CN117210216B - Instant ultrahigh Wen Jiaoning acid resistant and preparation method thereof - Google Patents
Instant ultrahigh Wen Jiaoning acid resistant and preparation method thereof Download PDFInfo
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- CN117210216B CN117210216B CN202311483872.3A CN202311483872A CN117210216B CN 117210216 B CN117210216 B CN 117210216B CN 202311483872 A CN202311483872 A CN 202311483872A CN 117210216 B CN117210216 B CN 117210216B
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- 239000002253 acid Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 132
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 77
- 239000000725 suspension Substances 0.000 claims abstract description 41
- 239000000178 monomer Substances 0.000 claims abstract description 26
- -1 iron ion Chemical class 0.000 claims abstract description 11
- 239000000654 additive Substances 0.000 claims abstract description 8
- 230000000996 additive effect Effects 0.000 claims abstract description 8
- 238000005260 corrosion Methods 0.000 claims abstract description 8
- 230000007797 corrosion Effects 0.000 claims abstract description 8
- 239000003112 inhibitor Substances 0.000 claims abstract description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 239000003381 stabilizer Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 20
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 19
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 18
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 14
- 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 12
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 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 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 235000010265 sodium sulphite Nutrition 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 5
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 3
- 150000007942 carboxylates Chemical class 0.000 claims description 3
- 239000002262 Schiff base Substances 0.000 claims description 2
- 150000004753 Schiff bases Chemical class 0.000 claims description 2
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 2
- 229960003237 betaine Drugs 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 150000002462 imidazolines Chemical class 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims 1
- 229920002401 polyacrylamide Polymers 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 230000009466 transformation Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 47
- 238000006243 chemical reaction Methods 0.000 description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 238000006116 polymerization reaction Methods 0.000 description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 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 description 18
- 239000003999 initiator Substances 0.000 description 17
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- 239000002562 thickening agent Substances 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 230000000977 initiatory effect Effects 0.000 description 10
- 239000012966 redox initiator Substances 0.000 description 10
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- VWSLLSXLURJCDF-UHFFFAOYSA-N 2-methyl-4,5-dihydro-1h-imidazole Chemical compound CC1=NCCN1 VWSLLSXLURJCDF-UHFFFAOYSA-N 0.000 description 8
- 230000001105 regulatory effect Effects 0.000 description 8
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000012295 chemical reaction liquid Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- FWFUWXVFYKCSQA-UHFFFAOYSA-M sodium;2-methyl-2-(prop-2-enoylamino)propane-1-sulfonate Chemical group [Na+].[O-]S(=O)(=O)CC(C)(C)NC(=O)C=C FWFUWXVFYKCSQA-UHFFFAOYSA-M 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000004202 carbamide Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 239000012085 test solution Substances 0.000 description 5
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 4
- 229940045803 cuprous chloride Drugs 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 239000006184 cosolvent Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 3
- 229940001584 sodium metabisulfite Drugs 0.000 description 3
- 235000010262 sodium metabisulphite Nutrition 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- SXAMGRAIZSSWIH-UHFFFAOYSA-N 2-[3-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,2,4-oxadiazol-5-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NOC(=N1)CC(=O)N1CC2=C(CC1)NN=N2 SXAMGRAIZSSWIH-UHFFFAOYSA-N 0.000 description 1
- ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2 ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 0.000 description 1
- OPRIWFSSXKQMPB-UHFFFAOYSA-N 2-methyl-2-(prop-2-enoylamino)propane-1-sulfonic acid;sodium Chemical compound [Na].OS(=O)(=O)CC(C)(C)NC(=O)C=C OPRIWFSSXKQMPB-UHFFFAOYSA-N 0.000 description 1
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001409 amidines Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229940116335 lauramide Drugs 0.000 description 1
- ILRSCQWREDREME-UHFFFAOYSA-N lauric acid amide propyl betaine Natural products CCCCCCCCCCCC(N)=O ILRSCQWREDREME-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000012224 working solution Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses an instant ultrahigh Wen Jiaoning acid resistant and a preparation method thereof, and belongs to the technical field of oil and gas exploitation polymers. The gel acid takes suspension of polyacrylamide derivatives as a main agent, the mole ratio of a functional monomer 2-acrylamide-2-methylpropanesulfonic acid sodium unit in the structure of the polyacrylamide derivatives is 25-100%, the polymer suspension can be uniformly dispersed and quickly swelled and dissolved in hydrochloric acid solution, and an ultra-high Wen Jiaoning acid-resistant system is obtained after corrosion inhibitor, cleanup additive and iron ion stabilizer are added. The instant ultrahigh Wen Jiaoning acid can be completely dissolved in hydrochloric acid solution for 5 min, and the temperature resistance can be up to 200 ℃. The invention solves the problems that the current gelled acid system has poor temperature resistance, can not be used for deep and ultra-deep reservoir transformation, has poor dispersibility of a polymer in a hydrochloric acid solution and is slow to dissolve, and provides the gelled acid system which has excellent temperature resistance and can be rapidly prepared.
Description
Technical Field
The invention belongs to the technical field of oil and gas exploitation polymers, and particularly relates to an instant ultrahigh Wen Jiaoning acid resistant and a preparation method thereof.
Background
Acidizing and fracturing are key measures for improving the yield of carbonate reservoirs, acid liquor with certain viscosity is used as a medium, and diversion channels are formed by eroding the carbonate rock stratum so as to improve the permeability of the stratum and achieve the purpose of yield increase. The gelled acid is the most widely used acidic working solution, and is formed into high-viscosity acidic liquid by taking hydrochloric acid with a certain concentration as a solvent and adding a thickening agent. Polymers are commonly used thickeners, whose network structure formed upon dissolution in hydrochloric acid solution impedes the movement of hydrogen ions in solution, resulting in a decrease in their diffusion rate. Therefore, the reaction rate of the gelled acid with the core is slowed down when the gelled acid is used for fracturing reformation, so that the acting distance is increased.
In recent years, with the development and exploration of oil gas gradually oriented to deep and ultra-deep reservoirs, new requirements are put on the performance of a gelled acid system. The well temperature of deep and ultra-deep reservoirs is usually over 160 ℃, and under the condition, the polymer in the gelled acid can be hydrolyzed under the double functions of high hydrogen ion concentration and high temperature environment to flocculate and precipitate, so that the gelled acid is disabled. The main means for solving the problem is to increase the content of functional monomers with excellent temperature resistance, such as 2-acrylamido-2-methylpropanesulfonic acid, in the thickener structure so as to slow down the hydrolysis rate of the thickener under the condition of high temperature and strong acid, and ensure that the thickener still can keep good rheological property under the condition of high temperature and strong acid.
In addition, in the preparation process of the gelled acid, the polymer particles have poor dispersibility in hydrochloric acid solution due to higher hydrochloric acid concentration, and are easy to agglomerate to cause slow swelling. The solution to this problem has been to develop polymeric suspending agents that disperse and swell rapidly.
Disclosure of Invention
The invention aims to provide an instant ultrahigh Wen Jiaoning acid resistant acid and a preparation method thereof, aiming at the problems that the current gelled acid system has poor temperature resistance, can not be used for deep and ultra-deep reservoir transformation, has poor dispersibility of a polymer in a hydrochloric acid solution and is slow to dissolve, so as to obtain the gelled acid system which has excellent temperature resistance and can be rapidly prepared.
The invention takes suspension liquid of polyacrylamide derivatives as a main agent, the mole ratio of a functional monomer 2-acrylamide-2-methylpropanesulfonic acid sodium unit in the structure of the polyacrylamide derivatives is 25-100%, the polymer suspension liquid can be uniformly dispersed and quickly swelled and dissolved in hydrochloric acid solution, and an ultra-high Wen Jiaoning acid-resistant system is obtained after corrosion inhibitor, cleanup additive and iron ion stabilizer are added. The instant ultrahigh Wen Jiaoning acid can be completely dissolved in hydrochloric acid solution for 5 min, and the temperature resistance can be up to 200 ℃. The method for preparing the instant ultrahigh Wen Jiaoning acid resistant acid has the advantages of mild reaction conditions and simple production process, and is suitable for large-scale production.
The invention provides instant ultrahigh Wen Jiaoning acid resistant acid, which comprises the following components in parts by mass:
1-5 parts of polymer suspension liquid,
1-5 parts of corrosion inhibitor,
0.5 to 2 parts of cleanup additive,
0.5 to 2 parts of iron ion stabilizer,
86-97 parts of hydrochloric acid solution;
the polymer is a polyacrylamide derivative, preferably a copolymer of acrylamide and/or acrylic acid and 2-acrylamide-2-methylpropanesulfonic acid, or a homopolymer of 2-acrylamide-2-methylpropanesulfonic acid, and the molar content of a functional monomer 2-acrylamide-2-methylpropanesulfonic acid unit in the structure is 25% -100%; preferably, the molecular weight of the polymer is 1000-2000 ten thousand.
Further, the mass content of the polymer in the polymer suspension is 20% -50%.
Further, the polymer suspension is obtained by dispersing the polymer powder in a dispersion of a liquid, such as mineral oil, having a viscosity capable of dispersing and suspending the polymer powder to form a uniform and stable suspension.
The polymer suspension enables the polymer to be used as a thickening agent to be rapidly dispersed and dissolved in the hydrochloric acid solution, and solves the problems that the thickening agent is slow in dissolution rate and easy to form fish eyes in high-concentration hydrochloric acid.
Further, the mass content of the polymer in the gelled acid is preferably 0.5% -2.0%.
Further, the corrosion inhibitor is one or two of imidazolines, thiourea and Schiff bases, preferably 2-methylimidazoline.
Further, the cleanup additive is any one or two of alkyl sulfonate and betaine, preferably sodium dodecyl sulfonate or lauramide propyl hydroxysulfobetaine.
Further, the iron ion stabilizer is any one or more of a reducing agent, an organic carboxylate and an amino carboxylate; the reducing agent is preferably sodium sulfite, the organic carboxylate is preferably low molecular weight sodium polyacrylate, and the amino carboxylate is preferably sodium ethylenediamine tetraacetate.
Further, the mass concentration of the hydrochloric acid solution (or hydrochloric acid) is preferably 5% -30%.
The invention also provides a preparation method of the instant ultrahigh Wen Jiaoning acid resistant acid, which comprises the following steps:
and (3) dissolving the polymer suspension, the cleanup additive, the corrosion inhibitor and the iron ion stabilizer in the hydrochloric acid solution according to the component proportion, and obtaining the instant ultrahigh Wen Jiaoning acid-resistant solution after the polymer is completely dissolved.
In the above technical scheme of the invention, the polymer is a copolymer of acrylamide and/or acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid, or a homopolymer of 2-acrylamido-2-methylpropanesulfonic acid, preferably a polymer prepared by the following structural formula and the following method.
The polymer has the following structural general formula:
wherein a, b and c represent the mole percentage of the corresponding structural units in the three structural units of the polymer, a: b: c= (0-75): (0-25): (25-100), and a+b+c=100%, and the viscosity average molecular weight of the polymer is preferably 1000-2500 ten thousand.
The polymer is prepared by the following method:
(1) Mixing 2-acrylamido-2-methylpropanesulfonic acid and acrylic acid with deionized water, and stirring until the solid is completely dissolved;
(2) Adding a pH regulator into the solution obtained in the step (1), and regulating the pH value to be 5.0-10.0;
(3) Adding acrylamide and cosolvent into the solution obtained in the step (2) for mixing, and simultaneously adding deionized water and stirring until the solid is completely dissolved to obtain a reaction solution;
(4) Transferring the obtained reaction liquid into a reaction container, regulating the reaction temperature to an initiation temperature, introducing nitrogen into the reaction container to remove oxygen, and sequentially adding a redox initiator, a chain transfer agent, a high-temperature initiator and a co-initiator under the condition of introducing nitrogen to perform polymerization reaction, wherein the initiation temperature is-10-50 ℃, and the mass ratio of a low-temperature redox initiator to a high-temperature initiator is (0.01-10): 1, a step of;
(5) After polymerization, granulating, drying and crushing to obtain a polymer product.
Wherein, the mixture ratio of the raw material components is as follows: 100-400 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid, 0-50 parts by mass of acrylic acid, 20-78 parts by mass of pH regulator, 0-150 parts by mass of acrylamide, 0-20 parts by mass of cosolvent, 0.001-0.2 part by mass of low-temperature redox initiator, 0-1.0 part by mass of chain transfer agent, 0.001-0.1 part by mass of auxiliary initiator and 0.001-0.1 part by mass of high-temperature initiator; and the mass of the 2-acrylamido-2-methylpropanesulfonic acid in the monomer is 50% -100% of the total mass of the 2-acrylamido-2-methylpropanesulfonic acid, the acrylic acid and the acrylamide.
The chain transfer agent is one of sodium formate, sodium hypophosphite and isopropanol; the auxiliary initiator is any one of organic micromolecular amines, cuprous salts and ferrous salts, preferably N, N, N ', N' -tetramethyl ethylenediamine and cuprous chloride; the cosolvent is urea; the pH regulator is preferably any one of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.
In the method, the low-temperature redox initiator is any one or more of ammonium persulfate, potassium persulfate, tert-butyl hydroperoxide, sodium bisulphite, sodium metabisulfite and sodium sulfite; the high-temperature initiator is a water-soluble azo initiator, preferably any one of azo diisobutyl amidine hydrochloride, azo diiso Ding Mi hydrochloride and azo diisopropylimidazoline. The mass ratio of the low-temperature redox initiator to the high-temperature initiator is preferably (0.005-3): 1, more preferably (0.005 to 2): 1.
the copolymer with the molecular weight of more than 1000 ten thousand and the molar content of 2-acrylamido-2-methylpropanesulfonic acid of more than 50% is difficult to prepare due to the large steric hindrance and the large reactivity of the 2-acrylamido-2-methylpropanesulfonic acid, and no example is reported so far. The invention combines low-temperature initiation and high-temperature initiation, and can realize the synthesis of the ultra-high molecular weight high-functional monomer content copolymer by reasonably proportioning (0.05-2) the low-temperature redox initiator and the high-temperature initiator and combining the regulation and control of the initiation temperature. Because of the larger space position of the functional monomer and the influence of electronic effect, the energy required by the initiator to initiate the functional monomer is higher, and the polymer of the functional monomer is mainly in a high-temperature stage. Therefore, when the ratio of the low-temperature redox initiator to the high-temperature initiator is less than 0.05, the heat released in the low-temperature initiation stage is insufficient to decompose the high-temperature initiator, and the polymerization of the functional monomer cannot be initiated, so that the re-growth of the molecular chain cannot be realized; when the ratio is more than 2, the number of initial molecular chains initiated at a low temperature stage increases, so that the number of monomers per molecular chain decreases, thereby decreasing the molecular weight of the polymer. The polymer with the molecular weight of over 1500 ten thousand can be prepared by controlling the dosage and the proportion of the low-temperature redox initiator and the high-temperature initiator and the regulation and control of the monomer, other auxiliary agents and the initiation temperature, wherein the molar content of the functional monomer 2-acrylamide-2-methylpropanesulfonic acid is over 50 percent.
In the method, the initiation temperature in the step (4) is preferably 5-20 ℃, and the occurrence probability of chain transfer and chain termination is reduced at the initiation temperature of 5-20 ℃, so that the chain growth probability is increased, thereby being beneficial to forming long-chain macromolecules; after the reaction is carried out to a certain extent, the temperature of the reaction system is increased, the high-temperature initiator is activated, the reaction is initiated again, and the re-growth of the molecular chain is realized. By combining the control of the ratio of the low-temperature redox initiator to the high-temperature initiator and the regulation and control of the monomer and other auxiliary agents, the polymer with ultra-high molecular weight (molecular weight more than 1000 ten thousand) and/or ultra-high functional monomer content (functional monomer mass content more than 50%) can be obtained. When the initiation temperature is 5-20 ℃, and the mass ratio of the low-temperature redox initiator to the high-temperature initiator is (0.05-2): 1. when the monomer ratio is regulated, the ultra-high molecular weight high functional monomer content polymer with the molar ratio of 2-acrylamide-2-methylpropanesulfonic acid being more than 50 percent and the molecular weight being more than 1000 ten thousand, even 1500 ten thousand can be obtained.
In the method, after the granulation in the step (5), inorganic alkali can be added for post-hydrolysis, wherein the inorganic alkali is one of sodium hydroxide or potassium hydroxide, and the post-hydrolysis is carried out by uniformly mixing the granulated polymer with the inorganic alkali and then placing the mixture in an oven at 80 ℃ for reaction. The mass ratio of the deionized water in the step (1) and the step (2) is 200-400 parts by mass.
Compared with the prior art, the invention has the following beneficial effects and characteristics:
1. the temperature resistance of the gelled acid is obviously improved. The temperature resistance of the gelled acid is generally 160 ℃, and the gelled acid which meets the requirement for a reservoir with higher well temperature is not yet reported. Compared with the existing gelled acid, the instant ultrahigh Wen Jiaoning acid resistant polymer (thickener) prepared by the invention increases the content of 2-acrylamide-2-methylpropanesulfonic acid units in the molecular structure, and inhibits the hydrolysis rate of the thickener in high-temperature and high-acid environments, thereby improving the temperature resistance of the gelled acid. The instant ultrahigh Wen Jiaoning acid resistant has the viscosity of more than 20 mPa.s after being sheared for 90 min at the constant temperature of 200 ℃, and the sheared solution is in a uniform state and does not split phases. The instant ultrahigh Wen Jiaoning acid resistant acid has excellent temperature resistance, and can be used in the oilfield acidizing fracturing transformation technology.
2. Realizes the rapid preparation of the gelled acid. In the existing gelled acid preparation technology, polymer solid particles are directly added into hydrochloric acid solution, so that polymer agglomeration phenomenon can occur, and the polymer swelling process is slow and insufficient in dissolution. The method of the invention takes polymer suspension as a main agent, and utilizes the characteristic that the polymer can be uniformly dispersed in the suspension to realize rapid swelling and dissolution of the polymer in hydrochloric acid solution.
3. The method is simple, quick and efficient, and is suitable for large-scale industrial production.
Drawings
Fig. 1 is a photograph of a polymer suspension (a) and a polymer powder (b) after dissolution in hydrochloric acid of 0.5. 0.5 h.
FIG. 2 is a graph showing the temperature and shear resistance test (170 s) of the sample of example 1 -1 30-200 ℃ result diagram.
FIG. 3 is a graph showing the temperature and shear resistance test (170 s) of the sample of example 5 -1 30-200 ℃ result diagram.
FIG. 4 is a graph showing the temperature and shear resistance test (170 s) of the sample of example 7 -1 30-160 ℃ result graph.
FIG. 5 is a graph showing the temperature and shear resistance test (170 s) of the sample of example 8 -1 30-160 ℃ result graph.
FIG. 6 is a nuclear magnetic resonance spectrum of the polymer in example 2.
FIG. 7 is a nuclear magnetic resonance spectrum of the polymer in example 5.
Detailed Description
The invention will be further described with reference to specific examples. The following examples are only for more clearly illustrating the technical aspects of the present invention, and are not intended to limit the scope of the present invention.
Example 1
5.0 g g polymer suspension, 2.0 g 2-methylimidazoline, 0.5 g sodium dodecyl sulfonate and 0.5 g sodium sulfite are added into a hydrochloric acid solution with the mass concentration of 92.0 and g percent and 20 percent, and after the polymer is completely dissolved, a gelled acid solution with the mass concentration of 2.0 percent of the polymer is obtained. The polymer suspension used had a mass content of 40% and a molar content of sodium 2-acrylamido-2-methylpropanesulfonate units in the polymer structure of 50% and a molecular weight of 1500 ten thousand.
The polymer in this example was prepared by the following method:
(1) 186 g of 2-acrylamido-2-methylpropanesulfonic acid, 20 g acrylic acid and 398, 398 g deionized water were placed in a 2000 mL beaker and stirred until the solids dissolved;
(2) 47 g sodium hydroxide was added to the beaker with stirring and the test solution ph=8.6;
(3) Adding 44 g acrylamide and 5 g urea into a beaker, adding 300 g deionized water, and stirring until the solid is completely dissolved;
(4) Transferring the reaction liquid into a 2000 mL reaction container, and regulating the temperature of a reaction system to 5 ℃; introducing nitrogen for 15 min to remove oxygen in the system, and sequentially adding tert-butyl hydroperoxide 0.001 g, sodium metabisulfite 0.001 g, cuprous chloride 0.01 g and azodiiso Ding Mi hydrochloride 0.01 g into a reaction vessel to perform polymerization reaction; stopping introducing nitrogen for 10 min, starting polymerization of the polymerization system, heating, and continuing to react after the temperature of the polymerization system reaches 50 ℃ and the temperature of the polymerization system reaches 2 h and is 5-6 h;
(5) Granulating, drying and crushing after the polymerization reaction is completed to obtain a polymer product. The viscosity average molecular weight of the polymer is 1500 ten thousand measured by a viscosity method, and the molar content of the functional monomer 2-acrylamide-2-methylpropanesulfonic acid unit in the polymer is 50.1 percent measured by nuclear magnetic resonance hydrogen spectrum.
Example 2
5.0 g g polymer suspension, 5.0 g 2-methylimidazoline, 2.0 g sodium dodecyl sulfonate and 2.0 g sodium sulfite are added into 86.0 g mL hydrochloric acid solution with mass concentration of 30%, and after the polymer is completely dissolved, the gelled acid solution with mass concentration of 2.0% of the polymer is obtained. The polymer suspension used had a polymer mass content of 40% and a molar ratio of sodium 2-acrylamido-2-methylpropanesulfonate units in the polymer structure of 50% and a viscosity average molecular weight of 1200 ten thousand.
The polymer in this example was prepared by the following method:
(1) 186 g of 2-acrylamido-2-methylpropanesulfonic acid and 400 g deionized water were placed in a 2000 mL beaker and stirred until the solids dissolved;
(2) Slowly add 36 g sodium hydroxide to the beaker with stirring, test solution ph=7.8;
(3) 64 g acrylamide is added into a beaker, and 310 g deionized water is added and stirred until the solid is completely dissolved;
(4) Transferring the reaction liquid into a 2000 mL reaction container, and regulating the temperature of a reaction system to be 2 ℃; introducing nitrogen for 15 min to remove oxygen in the system, and sequentially adding isopropanol 0.01, g, tert-butyl hydroperoxide 0.1, g, sodium metabisulfite 0.1, g, triethylamine 0.01, g and azodiisobutylamidine hydrochloride 0.1, g into a reaction container; stopping introducing nitrogen for 10 min, starting polymerization of the polymerization system, heating, and continuing to react at a temperature of 2 h polymerization system reaching 55 ℃ for 5-6 h;
(5) Granulating, drying and crushing after the polymerization reaction is completed to obtain a polymer product; the viscosity average molecular weight of the polymer is 1200 ten thousand measured by a viscosity method, and the molar content of the functional monomer 2-acrylamide-2-methylpropanesulfonic acid unit in the polymer is 50.0 percent measured by nuclear magnetic resonance hydrogen spectrum. Nuclear magnetic resonance spectroscopy analysis is shown in fig. 6: letters marked in the molecular structure respectively correspond to corresponding positions on the nuclear magnetic patternHChemical shift of (c). Only acrylamide and 2-acrylamido-2-methylpropanesulfonic acid were present in the molecular structure, so a+c=100, a+n+c p=2.0 and q c=2.0 were obtained from the molecular structure analysis and integration results, and 2p=2n=q was found from the molecular structure characteristics, and a=50 and c=50 were calculated by combining the above equations, so the molar content of the functional monomer 2-acrylamido-2-methylpropanesulfonic acid unit in example 2 was 50.0%.
Example 3
5.0 g polymer suspension, 2.0 g thiourea, 0.5 g sodium dodecyl sulfonate and 0.5 g sodium acetate are added into 5% hydrochloric acid solution with the mass concentration of 92 g, and after the polymer is completely dissolved, the gelled acid solution with the mass concentration of 1.0% of the polymer is obtained. The suspension used had a polymer mass content of 20% and a molar ratio of sodium 2-acrylamido-2-methylpropanesulfonate units in the polymer structure of 25% and a viscosity average molecular weight of 2500 ten thousand.
The polymer in this example was prepared by the following method:
(1) 123 g of 2-acrylamido-2-methylpropanesulfonic acid and 400 g deionized water were placed in a 2000 mL beaker and stirred until the solids dissolved;
(2) 24 g sodium hydroxide was added to the beaker with stirring and the test solution ph=8.0;
(3) 127 g acrylamide and 20 g urea are added into a beaker, and 316 g deionized water is added and stirred until the solids are completely dissolved;
(4) Transferring the reaction liquid into a 2000 mL reaction container, and regulating the temperature of a reaction system to 5 ℃; introducing nitrogen for 15 min to remove oxygen in the system, and sequentially adding ammonium persulfate 0.005 and g, sodium bisulphite 0.01 and g, cuprous chloride 0.01 and g and azodiiso Ding Mi hydrochloride 0.01 and g into a reaction container; stopping introducing nitrogen; after 5 min, the polymerization system starts to polymerize and heat, the temperature of the polymerization system reaches 60 ℃, and the reaction is continued for 4-5 h;
(5) Granulating, drying and crushing after the polymerization reaction is completed to obtain a polymer product; the viscosity average molecular weight of the polymer is 2500 ten thousand measured by a viscosity method, and the molar content of the functional monomer 2-acrylamide-2-methylpropanesulfonic acid unit in the polymer is 25.0 percent measured by nuclear magnetic resonance hydrogen spectrum.
Example 4
5.0 g polymer suspension, 2.0 g alkyl imidazoline, 0.5 g sodium dodecyl sulfonate and 0.5 g thiourea are added into 30% hydrochloric acid solution with the mass concentration of 92 g, and after the polymer is completely dissolved, a gelled acid solution with the mass concentration of 1.5% of the polymer is obtained, wherein the mass content of the polymer in the suspension is 30%, and the molar ratio of 2-acrylamide-2-sodium methylpropanesulfonate units in the polymer structure is 100%.
The polymer in this example was prepared by the following method:
(1) 400 g of 2-acrylamido-2-methylpropanesulfonic acid and 300 g deionized water were placed in a 2000 mL beaker and stirred until the solids dissolved;
(2) Slowly add 77.5 g sodium hydroxide to the beaker with stirring, test solution ph=8.2;
(3) Adding 5 g urea into a beaker, adding 217.5 g deionized water, and stirring until the solid is completely dissolved to obtain a reaction solution;
(4) Transferring the reaction liquid into a 2000 mL reaction container, and regulating the temperature of a reaction system to 10 ℃; introducing nitrogen for 15 min to remove oxygen in the system, and sequentially adding 1.0 g of sodium hypophosphite, 0.005 g of potassium persulfate, 0.01 g of sodium sulfite, 0.01 g of N, N' -tetramethyl ethylenediamine and 0.01 g of azodiisobutylamidine hydrochloride into a reaction container; stopping introducing nitrogen for 30 min, starting polymerization of the polymerization system, heating, and continuing to react for 7-8 h when the temperature of the polymerization system reaches 45 ℃ at 3 h;
(5) Granulating, drying and crushing after the polymerization reaction is completed to obtain a polymer product; the viscosity average molecular weight of the polymer is 100 ten thousand as measured by a viscosity method, and the molar content of the functional monomer 2-acrylamide-2-methylpropanesulfonic acid unit in the polymer is 100.0% as measured by nuclear magnetic resonance hydrogen spectrum.
Example 5
5.0 g g polymer suspension, 3.0 g 2-methylimidazoline, 0.5 g sodium dodecyl sulfonate and 0.5 g thiourea are added into a hydrochloric acid solution with the mass concentration of 91 g and 20%, and after the polymer is completely dissolved, a gelled acid solution with the mass concentration of 2.0% of the polymer is obtained. The polymer mass content in the suspension used was 40% and the molar ratio of the sodium 2-acrylamido-2-methylpropanesulfonate units in the polymer structure was 75% with a viscosity average molecular weight of 1200 ten thousand.
The polymer in this example was prepared by the following method:
(1) 225 g of 2-acrylamido-2-methylpropanesulfonic acid and 400 g deionized water were placed in a 2000 mL beaker and stirred until the solids dissolved;
(2) Slowly add 43.5 g sodium hydroxide to the beaker with stirring, test solution ph=8.0;
(3) 25 g acrylamide and 5 g urea are added into a beaker, and 301.5 g deionized water is added and stirred until the solid is completely dissolved;
(4) Transferring the reaction liquid into a 2000 mL reaction container, and regulating the temperature of a reaction system to 20 ℃; introducing nitrogen for 15 min to remove oxygen in the system, and sequentially adding tert-butyl hydroperoxide 0.005 and g, sodium sulfite 0.01 and g, cuprous chloride 0.1 and g and azodiiso Ding Mi hydrochloride 0.05 and g into a reaction container; stopping introducing nitrogen; 20 After the min, the polymerization system starts to polymerize and heat, the temperature of the polymerization system reaches 50 ℃, the reaction is continued for 6 to 7 h,
(5) Granulating, drying and crushing after polymerization to obtain a polymer product; the viscosity average molecular weight of the polymer is 1200 ten thousand measured by a viscosity method, and the molar content of the functional monomer 2-acrylamide-2-methylpropanesulfonic acid unit in the polymer is 75.0 percent measured by nuclear magnetic resonance hydrogen spectrum. Nuclear magnetic resonance spectroscopy analysis is shown in fig. 7: letters marked in the molecular structure respectively correspond to corresponding positions on the nuclear magnetic patternHChemical shift of (c). Only acrylamide and 2-acrylamido-2-methylpropanesulfonic acid were present in the molecular structure, so a+c=100, a+n+c=p=2.0 and q=c=3.0 were obtained from the molecular structure analysis and integration results, and 2p=2n=q was found from the molecular structure characteristics, and a=25 and c=75 were calculated by combining the above equations, so the molar content of the functional monomer 2-acrylamido-2-methylpropanesulfonic acid unit in example 6 was 75.0%.
Example 6
1.0 g polymer suspension, 1.0 g of 2-methylimidazoline, 0.5 g sodium dodecyl sulfonate and 0.5 g thiourea are added into a hydrochloric acid solution with the mass concentration of 97 g and 25%, and after the polymer is completely dissolved, a gelled acid solution with the mass concentration of 0.5% of the polymer is obtained, wherein the mass content of the polymer in the suspension is 50%, the molar ratio of 2-acrylamido-2-sodium methylpropanesulfonate units in the polymer structure is 100%, and the viscosity average molecular weight is 100 ten thousand.
Example 7
5.0 g g polymer suspension, 2.0 g 2-methylimidazoline, 0.5 g sodium dodecyl sulfonate and 0.5 g thiourea are added into a hydrochloric acid solution with the mass concentration of 92 and g percent and a gelled acid solution with the mass concentration of 1.5 percent of the polymer is obtained after the polymer is completely dissolved. The suspension used had a polymer mass content of 30% and a molar ratio of sodium 2-acrylamido-2-methylpropanesulfonate units in the polymer structure of 50% and a viscosity average molecular weight of 1500 ten thousand.
Example 8
5.0 g g polymer suspension, 2.0 g 2-methylimidazoline, 0.5 g sodium dodecyl sulfonate and 0.5 g thiourea are added into a hydrochloric acid solution with the mass concentration of 92 and g percent and a gelled acid solution with the mass concentration of 1.5 percent of the polymer is obtained after the polymer is completely dissolved. The polymer mass content in the suspension used was 30% and the molar ratio of the sodium 2-acrylamido-2-methylpropanesulfonate units in the polymer structure was 75% with a viscosity average molecular weight of 1200 ten thousand.
Example 9
2.5 g g polymer suspension, 2.0 g 2-methylimidazoline, 0.5 g sodium dodecyl sulfonate and 0.5 g thiourea are added into a hydrochloric acid solution with the mass concentration of 100 mL and 30%, and after the polymer is completely dissolved, a gelled acid solution with the mass concentration of 1.0% of the polymer is obtained. The mass content of the polymer in the used suspension is 40%, the molar ratio of the 2-acrylamido-2-methylpropanesulfonic acid sodium in the polymer structure is 75%, and the viscosity average molecular weight is 1200 ten thousand.
Example 10
The dissolution performance test of the instant high-temperature-resistant gelled acid comprises the following steps:
(1) Adding 37% hydrochloric acid into a 100 mL blue mouth bottle, and adding water to dilute to 20%; (2) 2.5 g of the polymer suspension was added to 50g of 20% hydrochloric acid solution, while the same mass of polymer powder as the polymer in the suspension was added to another 50g mass concentration of 20% hydrochloric acid solution as a comparison, stirring was started and timing was started, and the time required for complete dissolution of the polymer was observed, and the comparison result is shown in FIG. 1. It can be seen that the polymer suspension was completely dissolved after 0.5. 0.5 h in hydrochloric acid, while the polymer powder remained undissolved particles after 0.5. 0.5 h, indicating that the polymer suspension dissolved faster.
Example 11
Temperature and shear resistance test of example 1:
the gelled acid solution obtained in example 1 was poured into a measuring cup and set to a shear rate of 170 s -1 The temperature is 30-200 ℃, and the temperature is raised to 200 ℃ and then the mixture is sheared for 90 min at constant temperature.
The test result is shown in figure 2, the final viscosity of the gelled acid solution is 48 mPas, which is far higher than the requirement of industry standard SY/T6214-1996 evaluation method of acid thickener (more than or equal to 20 mPas), and the gelled acid system can be used for acidizing and fracturing at 200 ℃.
Example 12
Temperature and shear resistance test of example 5:
the gelled acid solution obtained in example 5 was poured into a measuring cup and set to a shear rate of 170 s -1 The temperature is 30-200 ℃, and the temperature is raised to 200 ℃ and then the mixture is sheared for 90 min at constant temperature.
The test result is shown in FIG. 3, the final viscosity of the gelled acid solution is 109 mPas, which is far higher than the requirement of industry standard SY/T6214-1996 evaluation method of acid thickener (more than or equal to 20 mPas), and the gelled acid system can be used for acidizing and fracturing at 200 ℃.
Example 13
Temperature and shear resistance test of example 7:
the gelled acid solution obtained in example 7 was poured into a measuring cup and set to a shear rate of 170 s -1 The temperature is 30-160 ℃, and the temperature is raised to 160 ℃ and then the mixture is sheared for 90 min at constant temperature.
The test result is shown in FIG. 4, the final viscosity of the gelled acid solution is 38 mPas, which is far higher than the requirement of the industry standard SY/T6214-1996 evaluation method for acid thickener (more than or equal to 20 mPas), and the gelled acid system can be used for acidizing and fracturing at 160 ℃.
Example 14
Temperature and shear resistance test of example 8:
the gelled acid solution obtained in example 8 was poured into a measuring cup and set to a shear rate of 170 s -1 The temperature is 30-160 ℃, and the temperature is raised to 160 ℃ and then the mixture is sheared for 90 min at constant temperature.
The test result is shown in FIG. 5, the final viscosity of the gelled acid solution is 38 mPas, which is far higher than the requirement of industry standard SY/T6214-1996 evaluation method of acid thickener (more than or equal to 20 mPas), and the gelled acid system can be used for acidizing and fracturing at 160 ℃.
Claims (3)
1. The instant ultrahigh Wen Jiaoning acid resistant acid is characterized by comprising the following components in parts by mass:
1-5 parts of polymer suspension liquid,
1-5 parts of corrosion inhibitor,
0.5 to 2 parts of cleanup additive,
0.5 to 2 parts of iron ion stabilizer,
86-97 parts of hydrochloric acid solution;
the polymer is a copolymer of acrylamide and/or acrylic acid and 2-acrylamide-2-methylpropanesulfonic acid, and the molar content of a functional monomer 2-acrylamide-2-methylpropanesulfonic acid sodium unit in the polymer structure is 50% -75%; the mass content of the polymer in the polymer suspension is 20% -50%; the mass concentration of the hydrochloric acid solution is 5% -30%; the mass content of the polymer in the gelled acid is 0.5% -2.0%; the molecular weight of the polymer is 1000-2000 ten thousand;
the corrosion inhibitor is one or two of imidazolines, thiourea and Schiff bases; the cleanup additive is any one or two of alkyl sulfonate and betaine; the iron ion stabilizer is any one or more of sodium sulfite, organic carboxylate and amino carboxylate.
2. The instant ultra-high Wen Jiaoning acid resistant polymer suspension according to claim 1, wherein the polymer suspension is obtained by dispersing a polymer powder in a dispersion having a viscosity capable of dispersing and suspending the polymer powder to form a uniform and stable suspension.
3. A process for the preparation of instant ultra-high Wen Jiaoning acid resistant according to claim 1 or 2, comprising the following:
according to the composition ratio in claim 1, the polymer suspension, the cleanup additive, the corrosion inhibitor and the iron ion stabilizer are dissolved in the hydrochloric acid solution, and the instant super-high Wen Jiaoning acid-resistant solution is obtained after the polymer is completely dissolved.
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