ℃ x 120MPa with 5% of the oil well cement retarder provided in comparative example 1.
FIG. 5 is a graph of the thickening of a cement slurry at 130 ℃ x 70MPa with an oil well cement retarder loading of 2% as provided in comparative example 2.
Detailed Description
In order to make the technical features, objects and advantageous effects of the present application more clearly understood, the technical aspects of the present application will now be described in detail with reference to the following specific examples, but should not be construed as limiting the scope of the present application.
It should be noted that the term "comprising" in the description of the application and the claims and any variations thereof in the above-described figures is intended to cover a non-exclusive inclusion, such as a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements that are expressly listed or inherent to such process, method, article, or apparatus.
The "range" disclosed herein is given in the form of a lower limit and an upper limit. There may be one or more lower limits and one or more upper limits, respectively. The given range is defined by selecting a lower limit and an upper limit. The selected lower and upper limits define the boundaries of the particular ranges. All ranges defined in this way are combinable, i.e. any lower limit can be combined with any upper limit to form a range. For example, ranges of 60-120 and 80-110 are listed for specific parameters, with the understanding that ranges of 60-110 and 80-120 are also contemplated. Furthermore, if the minimum range values listed are 1 and 2 and the maximum range values listed are 3,4 and 5, then the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5.
In the present application, unless otherwise indicated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" have been listed throughout this disclosure, and "0-5" is only a shorthand representation of a combination of these values.
In the present application, all the embodiments and preferred embodiments mentioned in the present application may be combined with each other to form new technical solutions, unless otherwise specified.
In the present application, all technical features mentioned in the present application and preferred features may be combined with each other to form a new technical solution unless specifically stated otherwise.
The present application will be further described in detail with reference to the accompanying drawings, figures and examples, in order to make the objects, technical solutions and advantages of the present application more apparent. The following described embodiments are some, but not all, examples of the present application and are merely illustrative of the present application and should not be construed as limiting the scope of the application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The embodiment provides an ultra-high temperature oil well cement retarder, which is prepared by a preparation method comprising the following specific steps:
(1) Respectively weighing 72.4 parts by weight of 2-acrylamido-2-methylpropanesulfonic acid, 17 parts by weight of itaconic acid and 10.6 parts by weight of diethyl 4-vinylbenzylphosphonate, completely dissolving the materials in 140 parts by weight of deionized water, and slowly adding 12.6 parts by weight of sodium hydroxide into the obtained solution to adjust the pH value of the solution to 4-5;
(2) Then, adding 0.4 part by weight of 3-mercaptopropionic acid into the solution obtained in the step (1), and slowly heating to 60 ℃ at a stirring rate of 200r/min plus or minus 20 r/min; dissolving 1.5 parts by weight of potassium persulfate in 10 parts by weight of deionized water, slowly dripping the potassium persulfate into the solution system within about 30min, and slowly heating to 80 ℃ at a heating rate of 0.6 ℃/min for continuous reaction for 4h;
(3) And (3) adding 1.13 parts by weight of sodium sulfite into 264.5 parts by weight of the solution obtained in the step (2), continuously treating for 30min, and naturally cooling to room temperature to obtain a viscous liquid polymer solution, namely the ultrahigh-temperature oil well cement retarder, and marking as S1. The ultra-high temperature oil well cement retarder S1 comprises a polymer retarder, and the molecular structural formula of the polymer retarder is shown as the formula (1.1):
in the formula (1.1), the ratio of a to b to c is 67:25:8.
Example 2
The embodiment provides an ultra-high temperature oil well cement retarder, which is prepared by a preparation method comprising the following specific steps:
(1) 67.7 parts by weight of 2-acrylamido-2-methylpropanesulfonic acid, 13.1 parts by weight of itaconic acid and 19.2 parts by weight of diethyl 4-vinylbenzylphosphonate were weighed respectively and completely dissolved in 175 parts by weight of deionized water, and 11.3 parts by weight of sodium hydroxide was slowly added to the resulting solution to adjust the pH of the solution to 4-5;
(2) Then, adding 0.5 part by weight of mercaptoethanol into the solution obtained in the step (1), and slowly heating to 55 ℃ at a stirring rate of 200r/min +/-20 r/min; then 2 parts by weight of ammonium persulfate is dissolved in 10 parts by weight of deionized water, and is slowly added into the solution system dropwise within 30min, and then the temperature is slowly increased to 80 ℃ at the heating rate of 1 ℃/min for continuous reaction for 4 hours;
(3) And (2) adding 1.28 parts by weight of sodium sulfite into 298.8 parts by weight of the solution obtained in the step (2), continuously treating for 30min, and naturally cooling to room temperature to obtain a viscous liquid polymer solution, namely the ultrahigh-temperature oil well cement retarder, and marking the viscous liquid polymer solution as S2. The ultra-high temperature oil well cement retarder S2 contains a polymer retarder, and the molecular structural formula of the polymer retarder is shown as formula (1.2):
in the formula (1.2), the ratio of a to b to c is 65:20:15.
Example 3
The embodiment provides an ultra-high temperature oil well cement retarder, which is prepared by a preparation method comprising the following specific steps:
(1) 71.7 parts by weight of 2-acrylamido-2-methylpropanesulfonic acid, 17.8 parts by weight of itaconic acid and 10.5 parts by weight of 2,2' - ((4-vinylbenzyl) aminoidene) diacetic acid were weighed respectively and completely dissolved in 140 parts by weight of deionized water, and 14 parts by weight of sodium hydroxide was slowly added to the resulting solution to adjust the pH of the solution to 4 to 5;
(2) Then, adding 0.3 part by weight of 3-mercaptoacetic acid into the solution obtained in the step (1), and slowly heating to 60 ℃ at a stirring rate of 200r/min plus or minus 20 r/min; then 1 part by weight of ammonium persulfate is dissolved in 10 parts by weight of deionized water, and is slowly added into the solution system dropwise within 30 minutes, and then the temperature is slowly increased to 80 ℃ at the heating rate of 0.6 ℃/min for continuous reaction for 4 hours;
(3) And (3) adding 2 parts by weight of sodium bisulphite into 265.3 parts by weight of the solution obtained in the step (2), continuously treating for 50min, and naturally cooling to room temperature to obtain a viscous liquid polymer solution, namely the ultrahigh-temperature oil well cement retarder, and marking the viscous liquid polymer solution as S3. The ultra-high temperature oil well cement retarder S3 contains a polymer retarder, and the molecular structural formula of the polymer retarder is shown as formula (1.3):
in the formula (1.3), the ratio of a to b to c is 66:26:8.
Example 4
The embodiment provides an ultra-high temperature oil well cement retarder, which is prepared by a preparation method comprising the following specific steps:
(1) 69.5 parts by weight of 2-acrylamido-2-methylpropanesulfonic acid, 11.7 parts by weight of itaconic acid and 18.8 parts by weight of 2,2' - ((4-vinylbenzyl) aminoidene) diacetic acid were weighed respectively and completely dissolved in 223 parts by weight of deionized water, and 14.2 parts by weight of sodium hydroxide was slowly added to the resulting solution and the pH of the solution was adjusted to 4 to 5;
(2) Then, adding 0.9 weight part of n-dodecyl mercaptan into the solution obtained in the step (1), and slowly heating to 65 ℃ at a stirring rate of 200r/min plus or minus 20 r/min; dissolving 0.8 part by weight of azodiiso Ding Mi hydrochloride in 10 parts by weight of deionized water, slowly dropwise adding the solution into the solution system within about 30 minutes, and slowly heating to 80 ℃ at a heating rate of 0.5 ℃/min for continuous reaction for 5 hours;
(3) Adding 1.6 parts by weight of potassium hydrogen sulfite into the solution of 348.9 parts by weight obtained in the step (2) and continuously treating for 30min, naturally cooling to room temperature to obtain a viscous liquid polymer solution, namely the ultrahigh-temperature oil well cement retarder, and marking the viscous liquid polymer solution as S4. The ultra-high temperature oil well cement retarder S4 contains a polymer retarder, and the molecular structural formula of the polymer retarder is shown as formula (1.4):
in the formula (1.4), the ratio of a to b to c is 67:18:15.
Example 5
The embodiment provides an ultra-high temperature oil well cement retarder, which is prepared by a preparation method comprising the following specific steps:
(1) 62.4 parts by weight of 2-acrylamido-2-methylpropanesulfonic acid, 18.6 parts by weight of itaconic acid and 19 parts by weight of N-trimethyl- (4-vinylbenzyl) ammonium chloride are respectively weighed and completely dissolved in 140 parts by weight of deionized water, 11.4 parts by weight of sodium hydroxide is slowly added to the obtained solution, and the pH value of the solution is adjusted to 4-5;
(2) Then, adding 0.5 part by weight of 3-mercaptopropionic acid into the solution obtained in the step (1), and slowly heating to 60 ℃ at a stirring rate of 200r/min plus or minus 20 r/min; then 1 part by weight of potassium persulfate is dissolved in 10 parts by weight of deionized water, and is slowly added into the solution system dropwise within 30min, and then the temperature is slowly increased to 85 ℃ at the heating rate of 0.8 ℃/min for continuous reaction for 2h;
(3) And (3) adding 1.6 parts by weight of potassium hydrogen sulfite into 262.9 parts by weight of the solution obtained in the step (2), continuously treating for 30min, naturally cooling to room temperature to obtain a viscous liquid polymer solution, namely the ultrahigh-temperature oil well cement retarder, and marking as S5. The ultra-high temperature oil well cement retarder S5 contains a polymer retarder, and the molecular structural formula of the polymer retarder is shown as the formula (1.5):
in the formula (1.5), the ratio of a to b to c is 57:27:17.
Example 6
The embodiment provides an ultra-high temperature oil well cement retarder, which is prepared by a preparation method comprising the following specific steps:
(1) 67.8 parts by weight of 2-acrylamido-2-methylpropanesulfonic acid, 16.5 parts by weight of itaconic acid and 15.7 parts by weight of diethyl 4-vinylbenzylphosphonate were weighed respectively and completely dissolved in 300 parts by weight of deionized water, and 10.2 parts by weight of sodium hydroxide was slowly added to the resulting solution to adjust the pH of the solution to 4-5;
(2) Then, adding 0.8 part by weight of n-butyl mercaptan into the solution obtained in the step (1), and slowly heating to 55 ℃ at a stirring rate of 200r/min +/-20 r/min; then 2 parts by weight of ammonium persulfate is dissolved in 10 parts by weight of deionized water, and is slowly added into the solution system dropwise within 30 minutes, and then the temperature is slowly increased to 80 ℃ at the heating rate of 0.5 ℃/min for continuous reaction for 3 hours;
(3) Adding 1.8 parts by weight of potassium sulfite into 423 parts by weight of the solution obtained in the step (2), continuously treating for 60min, and naturally cooling to room temperature to obtain a viscous liquid polymer solution, namely the ultrahigh-temperature oil well cement retarder, and marking as S6. The ultra-high temperature oil well cement retarder S6 contains a polymer retarder, and the molecular structural formula of the polymer retarder is shown as formula (1.6):
in the formula (1.6), the ratio of a to b to c is 53:37:10.
Comparative example 1
The comparative example provides an oil well cement retarder which is prepared by a preparation method comprising the following specific steps:
(1) 77 parts by weight of 2-acrylamide-2-methylpropanesulfonic acid and 23 parts by weight of itaconic acid are respectively weighed and completely dissolved in 140 parts by weight of deionized water, and 14.2 parts by weight of sodium hydroxide is slowly added into the obtained solution to adjust the pH value of the solution to 4-5;
(2) Then, adding 0.4 part by weight of 3-mercaptopropionic acid into the solution obtained in the step (1), and slowly heating to 60 ℃ at a stirring rate of 200r/min plus or minus 20 r/min; dissolving 1.5 parts by weight of potassium persulfate in 10 parts by weight of deionized water, slowly dropwise adding the solution into the solution system within about 30min, and slowly heating to 80 ℃ at a heating rate of 0.6 ℃/min for continuous reaction for 4h;
(3) And (3) adding 1.13 parts by weight of sodium sulfite into 266.1 parts by weight of the solution obtained in the step (2), continuously treating for 30min, and naturally cooling to room temperature to obtain a viscous liquid polymer solution, namely the oil well cement retarder.
Comparative example 2
The comparative example provides an oil well cement retarder which is prepared by a preparation method comprising the following specific steps:
(1) Respectively weighing 72.4 parts by weight of 2-acrylamido-2-methylpropanesulfonic acid, 17 parts by weight of itaconic acid and 10.6 parts by weight of diethyl 4-vinylbenzylphosphonate, completely dissolving the materials in 140 parts by weight of deionized water, and slowly adding 12.6 parts by weight of sodium hydroxide into the obtained solution to adjust the pH value of the solution to 4-5;
(2) Then, adding 0.4 part by weight of 3-mercaptopropionic acid into the solution obtained in the step (1), and slowly heating to 60 ℃ at a stirring rate of 200r/min plus or minus 20 r/min; and then 1.5 parts by weight of potassium persulfate is dissolved in 10 parts by weight of deionized water, and is slowly dripped into the solution system within 30 minutes, and then the temperature is slowly raised to 80 ℃ at the heating rate of 0.6 ℃/min for continuous reaction for 4 hours, and the solution is naturally cooled to room temperature, so that a viscous liquid polymer solution is obtained, and the oil well cement retarder is obtained.
Comparative example 3
The comparative example provides an oil well cement retarder which is prepared by a preparation method comprising the following specific steps:
(1) Respectively weighing 33.7 parts by weight of 2-acrylamido-2-methylpropanesulfonic acid, 31.8 parts by weight of itaconic acid and 34.5 parts by weight of diethyl 4-vinylbenzylphosphonate, completely dissolving the materials in 140 parts by weight of deionized water, and slowly adding 12.6 parts by weight of sodium hydroxide into the obtained solution to adjust the pH value of the solution to 4-5;
(2) Then, adding 0.4 part by weight of 3-mercaptopropionic acid into the solution obtained in the step (1), and slowly heating to 60 ℃ at a stirring rate of 200r/min plus or minus 20 r/min; dissolving 1.5 parts by weight of potassium persulfate in 10 parts by weight of deionized water, slowly dripping the potassium persulfate into the solution system within about 30min, and slowly heating to 80 ℃ at a heating rate of 0.6 ℃/min for continuous reaction for 4h;
(3) And (3) adding 1.13 parts by weight of sodium sulfite into 264.5 parts by weight of the solution obtained in the step (2) and continuously treating for 30min, and naturally cooling to room temperature to obtain a viscous liquid polymer solution, namely the oil well cement retarder.
The oil well cement retarder comprises a polymer retarder, and the molecular structural formula of the polymer retarder is shown as the formula (1.7):
in the formula (1.7), the ratio of a to b to c is 30:45:25.
Test example 1
The test example comprises the steps of firstly washing the ultra-high temperature oil well cement retarder S1 provided in the embodiment 1 by acetone, then performing vacuum freeze drying to obtain a purified product, and performing infrared spectrum analysis on the purified product, wherein the obtained result is shown in figure 1, and as can be seen from figure 1, 3448cm -1 The peak at the position is the telescopic vibration absorption peak of N-H in AMPS; 2940cm -1 、2984cm -1 The peaks at the positions are respectively-CH 3 and-CH 2 -a telescopic vibration absorption peak; 1723cm -1 The peak at the position is the stretching vibration peak of-COOH group in IA, 1659cm -1 The peak at the position is the stretching vibration peak of-C=O in the amide group in AMPS; 1256cm -1 The peak at p=o characteristic absorption peak; 1012cm -1 The peak at the position is P-O-C characteristic absorption peak, 962cm -1 The peak at the position is the characteristic absorption peak of P-O; 1485cm -1 、1467cm -1 And 1410cm -1 The peak of (C) is the characteristic absorption peak of benzene ring, 726cm -1 The peak at the position is the out-of-plane bending vibration peak of the benzene ring; at 1620-1650cm -1 No c=c characteristic absorption peak was found, indicating that all the comonomer was involved in copolymerization, and example 1 produced a polymer having a molecular structure as shown in formula (1.1).
Test example 2
The test example is based on the oil and gas industry standard SY/T5504.1-2013 evaluation method of oil well Cement Admixture part 1: the comprehensive properties of the retarders prepared in examples 1 to 6 and comparative examples 1 to 3 were evaluated in accordance with the regulations in GB/T19139-2012, oil well cement test method, and the evaluation results are shown in Table 1 and FIGS. 2 to 5.
TABLE 1
Note that: the cement used in the application is Jiahua G-grade oil well cement (high sulfur resistance, HSR). # represents the mass percent of cement, and represents the strength curing temperature of cement stone (experimental temperature +20℃).
The cement paste formulations in Table 1 at 110-180deg.C were: jiahua grade G oil well cement (HSR) +35% silica fume (BWOC, the same applies below) +3% micro silicon+x% retarder+4% fluid loss agent+1.2% dispersant+2% high temperature stabilizer+water;
the cement paste formulations in Table 1 at 200-240℃were: jiahua grade G oil well cement (HSR) +50% silica powder+3% micro silicon+10% anti-fading material+x% retarder+5% fluid loss agent+1.5% dispersant+4% high temperature stabilizer+water, the cement slurry density is 1.88G/cm 3 。
Wherein the silica powder is 200-mesh quartz sand, the grain diameter of the micro-silica is 0.1-0.3 mu m, the fluid loss agent is AMPS multipolymer product, the dispersing agent is deeply sulfonated aldehyde ketone polycondensate, the high-temperature stabilizer is a compound product of the AMPS multipolymer and superfine mineral material, the anti-fading material is high aluminate inorganic mineral material, and all additive products are from China petroleum group engineering institute of technology, inc.
As can be seen from the thickening curve graph of the cement paste with the addition of 1.5% of the ultra-high temperature oil well cement retarder provided by the embodiment 1 of the application at 110 ℃ multiplied by 70MPa shown in fig. 2, the thickening curve of the cement paste is normal, the initial consistency is low, the consistency curve is stable, the system thickening time is 503min, the thickening transition time is short (5 min), and the thickening transition time is basically right-angle thickening, which shows that the ultra-high temperature oil well cement retarder prepared by the embodiment 1 can effectively prolong the thickening time of a medium-temperature cement paste system and has less influence on the development of the mechanical strength of the cement paste.
As can be seen from the thickening curve graph of the cement slurry with the 5% addition of the ultra-high temperature oil well cement retarder at 240 ℃ multiplied by 120MPa, which is shown in the embodiment 1 of the application in the figure 3, the ultra-high temperature cement slurry thickening curve is normal, no abnormal gelation phenomena such as bulges, core inclusion and the like occur, the initial consistency is about 20Bc, and the slurry consistency is reduced along with the temperature rise but is finally maintained at about 10 Bc; the thickening time of the system is 330min, and the thickening curve is basically at a right angle.
As can be seen from the thickening graph of the cement slurry with the addition of 5% of the oil well cement retarder provided in the comparative example 1 shown in fig. 4 at 240 ℃ x 120MPa, the initial consistency of the cement slurry is higher, the consistency gradually decreases along with the temperature rise, the system consistency rapidly rises after the temperature rises to the experimental temperature, the thickening time is 108min, and the thickening time cannot be effectively prolonged along with the addition of the retarder, which indicates that the retarder performance of the oil well cement retarder prepared in the comparative example 1 is ineffective at 240 ℃.
As can be seen from the thickening curve graph of cement slurry with the addition of 2% of the oil well cement retarder provided in the comparative example 2 shown in fig. 5 at 130 ℃ multiplied by 70MPa, the thickening curve of cement slurry has abnormal gelation phenomena such as bulge and core inclusion and the like at about 120 ℃, and the temperature fluctuation is larger, which indicates that in the comparative example 2, the oil well cement retarder prepared without inorganic salt treatment is easy to cause abnormal thickening performance of a cement slurry system, and directly affects the safety of cementing operations such as deep wells and ultra-deep wells.
As can be seen from table 1, in the temperature range of 110-240 ℃, the ultra-high temperature oil well cement retarder S1 prepared in the embodiment 1 of the present application can effectively prolong the cement paste thickening time, and the cement paste thickening time can be linearly adjustable within 200-500min by changing the blending amount of the ultra-high temperature oil well cement retarder, and has a good linear relationship with the temperature and the adding amount; meanwhile, the addition sensitivity of the ultra-high temperature oil well cement retarder is 11.7 percent and 13.6 percent respectively at 130 ℃ and 240 ℃, which both meet the requirement of SY/T5504.1-2013 on addition sensitivityThe degree is less than or equal to 20 percent; in addition, the API water loss of the cement slurry system doped with the ultra-high temperature oil well cement retarder prepared in the embodiment 1 of the application<60mL, and sedimentation stability less than or equal to 0.04g/cm 3 The compressive strength of the cement stone is higher than 30.6MPa. The results show that the ultra-high temperature oil well cement retarder prepared by the embodiment 1 of the application has good compatibility with other additives such as a fluid loss agent and the like, and has small influence on the sedimentation stability of a system and the mechanical strength of cement stones.
From the experimental data in table 1, it can be seen that the ultra-high temperature oil well cement retarders S2-S6 prepared in examples 2-6 of the present application also have good ultra-high Wen Diaoning performance and adaptability, respectively. However, the oil well cement retarder prepared in comparative example 1 shows good setting property at 130 ℃, but when the temperature is 240 ℃, the thickening time of cement paste cannot be prolonged due to failure of the setting property; although the oil well cement retarder prepared in comparative example 2 has good retarder performance at 130 ℃ and 240 ℃, the retarder performance is inferior to that of the ultra-high temperature oil well cement retarder provided in the example, and the thickening curve at high temperature (more than 120 ℃) under low doping amount is easy to have abnormal gelation phenomena such as core inclusion and bulge (shown in figure 5), so that a cement slurry system has a certain construction risk; the method shows that the product obtained after the polymerization reaction is subjected to post-treatment by using the reducing inorganic salt, the molecular conformation can be reformed, and the oxidation initiator in the system is annihilated, so that the quality stability of the polymer product is ensured, and the cement paste high-temperature abnormal gelation caused by the polycarboxylic acid retarder can be further improved and relieved; in addition, the retarder effect of the oil well cement retarder prepared in comparative example 3 is basically consistent with that of the oil well cement retarder provided in comparative example 1, the ultra-high temperature retarder effect is weaker, and the water loss performance of a cement slurry system is adversely affected to a certain extent, mainly because the proportion of each monomer component in the molecular structure of the polymer retarder is unreasonable (namely, the molar ratio of a, b and c in the polymer retarder is not in the numerical range claimed by the application), specifically, the excessive strong adsorbability groups enable the retarder to have stronger competitive adsorption capacity for higher temperature water loss agents, so the water loss performance of the system is poor. Therefore, the ultra-high temperature oil well cement retarder provided by the embodiment of the application has better comprehensive performance than the oil well cement retarder prepared by the comparative example.
In summary, (1) the embodiment of the application improves the ultra-high temperature resistance, the stable coagulation regulating performance and the like of the polymer retarder through the measures of optimal design of a molecular structure, effective intervention of temperature-resistant and salt-resistant rigid groups, synergistic effect of multiple adsorption groups, efficient treatment of reducing inorganic salt and the like. In addition, the introduction of functional groups such as phosphonic acid groups, amino groups, quaternary ammonium salts, imidazole and the like can further improve the charge density of the polymer corrosion inhibitor and promote the ultra-high temperature adsorption stability of the polymer corrosion inhibitor, so that the thickening time of an ultra-high temperature cement slurry system can be effectively regulated and controlled.
(2) The ultra-high temperature oil well cement retarder provided by the embodiment of the application has the advantages of wide application temperature range (70-240 ℃), linearly adjustable cement paste thickening time within 200-500min in a temperature range of 110-240 ℃, good linear relation with temperature and addition, good compatibility with other additives and small influence on the mechanical properties of cement stones.
(3) The ultra-high temperature oil well cement retarder provided by the embodiment of the application has strong adaptability, is suitable for various cement slurry systems with conventional density, low density, high strength and toughness, latex and the like, can effectively ensure the well cementation construction safety, reduces the well cementation operation risk, and meets the well cementation technical requirements of complex and difficult wells such as deep wells, ultra-deep wells, wanmike exploratory wells, high-temperature high-pressure gas wells, unconventional oil gas wells, gas storage wells and the like.
(4) The preparation method of the ultra-high temperature oil well cement retarder provided by the embodiment of the application is simple, green, safe and environment-friendly, has the advantages of easily available raw materials and low production cost, and can realize industrial production and large-scale popularization and application.
The foregoing description of the embodiments of the application is not intended to limit the scope of the application, so that the substitution of equivalent elements or equivalent variations and modifications within the scope of the application shall fall within the scope of the patent. In addition, the technical features and the technical features, the technical features and the technical application can be freely combined for use.
Claims (21)
1. A polymer, which is characterized in that the molecular structural formula of the polymer is shown as a formula (1):
in the formula (1), a, b and c are all mole numbers, and the ratio of the three is 40-85:10-40:5-20;
R 1 is-H, -CH 3 -CH 2 One of COOH;
R 2 one selected from the following compounds:
is->
2. An ultra-high temperature oil well cement retarder, characterized in that the ultra-high temperature oil well cement retarder comprises the polymer as claimed in claim 1 and water, wherein the content of the polymer is 20-40% and the content of the water is 60-80% based on 100% of the total weight of the ultra-high temperature oil well cement retarder.
3. The method for preparing the ultra-high temperature oil well cement retarder according to claim 2, wherein the method comprises the following steps:
(1) Dissolving 2-acrylamido-2-methylpropanesulfonic acid monomer, unsaturated carboxylic acid monomer and rigid unsaturated monomer in deionized water, and adding alkaline substances into the obtained solution to adjust the pH value of the solution to 3-5; wherein the weight ratio of the 2-acrylamide-2-methylpropanesulfonic acid monomer, the unsaturated carboxylic acid monomer and the rigid unsaturated monomer is 45-92:4-32:4-30;
(2) Adding a chain transfer agent into the system obtained in the step (1), heating, adding an initiator, and continuously heating to perform polymerization reaction;
(3) And (3) adding a reducing inorganic salt into the solution obtained after the reaction in the step (2) to carry out aftertreatment, and obtaining a viscous liquid polymer solution after the aftertreatment is finished, namely the ultra-high temperature oil well cement retarder.
4. The method according to claim 3, wherein in the step (1), the unsaturated carboxylic acid monomer comprises one or a combination of several of itaconic acid, methacrylic acid, acrylic acid and crotonic acid.
5. The method according to claim 3 or 4, wherein in the step (1), the rigid unsaturated monomer comprises one or a combination of several of diethyl 4-vinylbenzylphosphonate, 2' - (4-vinylbenzylamino) diacetic acid, vinylbenzyltrimethylammonium chloride and N- (4-vinylbenzyl) -N, N-dimethylamine.
6. The method according to claim 3 or 4, wherein in the step (1), the alkaline substance comprises sodium hydroxide in an amount of 10 to 20 parts by weight.
7. A process according to claim 3, wherein in step (2), the chain transfer agent is used in an amount of 0.05 to 1.0% by mass based on the total mass of the monomers.
8. The production method according to claim 3 or 7, wherein in the step (2), the chain transfer agent comprises one or more of 3-mercaptopropionic acid, 3-mercaptoacetic acid, mercaptoethanol, n-butylmercaptan, n-dodecylmercaptan, and isopropanol.
9. A process according to claim 3, wherein in step (2) the initiator is used in an amount of 0.5 to 2.5% by weight based on the total mass of the monomers.
10. The method of claim 3 or 9, wherein in step (2), the initiator comprises one or more of ammonium persulfate, potassium persulfate, and azobisiso Ding Mi hydrochloride.
11. The process according to claim 3, wherein in the step (2), a chain transfer agent is added to the system obtained in the step (1), and the temperature is raised to 50 to 65℃and kept at the temperature for 10 to 30 minutes.
12. A method of preparing according to claim 3, wherein in step (2), the continuing to raise the temperature to effect the polymerization reaction comprises: heating to 70-90 ℃ and reacting for 2-5h at constant temperature.
13. The method according to claim 12, wherein the temperature rise rate of the temperature rise is 0.5 to 2 ℃/min.
14. The process according to claim 3, wherein in the step (3), the amount of the reducing inorganic salt is 0.2 to 1.0% by mass of the total mass of the solution obtained after the reaction in the step (2).
15. The method according to claim 3 or 14, wherein in the step (3), the reducing inorganic salt comprises one or more of sodium sulfite, sodium hydrogen sulfite, ammonium sulfite, potassium sulfite and potassium hydrogen sulfite.
16. The method according to claim 3 or 14, wherein in step (3), the post-treatment is performed for 30 to 60 minutes.
17. The method of claim 3 or 14, wherein step (3) further comprises: and after finishing the post-treatment, naturally cooling the system to room temperature to obtain a viscous liquid polymer solution, namely the ultra-high temperature oil well cement retarder.
18. Use of the polymer of claim 1 or the ultra-high temperature oil well cement retarder of claim 2 in complex operating well cementing operations.
19. The use of claim 18, wherein the complex operating well comprises a deep well, ultra-deep well, myriad meter scientific drilling well, high temperature high pressure well, unconventional oil well, or gas reservoir well.
20. A cement slurry comprising the polymer of claim 1 or the ultra-high temperature oil well cement retarder of claim 2.
21. A cement slurry according to claim 20, wherein the ultra-high temperature oil well cement retarder is added in an amount of 1.5-6.5% based on 100% by weight of the total cement contained in the cement slurry.
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