CN114437690A - Salt-tolerant plugging agent raw material composition, salt-tolerant plugging agent, preparation method and application of salt-tolerant plugging agent, and oil reservoir exploitation method - Google Patents
Salt-tolerant plugging agent raw material composition, salt-tolerant plugging agent, preparation method and application of salt-tolerant plugging agent, and oil reservoir exploitation method Download PDFInfo
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- CN114437690A CN114437690A CN202011205045.4A CN202011205045A CN114437690A CN 114437690 A CN114437690 A CN 114437690A CN 202011205045 A CN202011205045 A CN 202011205045A CN 114437690 A CN114437690 A CN 114437690A
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- plugging agent
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- 238000000034 method Methods 0.000 title claims abstract description 54
- 239000002994 raw material Substances 0.000 title claims abstract description 51
- 239000000203 mixture Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 145
- 150000003839 salts Chemical class 0.000 claims abstract description 115
- 229920005610 lignin Polymers 0.000 claims abstract description 99
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 37
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 25
- 229940123973 Oxygen scavenger Drugs 0.000 claims abstract description 23
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000002131 composite material Substances 0.000 claims abstract description 6
- 230000007071 enzymatic hydrolysis Effects 0.000 claims description 58
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 claims description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 229920001577 copolymer Polymers 0.000 claims description 21
- 229920001568 phenolic resin Polymers 0.000 claims description 19
- 239000005011 phenolic resin Substances 0.000 claims description 19
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 18
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 18
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 12
- 150000001299 aldehydes Chemical class 0.000 claims description 12
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 10
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 claims description 10
- 230000007935 neutral effect Effects 0.000 claims description 10
- 230000002255 enzymatic effect Effects 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 8
- 229920001732 Lignosulfonate Polymers 0.000 claims description 7
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 claims description 7
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 7
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 7
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 7
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 6
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 6
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 6
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 6
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 claims description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 229920005551 calcium lignosulfonate Polymers 0.000 claims description 4
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Natural products OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 3
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-isoascorbic acid Chemical compound OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 claims description 3
- 235000010350 erythorbic acid Nutrition 0.000 claims description 3
- 229920005546 furfural resin Polymers 0.000 claims description 3
- 229940015043 glyoxal Drugs 0.000 claims description 3
- 229920001519 homopolymer Polymers 0.000 claims description 3
- 229940026239 isoascorbic acid Drugs 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229920005552 sodium lignosulfonate Polymers 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 2
- 239000011148 porous material Substances 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 230000018044 dehydration Effects 0.000 description 22
- 238000006297 dehydration reaction Methods 0.000 description 22
- 238000003756 stirring Methods 0.000 description 17
- 239000000243 solution Substances 0.000 description 16
- 229910001425 magnesium ion Inorganic materials 0.000 description 15
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 13
- 239000011575 calcium Substances 0.000 description 13
- 229910001424 calcium ion Inorganic materials 0.000 description 13
- 239000000843 powder Substances 0.000 description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 9
- 230000033558 biomineral tissue development Effects 0.000 description 9
- 239000011780 sodium chloride Substances 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000032683 aging Effects 0.000 description 6
- 239000002981 blocking agent Substances 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000008399 tap water Substances 0.000 description 6
- 235000020679 tap water Nutrition 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000012267 brine Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000005465 channeling Effects 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
- 238000004090 dissolution Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 230000001502 supplementing effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 108010059892 Cellulase Proteins 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 229940106157 cellulase Drugs 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- ZNEMGFATAVGQSF-UHFFFAOYSA-N 1-(2-amino-6,7-dihydro-4H-[1,3]thiazolo[4,5-c]pyridin-5-yl)-2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound NC=1SC2=C(CN(CC2)C(CC=2OC(=NN=2)C=2C=NC(=NC=2)NC2CC3=CC=CC=C3C2)=O)N=1 ZNEMGFATAVGQSF-UHFFFAOYSA-N 0.000 description 1
- PQVHMOLNSYFXIJ-UHFFFAOYSA-N 4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]pyrazole-3-carboxylic acid Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(N1CC2=C(CC1)NN=N2)=O)C(=O)O PQVHMOLNSYFXIJ-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- NEAPKZHDYMQZCB-UHFFFAOYSA-N N-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]ethyl]-2-oxo-3H-1,3-benzoxazole-6-carboxamide Chemical compound C1CN(CCN1CCNC(=O)C2=CC3=C(C=C2)NC(=O)O3)C4=CN=C(N=C4)NC5CC6=CC=CC=C6C5 NEAPKZHDYMQZCB-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009933 burial Methods 0.000 description 1
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000012154 double-distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- -1 etc. Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/514—Compositions based on water or polar solvents containing organic compounds macromolecular compounds of natural origin, e.g. polysaccharides, cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/512—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/887—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/90—Compositions based on water or polar solvents containing organic compounds macromolecular compounds of natural origin, e.g. polysaccharides, cellulose
- C09K8/905—Biopolymers
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B33/00—Sealing or packing boreholes or wells
- E21B33/10—Sealing or packing boreholes or wells in the borehole
- E21B33/13—Methods or devices for cementing, for plugging holes, crevices or the like
- E21B33/138—Plastering the borehole wall; Injecting into the formation
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Geology (AREA)
- Mining & Mineral Resources (AREA)
- Geochemistry & Mineralogy (AREA)
- Physics & Mathematics (AREA)
- Biochemistry (AREA)
- Fluid Mechanics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Environmental & Geological Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of oil exploitation, and discloses a salt-tolerant plugging agent raw material composition, a salt-tolerant plugging agent, a preparation method and application thereof, and a method for oil reservoir exploitation. The salt-resistant plugging agent raw material composition comprises: the composite material comprises a nonionic acrylamide polymer, a cross-linking agent, an oxygen scavenger and water-soluble lignin. According to the salt-resistant plugging agent, the water-soluble lignin is added into the polyacrylamide gel system, so that the original flexible network system and the original rigid network are interpenetrated to generate a synergistic effect, the gelling strength of the polyacrylamide gel can be effectively improved, and the contradiction that the dosage needs to be increased when the strength is increased at present is solved; meanwhile, the effective plugging period is prolonged, and the requirement of plugging large pore channels of the ultra-deep well of the carbonate reservoir is met.
Description
Technical Field
The invention relates to the technical field of oil exploitation, in particular to a salt-tolerant plugging agent raw material composition, a salt-tolerant plugging agent and a preparation method thereof, application of the salt-tolerant plugging agent raw material composition or the salt-tolerant plugging agent in oil reservoir exploitation, and an oil reservoir exploitation method.
Background
The carbonate rock fracture-cave type oil reservoir in China is buried ultra-deep and has high temperature and high salinity. Taking the Tahe oil field as an example, the oil reservoir burial depth is more than 4000m, the temperature of the main reservoir is 140 ℃ at 100-2+，Mg2+Is 5-8 g/L). With the extension of the development time of the oil field, the comprehensive water content continuously rises, and corresponding plugging regulating measures are required to plug a water channeling channel.
The existing gel plugging agent is compounded and injected into a stratum by taking a polyacrylamide aqueous solution as a thickening agent and taking phenolic resin or metal chromium as a cross-linking agent, and the gel is formed by in-situ cross-linking in the deep part of the stratum so as to plug water. The plugging agent has good oil-water selectivity and toughness, but is poor in temperature resistance and salt resistance, and particularly, under the influence of high salinity and high calcium and magnesium ions, dehydration shrinkage occurs quickly to cause gel breaking and affect the plugging effect.
Disclosure of Invention
The invention aims to overcome the problems that the existing gel plugging agent cannot be effectively applied to higher temperature, higher salinity and high calcium and magnesium ions and realize water plugging for a longer time, and provides a raw material composition of a salt-resistant plugging agent, a salt-resistant plugging agent and a preparation method thereof, application of the raw material composition of the salt-resistant plugging agent or the salt-resistant plugging agent in oil reservoir exploitation and a method for oil reservoir exploitation. The salt-resistant plugging agent can effectively plug a water channeling channel in a longer time range under the environment with higher temperature, higher mineralization and high calcium and magnesium ions.
In order to achieve the above object, a first aspect of the present invention provides a salt-tolerant plugging agent raw material composition, comprising: the composite material comprises a nonionic acrylamide polymer, a cross-linking agent, an oxygen scavenger and water-soluble lignin.
In a second aspect, the present invention provides a method for preparing a salt-tolerant blocking agent, comprising:
(1) dissolving water-soluble lignin in the presence of a solvent to obtain a water-soluble lignin solution;
(2) and mixing the water-soluble lignin solution with the nonionic acrylamide polymer, and then mixing the obtained mixed material with a cross-linking agent and an oxygen scavenger to obtain the salt-resistant plugging agent.
In a third aspect, the invention provides a salt-resistant plugging agent prepared by the method.
The fourth aspect of the invention provides the application of the salt-tolerant plugging agent raw material composition or the salt-tolerant plugging agent in oil reservoir exploitation, in particular in carbonate oil reservoir exploitation.
In a fifth aspect, the present invention provides a method of reservoir exploration, the method comprising: injecting the salt-resistant plugging agent into the stratum, and enabling the salt-resistant plugging agent to be crosslinked in situ in the stratum to form gel.
According to the invention, the lignin polymer is used as a rigid structure and introduced into a traditional polyacrylamide gel system, so that the flexible network and the rigid network are interpenetrated, a rigid-flexible gel interpenetrating network can be formed, and the unique network structure and synergistic effect endow the gel with stronger plugging capability and section improving capability, so that the salt resistance of the existing acrylamide gel at high temperature can be improved, the network collapse under high salt is inhibited, the salt resistance stability at high temperature is improved, and the additional value of the lignin polymer can be improved.
The salt-resistant plugging agent provided by the invention has the advantages of simple preparation method, good stability of the formed gel and high strength, and can effectively plug a water channeling passage for a long time within 60 days in an environment with a total mineralization as high as 200000mg/L and a calcium and magnesium ion concentration as high as 10000mg/L at a higher temperature of 110-140 ℃.
Compared with the existing gel plugging agent, the salt-resistant plugging agent provided by the invention has higher plugging rate and longer plugging time, and can be suitable for large pore path plugging operation in an ultra-deep well of a carbonate reservoir (such as a Tahe oil field).
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In order to achieve the above object, the first aspect of the present invention provides a salt-tolerant plugging agent raw material composition comprising: the composite material comprises nonionic acrylamide polymer, a cross-linking agent, an oxygen scavenger and water-soluble lignin.
The components in the raw material composition of the salt-resistant plugging agent can be stored independently or can be stored together with more than two components. The salt-resistant plugging agent raw material composition needs to have a solvent when in use, but can be sold as a product when the solvent is not contained, and a preset amount of solvent can be added when in use.
Preferably, the salt-resistant plugging agent raw material composition further contains a solvent.
In the present invention, the content of the water-soluble lignin is 0.1 to 10 wt%, for example, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10 wt% and any range between any two values, preferably 0.2 to 8 wt%, based on the total weight of the salt-resistant plugging agent raw material composition.
Preferably, the water-soluble lignin is lignosulfonate and/or modified enzymatic lignin.
Preferably, the lignosulfonate is at least one of sodium lignosulfonate, calcium lignosulfonate, and potassium lignosulfonate.
Preferably, the water-soluble lignin is modified enzymatic hydrolysis lignin.
Preferably, the preparation method of the modified enzymatic hydrolysis lignin comprises the following steps: dissolving enzymatic hydrolysis lignin at 40-50 deg.C and pH of 10-12 to obtain modified enzymatic hydrolysis lignin solution, and adjusting pH of the modified enzymatic hydrolysis lignin solution to neutral to obtain modified enzymatic hydrolysis lignin.
Preferably, the method further comprises: before adjusting the pH value of the enzymatic hydrolysis lignin solution to be neutral, aging the modified enzymatic hydrolysis lignin solution.
Wherein aging means allowing the solution to stand for a period of time under certain conditions. The time of the aging treatment is preferably 4 to 8 hours.
The enzymatic hydrolysis lignin generally refers to cellulase enzymatic hydrolysis lignin, and can be prepared by subjecting residues of a biomass raw material subjected to cellulase hydrolysis to an organic solvent extraction method or an alkali-soluble acid-precipitation method. The enzymatic lignin can be obtained by self-manufacture or commercial purchase, for example, enzymatic lignin available from Shandong Longli Biotech, Inc.
In the present invention, pH neutral means a range of pH 7. + -. 0.5.
In the present invention, water can be used as a modifying medium for enzymatic hydrolysis of lignin to prepare a modified enzymatic hydrolysis lignin solution. The water used may be water commonly used in the art, such as tap water, distilled water, mineral water, double distilled water, etc., and water with high salinity (greater than 200000mg/L) (such as water at the oil field site of carbonate reservoir or its corresponding simulated salt water) is not suitable.
In the present invention, the pH may be brought to 10 to 12 by an alkali regulator, which may be an alkaline substance conventionally used in the art, preferably, the alkali regulator is selected from at least one of potassium hydroxide, sodium hydroxide and sodium carbonate.
Wherein, the dosage of the pH regulator can be adjusted by the person skilled in the art according to the required pH.
The time for dissolving the enzymatic hydrolysis lignin can be selected from a wide range as long as the enzymatic hydrolysis lignin can be completely dissolved, and is preferably 1 to 2 hours.
In the present invention, the modified enzymatic hydrolysis lignin content in the modified enzymatic hydrolysis lignin solution is preferably 0.1 to 10 wt%, and may be, for example, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10 wt% or any range therebetween, and is preferably 0.2 to 8 wt%. Wherein the weight of the modified enzymatic hydrolysis lignin is based on the weight of the enzymatic hydrolysis lignin.
In the present invention, the pH may be adjusted to be neutral by an acid regulator, which may be an acidic substance conventionally used in the art, preferably, the acid regulator is selected from at least one of hydrochloric acid, sulfuric acid, acetic acid, and citric acid.
Preferably, after the pH value of the enzymatic hydrolysis lignin solution is adjusted to be neutral, the enzymatic hydrolysis lignin solution is dried to obtain a modified enzymatic hydrolysis lignin solid. The modified enzymatic hydrolysis lignin solid can also be subjected to a pulverization treatment, such as a grinding treatment, to obtain a powdery product.
It is understood that when the water-soluble lignin is modified enzymatic lignin, metal ions may be introduced into the composition, and the content thereof may be calculated according to the amount thereof.
In the present invention, the content of the nonionic acrylamide polymer is preferably 0.1 to 1.5 wt%, for example, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1, 1.1, 1.2, 1.3, 1.4, 1.5 wt% and any range between any two values, preferably 0.2 to 1 wt%, based on the total weight of the salt-resistant plugging agent raw material composition.
In the present invention, the kind of the nonionic acrylamide polymer may be selected with reference to the prior art. In the present invention, the nonionic acrylamide polymer is preferably at least one selected from the group consisting of an acrylamide homopolymer, an N, N-dimethylacrylamide homopolymer, an acrylamide/N, N-dimethylacrylamide copolymer, an acrylamide/N-vinylpyrrolidone copolymer, an N, N-dimethylacrylamide/N-vinylpyrrolidone copolymer, and an acrylamide/N, N-dimethylacrylamide/N-vinylpyrrolidone copolymer, and is more preferably an acrylamide/N-vinylpyrrolidone copolymer.
The non-ionic acrylamide polymer can be synthesized according to the prior art or obtained commercially, and can be, for example, a non-ionic polyacrylamide available from Shandong Baomo biochemical industry.
In the present invention, the viscosity average molecular weight of the nonionic acrylamide polymer is preferably 400 to 1500 ten thousand, preferably 500 to 1000 ten thousand.
In the present invention, the content of the cross-linking agent is preferably 0.5 to 5 wt%, for example, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1, 1.2, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5 wt% and any range between any two values, preferably 0.8 to 4 wt%, based on the total weight of the salt-resistant plugging agent raw material composition.
According to the invention, the salt-resistant plugging agent raw material composition contains the cross-linking agent, so that the gelling strength and plugging performance of the salt-resistant plugging agent can be further improved.
Preferably, the cross-linking agent is selected from at least one of water-soluble phenolic resin, water-soluble urea-formaldehyde resin and a mixture of the phenolic raw material and the aldehyde raw material, and more preferably the water-soluble phenolic resin and/or the mixture of the phenolic raw material and the aldehyde raw material.
Preferably, the water-soluble phenolic resin is prepared from phenol and formaldehyde under alkaline conditions according to a weight ratio of 0.2-0.75: 1, is polymerized. Preferably, the water-soluble phenolic resin obtained by the reaction is a solid-liquid mixture with the pH value of more than 11 and the solid content of more than 40 weight percent.
The water-soluble phenolic resin can be obtained by self-production or by commercial production, and for example, can be a water-soluble phenolic resin obtained from eastern squareness chemical industry ltd.
Preferably, the water-soluble urea-formaldehyde resin is a linear urea-formaldehyde resin, preferably prepared from formaldehyde and urea according to the weight ratio of 1-3: 1, is polymerized. Typically, the water-soluble urea-formaldehyde resin is a solid-liquid mixture having a pH greater than 9 and a solids content greater than 40% by weight.
In the present invention, the phenolic raw material and the aldehyde raw material respectively mean materials which provide a phenol and an aldehyde. For example, hexamethylenetetramine can be decomposed to give formaldehyde, and therefore, it can be used as an aldehyde raw material.
Preferably, the phenolic feedstock is selected from at least one of catechol, resorcinol and hydroquinone, more preferably hydroquinone.
Preferably, the aldehyde raw material is selected from at least one of formaldehyde, glyoxal, hexamethylenetetramine and furan alcohol, and more preferably hexamethylenetetramine.
When the crosslinking agent is a mixture of a phenolic material and an aldehyde material, the content of the phenolic material is 0.6 to 2 wt%, such as 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1, 1.2, 1.4, 1.6, 1.8, 2 wt% and any range therebetween, and the content of the aldehyde material is 0.6 to 2 wt%, such as 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1, 1.2, 1.4, 1.6, 1.8, 2 wt% and any range therebetween, based on the total weight of the salt-resistant plugging agent raw material composition in the presence of a solvent.
Preferably, the ratio of the amount of the phenolic raw material to the amount of the aldehyde raw material is 1: 0.5-2.
In the present invention, preferably, the content of the oxygen scavenger is 0.01 to 2 wt%, based on the total weight of the salt-tolerant plugging agent raw material composition, such as 0.01, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1, 1.2, 1.4, 1.6, 1.8, 2 wt% and any range between any two values, preferably 0.05 to 0.5 wt%.
In the present invention, the kind and amount of the oxygen scavenger can be selected with reference to the prior art. In the present invention, preferably, the oxygen scavenger is at least one of sodium thiosulfate, sodium sulfite, sodium bisulfite, sodium hydrosulfite, isoascorbic acid and thiourea.
In the present invention, preferably, the solvent is water.
In the present invention, water is used as the solvent and reaction medium in the salt-tolerant plugging agent system, and the selection of the solvent and the reaction medium is not particularly limited in the present invention. The water can be natural water which can be rivers, lakes, atmospheric water, seawater, underground water and the like, and artificial water which can be tap water, distilled water, deionized water or heavy water.
Generally, in practical applications, the water used is often water at the site of the oil field or its corresponding simulated brine. Preferably, the degree of mineralization of the water is below 200,000mg/L, and the content of calcium and magnesium ions is below 10,000 mg/L.
In the present invention, the content of calcium and magnesium ions is the sum of the contents of calcium and magnesium ions in water, and can be determined by the ICP-MS method.
It should be understood that the salt-resistant plugging agent raw material composition may contain impurities derived from water according to the mineralization degree of water, but in the calculation process, the impurities and the water are calculated as a whole.
In a preferred embodiment of the present invention, the salt-tolerant plugging agent raw material composition comprises: the composite material comprises nonionic acrylamide polymer, a cross-linking agent, an oxygen scavenger and water-soluble lignin. Wherein the weight ratio of the nonionic acrylamide polymer to the crosslinking agent to the oxygen scavenger to the enzymatic hydrolysis lignin is (0.1-1.5): (0.5-5): (0.01-2): (0.1-10), more preferably (0.2-1): (0.8-4): (0.05-0.5): (0.2-8). Wherein, the weight ratio of each component can also be the ratio formed by any one point value in the range.
In a preferred embodiment of the present invention, the salt-tolerant plugging agent raw material composition comprises: the composite material comprises a nonionic acrylamide polymer, a cross-linking agent, an oxygen scavenger, water-soluble lignin and water. Based on the total weight of the salt-resistant plugging agent raw material composition, the content of the non-ionic acrylamide polymer is 0.1-1.5 wt%, the content of the cross-linking agent is 0.5-5 wt%, the content of the oxygen scavenger is 0.1-2 wt%, and the content of the water-soluble lignin is 0.1-10 wt%. More preferably, based on the total weight of the salt-tolerant plugging agent raw material composition, the content of the non-ionic acrylamide polymer is 0.2-1 wt%, the content of the cross-linking agent is 0.8-4 wt%, the content of the oxygen scavenger is 0.05-0.5 wt%, the content of the water-soluble lignin is 0.2-8 wt%, and the balance is water. Within the preferable range, the gelling strength and the plugging performance of the salt-resistant plugging agent can be further improved.
The invention provides a preparation method of a salt-resistant plugging agent, which comprises the following steps:
(1) dissolving water-soluble lignin in the presence of a solvent to obtain a water-soluble lignin solution;
(2) and mixing the water-soluble lignin solution with the nonionic acrylamide polymer, and then mixing the obtained mixed material with a cross-linking agent and an oxygen scavenger to obtain the salt-resistant plugging agent.
In the present invention, in step (1), the conditions and manner of the dissolution may not be particularly limited as long as the material can be sufficiently dissolved.
The dissolution can be carried out at normal temperature and normal pressure, and can be determined according to the specific environment when the salt-resistant plugging agent is prepared.
In the invention, in the step (2), in order to accelerate dissolution and mixing in the mixing process, mixing can be assisted by stirring, ultrasound and the like, so that the materials are dissolved more quickly and are distributed uniformly.
In the present invention, the amount of each component may be determined in accordance with the content of each component of the first aspect.
In a preferred embodiment of the invention, the amount of the non-ionic acrylamide polymer is 0.1-1.5 wt%, the amount of the cross-linking agent is 0.5-5 wt%, the amount of the oxygen scavenger is 0.01-2 wt%, and the amount of the water-soluble lignin is 0.1-10 wt%, based on the total weight of the salt-resistant plugging agent.
In a preferred embodiment of the invention, the amount of the non-ionic acrylamide polymer is 0.2-1 wt%, the amount of the cross-linking agent is 0.8-4 wt%, the amount of the oxygen scavenger is 0.05-0.5 wt%, and the amount of the water-soluble lignin is 0.2-8 wt%, based on the total weight of the salt-resistant plugging agent.
The kinds and properties of the components and the preparation method have been described in detail in the first aspect, and are not described herein again.
The solvent used may be a solvent as described in the first aspect.
In a third aspect, the invention provides the salt-resistant plugging agent prepared by the method.
The fourth aspect of the invention provides the application of the salt-tolerant plugging agent raw material composition or the salt-tolerant plugging agent in oil reservoir exploitation, in particular in carbonate oil reservoir exploitation.
In a fifth aspect, the present invention provides a method of reservoir exploration, the method comprising: injecting the salt-resistant plugging agent into the stratum, and enabling the salt-resistant plugging agent to be crosslinked in situ in the stratum to form gel.
The composition can gel at a high temperature of 110 ℃ and 140 ℃ within 6-48h to form a plug, and the plug is kept at the temperature for 60 days.
The salt-resistant plugging agent is suitable for exploitation of an oil reservoir in an ultra-deep well region of a carbonate oil reservoir, and preferably, the mineralization degree of water in the region is below 200000mg/L, and the content of calcium and magnesium ions is below 10000 mg/L.
The present invention will be described in detail below by way of examples.
In the following examples, acrylamide polymers were purchased from Shandong Baommo biochemical.
The enzymatic hydrolysis lignin is from Shandong Longli Biotech GmbH.
Calcium lignosulfonate was purchased from Nanyang Longxiang chemical technology, Inc.
Phenolic resins are available from eastern squarine chemical industry ltd, urea resins are available from southern Henan Huanshan industries ltd.
The reagents and materials used in the following examples are all commercially available without specific indication.
In the following examples, simulated brine is formulated according to the applicable reservoir environment, and the degree of mineralization of the simulated brine is 200000mg/L and the content of calcium and magnesium ions is 10000mg/L (it should be understood that the degree of mineralization and the content of calcium and magnesium ions are about values).
In the following embodiments, the darcy principle is applied to the test of the plugging performance, and the test method is as follows:
filling a simulation core (the diameter d of the core is 25mm, the length L of the core is 200mm), injecting water into the core at the flow rate of 2 ml/min (injection rate Q) after vacuumizing, and measuring the permeability (k) before core plugging0) (ii) a And then injecting 1.0-1.5PV salt-tolerant plugging agent into the core model, plugging two ends of the core by using a plug, putting the core into a constant temperature incubator for standing for a certain number of days, injecting water again until the pressure is stable, and obtaining the permeability (k') after the core is plugged, thereby calculating the plugging rate.
The plugging rate (eta) is taken as a parameter for representing the plugging performance of the plugging agent, and the calculation formula is as follows:
in the following examples and comparative examples, the polymer gel blocking agent gelled at 140 ℃, the gelling time was determined by the gel strength code method, and the elapsed time for converting the gel system from the solution to the strength code G was the gelling time.
In the following examples and comparative examples, the thermal stability was expressed by the dehydration rate, and the stability was examined by measuring the dehydration rate at different times. The determination method comprises the following steps: putting the polymer gel plugging agent into a closed stainless steel reaction kettle, placing the reaction kettle in a constant temperature box at a certain temperature for reaction, taking the reaction kettle out of the constant temperature box at fixed intervals, weighing the dehydrated mass of the gel by using a balance, wherein the ratio of the mass to the mass of the initial gel forming liquid is the dehydration rate.
Preparation example 1
The preparation example is used to illustrate the preparation method of the modified enzymatic hydrolysis lignin.
Adding 100g of enzymatic hydrolysis lignin into 900g of tap water, adding sodium hydroxide to adjust the pH to 12 at the temperature of 40 ℃, stirring for 1h until the enzymatic hydrolysis lignin is completely dissolved, aging for 4h, then adjusting the pH to be neutral, drying, and grinding to obtain modified enzymatic hydrolysis lignin powder L1.
Preparation example 2
The preparation example is used to illustrate the preparation method of the modified enzymatic hydrolysis lignin.
Adding 100g of enzymatic hydrolysis lignin into 900g of tap water, adding sodium carbonate to adjust the pH to 10 at the temperature of 50 ℃, stirring for 2h until the enzymatic hydrolysis lignin is completely dissolved, aging for 4h, then adjusting the pH to be neutral, drying and grinding to obtain modified enzymatic hydrolysis lignin powder L2.
Preparation example 3
The preparation example is used to illustrate the preparation method of the modified enzymatic hydrolysis lignin.
Adding 100g of enzymatic hydrolysis lignin into 900g of tap water, adding potassium hydroxide to adjust the pH value to 11, adjusting the temperature to 45 ℃, stirring for 2h until the enzymatic hydrolysis lignin is completely dissolved, aging for 4h, adjusting the pH value to be neutral, drying, and grinding to obtain modified enzymatic hydrolysis lignin powder L3.
Preparation example 4
The preparation example is used to illustrate the preparation method of the modified enzymatic hydrolysis lignin.
Adding 100g of enzymatic hydrolysis lignin into 900g of tap water, adding sodium carbonate to adjust the pH to 10 at the temperature of 50 ℃, stirring for 2h until the enzymatic hydrolysis lignin is completely dissolved, then adjusting the pH to be neutral, drying and grinding to obtain modified enzymatic hydrolysis lignin powder L4.
Example 1
This example illustrates the salt-resistant plugging agent and the preparation method thereof according to the present invention.
Adding 20g of modified enzymatic hydrolysis lignin powder L1 into 900g of simulated saline, stirring until the modified enzymatic hydrolysis lignin powder is completely dissolved, adding 8g of acrylamide/N-vinyl pyrrolidone copolymer (molecular weight is 760 ten thousand), stirring until the modified enzymatic hydrolysis lignin powder is completely dissolved, adding 25g of phenolic resin and 1g of sodium bisulfite, supplementing the mixture to the total weight of 1kg by using the simulated saline, and uniformly stirring to obtain the salt-resistant plugging agent.
And recording the gelling time of the salt-resistant plugging agent at 140 ℃ by adopting a gel strength code method.
After gelling, the salt-resistant plugging agent is stably kept for 60 days at 140 ℃, and then the dehydration rate and the plugging performance of the salt-resistant plugging agent are measured, and the results are shown in table 1.
Recording the gelling time of the salt-resistant plugging agent at 110 ℃, 120 ℃, 130 ℃ and 140 ℃ by adopting a gel strength code method; the dehydration rate and the plugging rate of the salt-resistant plugging agent after being maintained for 60 days at 110 ℃, 120 ℃, 130 ℃ and 140 ℃ are tested, and the test results are shown in table 2.
In addition, simulated saline water with different mineralization degrees and calcium and magnesium ion contents is used for preparing the salt-resistant plugging agent, the gelling time of the salt-resistant plugging agent is measured at 140 ℃, the dehydration rate and the plugging rate after 60 days of maintenance are measured, and the test results are shown in table 3.
Example 2
This example illustrates the salt-resistant plugging agent and the preparation method thereof according to the present invention.
Adding 80g of modified enzymatic hydrolysis lignin powder L2 into 900g of simulated saline, stirring until the modified enzymatic hydrolysis lignin powder is completely dissolved, adding 2g of acrylamide/N-vinyl pyrrolidone copolymer (with the molecular weight of 1000 ten thousand), stirring until the modified enzymatic hydrolysis lignin powder is completely dissolved, adding 30g of phenolic resin and 0.5g of sodium thiosulfate, supplementing the mixture to the total weight of 1kg by using the simulated saline, and uniformly stirring to obtain the salt-resistant plugging agent.
And recording the gelling time of the salt-resistant plugging agent at 140 ℃ by adopting a gel strength code method.
After gelling, the salt-resistant plugging agent is stably kept for 60 days at 140 ℃, and then the dehydration rate and the plugging performance of the salt-resistant plugging agent are measured, and the results are shown in table 1.
Example 3
This example illustrates the salt-resistant plugging agent and the preparation method thereof according to the present invention.
Adding 2g of modified enzymatic hydrolysis lignin powder L3 into 900g of simulated saline, stirring until the modified enzymatic hydrolysis lignin powder is completely dissolved, adding 10g of acrylamide/N-vinyl pyrrolidone copolymer (with the molecular weight of 510 ten thousand), stirring until the modified enzymatic hydrolysis lignin powder is completely dissolved, adding 8g of phenolic resin and 5g of sodium bisulfite, supplementing the mixture to the total weight of 1kg by using the simulated saline, and uniformly stirring to obtain the salt-resistant plugging agent.
And recording the gelling time of the salt-resistant plugging agent at 140 ℃ by adopting a gel strength code method.
After gelling, the salt-resistant plugging agent is stably kept for 60 days at 140 ℃, and then the dehydration rate and the plugging performance of the salt-resistant plugging agent are measured, and the results are shown in table 1.
Example 4
This example illustrates the salt-resistant plugging agent and the preparation method thereof.
The procedure was as in example 1 except that the amounts of the components added were varied, wherein the modified enzymatic hydrolysis lignin (100 g), the N, N-dimethylacrylamide/N-vinylpyrrolidone copolymer (molecular weight: 403 ten thousand) (1 g), the phenol resin (50 g), and the sodium hydrogen sulfite (0.1 g) were used.
And recording the gelling time of the salt-resistant plugging agent at 140 ℃ by adopting a gel strength code method.
After the salt-resistant plugging agent is gelatinized, the salt-resistant plugging agent is stably kept at 140 ℃ for 60 days, and then the dehydration rate and the plugging performance of the salt-resistant plugging agent are measured, and the results are shown in table 1.
Example 5
This example illustrates the salt-resistant plugging agent and the preparation method thereof according to the present invention.
The procedure was followed as in example 1 except that the modified enzymatic lignin (1 g), acrylamide/N, N-dimethylacrylamide copolymer (molecular weight: 1500 ten thousand) (15 g), phenol-formaldehyde resin (5 g), and sodium bisulfite (20 g) were added in different amounts.
And recording the gelling time of the salt-resistant plugging agent at 140 ℃ by adopting a gel strength code method.
After gelling, the salt-resistant plugging agent is stably kept for 60 days at 140 ℃, and then the dehydration rate and the plugging performance of the salt-resistant plugging agent are measured, and the results are shown in table 1.
Example 6
This example illustrates the salt-resistant plugging agent and the preparation method thereof according to the present invention.
The procedure was followed as described in example 1, except that an equal mass of modified enzymatic lignin L4 was used in place of modified enzymatic lignin L1.
And recording the gelling time of the salt-resistant plugging agent at 140 ℃ by adopting a gel strength code method.
After gelling, the salt-resistant plugging agent is stably kept for 60 days at 140 ℃, and then the dehydration rate and the plugging performance of the salt-resistant plugging agent are measured, and the results are shown in table 1.
Example 7
This example illustrates the salt-resistant plugging agent and the preparation method thereof according to the present invention.
The procedure was followed as described in example 1, except that an equivalent mass of calcium lignosulfonate was used in place of modified enzymatic lignin L1.
And recording the gelling time of the salt-resistant plugging agent at 140 ℃ by adopting a gel strength code method.
After gelling, the salt-resistant plugging agent is stably kept for 60 days at 140 ℃, and then the dehydration rate and the plugging performance of the salt-resistant plugging agent are measured, and the results are shown in table 1.
Example 8
This example illustrates the salt-resistant plugging agent and the preparation method thereof according to the present invention.
The procedure is as described in example 1, except that 25g of phenolic resin are replaced by 18g of hydroquinone and 18g of hexamethylenetetramine.
And recording the gelling time of the salt-resistant plugging agent at 140 ℃ by adopting a gel strength code method.
After gelling, the salt-resistant plugging agent is stably kept for 60 days at 140 ℃, and then the dehydration rate and the plugging performance of the salt-resistant plugging agent are measured, and the results are shown in table 1.
Example 9
This example illustrates the salt-resistant plugging agent and the preparation method thereof according to the present invention.
The procedure is as described in example 1, except that 12.5g of catechol and 12.5g of glyoxal are used instead of 25g of phenol-formaldehyde resin.
And recording the gelling time of the salt-resistant plugging agent at 140 ℃ by adopting a gel strength code method.
After gelling, the salt-resistant plugging agent is stably kept for 60 days at 140 ℃, and then the dehydration rate and the plugging performance of the salt-resistant plugging agent are measured, and the results are shown in table 1.
Example 10
This example illustrates the salt-resistant plugging agent and the preparation method thereof according to the present invention.
The procedure was followed as described in example 1, except that 25g of furfural resin was used instead of 25g of phenol resin.
And recording the gelling time of the salt-resistant plugging agent at 140 ℃ by adopting a gel strength code method.
After gelling, the salt-resistant plugging agent is stably kept for 60 days at 140 ℃, and then the dehydration rate and the plugging performance of the salt-resistant plugging agent are measured, and the results are shown in table 1.
Comparative example 1
This comparative example is used to illustrate a reference salt-tolerant blocking agent and a method for its preparation.
20g of acrylamide/N-vinyl pyrrolidone copolymer (molecular weight is 760 ten thousand) is dissolved in 900g of simulated saline water, 25g of phenolic resin and 1g of sodium thiosulfate are added, and the salt-resistant plugging agent is obtained by uniformly stirring.
And recording the gelling time of the salt-resistant plugging agent at 140 ℃ by adopting a gel strength code method.
After gelling, the salt-resistant plugging agent is kept at 140 ℃ for 60 days, and then the dehydration rate and the plugging performance of the salt-resistant plugging agent are measured, and the results are shown in table 1.
Comparative example 2
This comparative example is used to illustrate a reference salt-tolerant blocking agent and a method for its preparation.
Adding 28g of modified enzymatic hydrolysis lignin L1 into 1kg of simulated saline water, stirring until the modified enzymatic hydrolysis lignin is completely dissolved, then adding 25g of phenolic resin and 1g of sodium thiosulfate, and uniformly stirring to obtain the salt-resistant plugging agent.
And recording the gelling time of the salt-resistant plugging agent at 140 ℃ by adopting a gel strength code method.
After gelling, the salt-resistant plugging agent is kept at 140 ℃ for 60 days, and then the dehydration rate and the plugging performance of the salt-resistant plugging agent are measured, and the results are shown in table 1.
Comparative example 3
This comparative example is used to illustrate a reference salt-tolerant blocking agent and a method for its preparation.
The procedure is as described in example 1, except that, instead of the acrylamide/N-vinylpyrrolidone copolymer, an equal mass of partially hydrolyzed polyacrylamide (molecular weight 1240 ten thousand, degree of hydrolysis 10%) is used, and it is observed that the solution changes from a clear state to a suspension.
And recording the gelling time of the salt-resistant plugging agent at 140 ℃ by adopting a gel strength code method.
After gelling, the salt-resistant plugging agent is kept at 140 ℃ for 30 days, and then the dehydration rate and the plugging performance of the salt-resistant plugging agent are measured, and the results are shown in table 1.
Comparative example 4
This comparative example is used to illustrate a reference salt-tolerant blocking agent and a method for its preparation.
The procedure is as described in example 1, except that sodium thiosulfate is not used.
And recording the gelling time of the salt-resistant plugging agent at 140 ℃ by adopting a gel strength code method.
After the salt-resistant plugging agent is gelatinized, the salt-resistant plugging agent is kept at 140 ℃ for 30 days, and then the dehydration rate and the plugging performance of the salt-resistant plugging agent are measured, and the results are shown in table 1.
TABLE 1
| Example numbering | Gelling time/h | Percentage of dehydration/%) | Plugging Rate/% |
| Example 1 | 10 | 3.7(60 days) | 99.68 |
| Example 2 | 16 | 7.5(60 days) | 97.95 |
| Example 3 | 8 | 8.9(60 days) | 97.23 |
| Example 4 | 14 | 14.6(60 days) | 90.47 |
| Example 5 | 7 | 10.2(60 days) | 95.56 |
| Example 6 | 11 | 5.1(60 days) | 99.10 |
| Example 7 | 15 | 12.4(60 days) | 94.82 |
| Example 8 | 16 | 4.1(60 days) | 99.64 |
| Example 9 | 16 | 16.9(60 days) | 90.39 |
| Example 10 | 15 | 14.5(60 days) | 91.97 |
| Comparative example 1 | 6 | 70.4(60 days) | 43.51 |
| Comparative example 2 | 24 | 26.3(60 days) | 81.74 |
| Comparative example 3 | 18 | 48.2(30 days) | 60.29 |
| Comparative example 4 | 10 | 30.8(30 days) | 79.65 |
The results in table 1 show that the salt-resistant plugging agent provided by the invention has good thermal stability and plugging rate at 140 ℃, and has good plugging effect on the large pore canal of the ultra-deep well with high salinity and high calcium and magnesium ions in a carbonate reservoir.
TABLE 2
The results in table 2 show that the salt-resistant plugging agent can be stably maintained for 60 days at the temperature of 110-140 ℃, and has a good plugging effect.
TABLE 3
| Simulating salinity/content of calcium and magnesium ions in brine | Gelling time/h | Percentage of dehydration/%) | Plugging Rate/% |
| 100000mg/L/5000mg/L | 15 | 0.8 | 99.89 |
| 100000mg/L/10000mg/L | 15 | 1.0 | 99.85 |
| 150000mg/L/5000mg/L | 13 | 1.1 | 99.83 |
| 150000mg/L/10000mg/L | 13 | 1.6 | 99.80 |
| 200000mg/L/5000mg/L | 10 | 2.3 | 99.76 |
| 200000mg/L/10000mg/L | 10 | 3.7 | 99.68 |
The results in table 3 show that the salt-resistant plugging agent of the present invention can stably maintain at a high temperature of 140 ℃ for 60 days with a mineralization degree of 100000-200000mg/L and a calcium-magnesium ion concentration of 5000-10000mg/L, and has a good plugging rate and a significantly better effect on plugging large pore canals of ultra-deep wells of carbonate reservoirs.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (12)
1. A raw material composition of a salt-resistant plugging agent is characterized by comprising the following components in parts by weight: the composite material comprises a nonionic acrylamide polymer, a cross-linking agent, an oxygen scavenger and water-soluble lignin.
2. The salt-tolerant plugging agent raw material composition according to claim 1, wherein the salt-tolerant plugging agent raw material composition further comprises a solvent;
preferably, based on the total weight of the salt-resistant plugging agent raw material composition, the content of the non-ionic acrylamide polymer is 0.1-1.5 wt%, the content of the cross-linking agent is 0.5-5 wt%, the content of the oxygen scavenger is 0.01-2 wt%, and the content of the water-soluble lignin is 0.1-10 wt%;
more preferably, based on the total weight of the salt-resistant plugging agent raw material composition, the content of the non-ionic acrylamide polymer is 0.2-1 wt%, the content of the cross-linking agent is 0.8-4 wt%, the content of the oxygen scavenger is 0.05-0.5 wt%, and the content of the water-soluble lignin is 0.2-8 wt%.
3. The salt tolerant plugging agent feedstock composition of claim 1 or 2, wherein the water soluble lignin is lignosulfonate and/or modified enzymatic lignin;
preferably, the lignosulfonate is at least one of sodium lignosulfonate, calcium lignosulfonate, and potassium lignosulfonate.
4. The salt tolerant plugging agent feedstock composition of any one of claims 1-3, wherein said non-ionic acrylamide polymer is selected from at least one of acrylamide homopolymer, N-dimethylacrylamide homopolymer, acrylamide/N, N-dimethylacrylamide copolymer, acrylamide/N-vinylpyrrolidone copolymer, N-dimethylacrylamide/N-vinylpyrrolidone copolymer, and acrylamide/N, N-dimethylacrylamide/N-vinylpyrrolidone copolymer;
preferably, the nonionic acrylamide polymer is an acrylamide/N-vinyl pyrrolidone copolymer;
preferably, the viscosity average molecular weight of the nonionic acrylamide polymer is 400 to 1500 ten thousand, more preferably 500 to 1000 ten thousand.
5. The salt-tolerant plugging agent raw material composition according to any one of claims 1 to 4, wherein the cross-linking agent is selected from at least one of water-soluble phenolic resin, water-soluble urea-formaldehyde resin, water-soluble furfural resin and a mixture of phenolic raw materials and aldehyde raw materials;
preferably, the water-soluble phenolic resin is prepared from phenol and formaldehyde under alkaline conditions in a ratio of 0.2-0.75: 1 is polymerized;
preferably, the water-soluble urea-formaldehyde resin is prepared from formaldehyde and urea according to the weight ratio of 1-3: 1 is polymerized;
preferably, the phenolic raw material is selected from at least one of catechol, resorcinol and hydroquinone, more preferably hydroquinone;
preferably, the aldehyde raw material is selected from at least one of formaldehyde, glyoxal, hexamethylenetetramine and furan alcohol, and more preferably hexamethylenetetramine.
6. The salt-tolerant plugging agent raw material composition according to any one of claims 1 to 5, wherein the oxygen scavenger is at least one of sodium thiosulfate, sodium sulfite, sodium bisulfite, sodium hydrosulfite, isoascorbic acid and thiourea.
7. A method for preparing a salt-resistant plugging agent, which is characterized by comprising the following steps:
(1) dissolving water-soluble lignin in the presence of a solvent to obtain a water-soluble lignin solution;
(2) and mixing the water-soluble lignin solution with the nonionic acrylamide polymer, and then mixing the obtained mixed material with a cross-linking agent and an oxygen scavenger to obtain the salt-resistant plugging agent.
8. The method of claim 7, wherein the non-ionic acrylamide polymer is used in an amount of 0.1-1.5 wt%, the cross-linking agent is used in an amount of 0.5-5 wt%, the oxygen scavenger is used in an amount of 0.01-2 wt%, and the water-soluble lignin is used in an amount of 0.1-10 wt%, based on the total weight of the salt-resistant plugging agent;
preferably, based on the total weight of the salt-resistant plugging agent, the dosage of the nonionic acrylamide polymer is 0.2-1 wt%, the dosage of the crosslinking agent is 0.8-4 wt%, the dosage of the oxygen scavenger is 0.05-0.5 wt%, and the dosage of the water-soluble lignin is 0.2-8 wt%.
9. The method of claim 7 or 8, wherein the non-ionic acrylamide polymer is selected from at least one of acrylamide homopolymer, N-dimethylacrylamide homopolymer, acrylamide/N, N-dimethylacrylamide copolymer, acrylamide/N-vinylpyrrolidone copolymer, N-dimethylacrylamide/N-vinylpyrrolidone copolymer, and acrylamide/N, N-dimethylacrylamide/N-vinylpyrrolidone copolymer; and/or
The cross-linking agent is selected from at least one of water-soluble phenolic resin, water-soluble urea-formaldehyde resin, water-soluble furfural resin and a mixture of a phenolic raw material and an aldehyde raw material; and/or
The oxygen scavenger is at least one of sodium thiosulfate, sodium sulfite, sodium bisulfite, sodium hydrosulfite, isoascorbic acid and thiourea; and/or
The solvent is water; and/or
The water-soluble lignin is lignosulfonate and/or modified enzymatic hydrolysis lignin;
preferably, the preparation method of the modified enzymatic hydrolysis lignin comprises the following steps: dissolving enzymatic hydrolysis lignin at 40-50 deg.C and pH of 10-12 to obtain modified enzymatic hydrolysis lignin solution, and adjusting pH of the modified enzymatic hydrolysis lignin solution to neutral to obtain modified enzymatic hydrolysis lignin.
10. The salt-resistant plugging agent prepared by the method of any one of claims 7 to 9.
11. Use of the salt-tolerant plugging agent raw material composition of any one of claims 1-6 or the salt-tolerant plugging agent of claim 10 in reservoir exploitation, in particular in carbonate reservoir exploitation.
12. A method of reservoir exploitation, the method comprising: injecting the salt-tolerant plugging agent of claim 10 into a subterranean formation such that the salt-tolerant plugging agent crosslinks in situ in the subterranean formation to form a gel.
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| CN102807849A (en) * | 2012-04-06 | 2012-12-05 | 中国石油大学(华东) | Gel plugging agent for deep profile control of higher temperature oil reservoir and preparation method of gel plugging agent |
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| CN102807849A (en) * | 2012-04-06 | 2012-12-05 | 中国石油大学(华东) | Gel plugging agent for deep profile control of higher temperature oil reservoir and preparation method of gel plugging agent |
| CN103232839A (en) * | 2013-05-15 | 2013-08-07 | 中国石油大学(华东) | Water shutoff agent applicable to high-temperature high-salt oil reservoir water shutoff profile control |
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