CN114672291B - Lignin-based water shutoff and profile control system and preparation method and application thereof - Google Patents
Lignin-based water shutoff and profile control system and preparation method and application thereof Download PDFInfo
- Publication number
- CN114672291B CN114672291B CN202011552715.XA CN202011552715A CN114672291B CN 114672291 B CN114672291 B CN 114672291B CN 202011552715 A CN202011552715 A CN 202011552715A CN 114672291 B CN114672291 B CN 114672291B
- Authority
- CN
- China
- Prior art keywords
- lignin
- profile control
- water shutoff
- hydrolyzed
- chloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- 229920005610 lignin Polymers 0.000 title claims abstract description 170
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 139
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 150000001408 amides Chemical class 0.000 claims abstract description 69
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 37
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 23
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 23
- 239000000654 additive Substances 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 150000001412 amines Chemical class 0.000 claims description 39
- 239000003795 chemical substances by application Substances 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 238000006460 hydrolysis reaction Methods 0.000 claims description 29
- 230000007062 hydrolysis Effects 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- 238000005576 amination reaction Methods 0.000 claims description 17
- 230000000996 additive effect Effects 0.000 claims description 16
- 230000003301 hydrolyzing effect Effects 0.000 claims description 13
- 150000001263 acyl chlorides Chemical class 0.000 claims description 12
- 238000005917 acylation reaction Methods 0.000 claims description 12
- ZUGAOYSWHHGDJY-UHFFFAOYSA-K 5-hydroxy-2,8,9-trioxa-1-aluminabicyclo[3.3.2]decane-3,7,10-trione Chemical group [Al+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O ZUGAOYSWHHGDJY-UHFFFAOYSA-K 0.000 claims description 11
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 7
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 7
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 7
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 6
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 claims description 6
- ARBOVOVUTSQWSS-UHFFFAOYSA-N hexadecanoyl chloride Chemical compound CCCCCCCCCCCCCCCC(Cl)=O ARBOVOVUTSQWSS-UHFFFAOYSA-N 0.000 claims description 6
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 claims description 6
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-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
- ATHGHQPFGPMSJY-UHFFFAOYSA-N spermidine Chemical compound NCCCCNCCCN ATHGHQPFGPMSJY-UHFFFAOYSA-N 0.000 claims description 6
- PFNFFQXMRSDOHW-UHFFFAOYSA-N spermine Chemical compound NCCCNCCCCNCCCN PFNFFQXMRSDOHW-UHFFFAOYSA-N 0.000 claims description 6
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 6
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- -1 oleic acid acyl chloride Chemical class 0.000 claims description 5
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 4
- MRKXCQPDRPTZCG-IUQGRGSQSA-N (9e,12e,15e)-octadeca-9,12,15-trienoyl chloride Chemical compound CC\C=C\C\C=C\C\C=C\CCCCCCCC(Cl)=O MRKXCQPDRPTZCG-IUQGRGSQSA-N 0.000 claims description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 3
- 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
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-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
- 239000005642 Oleic acid Substances 0.000 claims description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000005700 Putrescine Substances 0.000 claims description 3
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 claims description 3
- 239000012346 acetyl chloride Substances 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims description 3
- 235000010350 erythorbic acid Nutrition 0.000 claims description 3
- 229940026239 isoascorbic acid Drugs 0.000 claims description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 3
- WTBAHSZERDXKKZ-UHFFFAOYSA-N octadecanoyl chloride Chemical compound CCCCCCCCCCCCCCCCCC(Cl)=O WTBAHSZERDXKKZ-UHFFFAOYSA-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
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 229940063673 spermidine Drugs 0.000 claims description 3
- 229940063675 spermine Drugs 0.000 claims description 3
- PVFOMCVHYWHZJE-UHFFFAOYSA-N trichloroacetyl chloride Chemical compound ClC(=O)C(Cl)(Cl)Cl PVFOMCVHYWHZJE-UHFFFAOYSA-N 0.000 claims description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 6
- 238000004880 explosion Methods 0.000 claims 2
- 229940018564 m-phenylenediamine Drugs 0.000 claims 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims 1
- 238000011084 recovery Methods 0.000 claims 1
- 230000000903 blocking effect Effects 0.000 abstract description 13
- 230000007613 environmental effect Effects 0.000 abstract description 8
- 238000010276 construction Methods 0.000 abstract description 6
- 239000002332 oil field water Substances 0.000 abstract description 2
- 239000000499 gel Substances 0.000 description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 239000000243 solution Substances 0.000 description 22
- 238000004132 cross linking Methods 0.000 description 20
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 238000003756 stirring Methods 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 10
- 230000001105 regulatory effect Effects 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 235000011121 sodium hydroxide Nutrition 0.000 description 8
- 230000033558 biomineral tissue development Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000001376 precipitating effect Effects 0.000 description 6
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 5
- 230000010933 acylation Effects 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- MLQBTMWHIOYKKC-KTKRTIGZSA-N (z)-octadec-9-enoyl chloride Chemical compound CCCCCCCC\C=C/CCCCCCCC(Cl)=O MLQBTMWHIOYKKC-KTKRTIGZSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 3
- LVYZJEPLMYTTGH-UHFFFAOYSA-H dialuminum chloride pentahydroxide dihydrate Chemical compound [Cl-].[Al+3].[OH-].[OH-].[Al+3].[OH-].[OH-].[OH-].O.O LVYZJEPLMYTTGH-UHFFFAOYSA-H 0.000 description 3
- 230000002255 enzymatic effect Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 235000015110 jellies Nutrition 0.000 description 3
- 239000008274 jelly Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 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
- 230000009471 action Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000012360 testing method 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
- C09K8/56—Compositions for consolidating loose sand or the like around wells without excessively decreasing the permeability thereof
- C09K8/57—Compositions based on water or polar solvents
- C09K8/575—Compositions based on water or polar solvents containing organic compounds
- C09K8/5751—Macromolecular compounds
- C09K8/5758—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
- C09K8/56—Compositions for consolidating loose sand or the like around wells without excessively decreasing the permeability thereof
- C09K8/57—Compositions based on water or polar solvents
- C09K8/575—Compositions based on water or polar solvents containing organic compounds
- C09K8/5751—Macromolecular compounds
- C09K8/5753—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- C09K8/56—Compositions for consolidating loose sand or the like around wells without excessively decreasing the permeability thereof
- C09K8/57—Compositions based on water or polar solvents
- C09K8/575—Compositions based on water or polar solvents containing organic compounds
- C09K8/5751—Macromolecular compounds
- C09K8/5756—Macromolecular compounds containing cross-linking agents
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Compounds Of Unknown Constitution (AREA)
- Sealing Material Composition (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of oil field water shutoff and profile control, in particular to a lignin-based water shutoff and profile control system, and a preparation method and application thereof. The preparation raw materials of the water shutoff profile control system comprise: hydrolyzed lignin amide, hydrolyzed polyacrylamide, aluminum-based cross-linking agents and additives. The water shutoff and profile control system can be controlled to form gel (18 h-8 d) within a wider oil reservoir temperature (35-115 ℃) range, the plugging rate is more than 98.3%, the breakthrough pressure is more than 4.5MPa/m, the temperature resistance is improved, and the strength is higher; the system has the characteristics of high viscosity, high blocking strength, high applicable temperature and the like, effectively reduces the production cost of the water blocking profile control system, meets the requirements of site construction on performance, economy and environmental protection, and has higher practicability.
Description
Technical Field
The invention relates to the technical field of oil field water shutoff and profile control, in particular to a lignin-based water shutoff and profile control system and a preparation method and application thereof.
Background
The profile control is to plug the high permeable layer by injecting a plugging agent system from the water injection well, thereby realizing the purpose of adjusting the absorption profile of the water injection layer section and achieving the balanced displacement of the reservoir, and being an effective way for improving the water flooding development effect. The water shutoff and profile control technology is an effective means for improving the heterogeneity of a reservoir under low oil price and realizing balanced displacement and stable production of an oil field. The existing plugging agent can be roughly divided into jelly, gel, sediment, granule, microsphere, foam, microorganism, etc., wherein the aluminum jelly is prepared from Al 3+ The polymer with carboxyl (-COO-) in the polynuclear hydroxyl bridging ion crosslinking solution is formed. Aluminum jelly is typically formulated into colloidal dispersions because of its relatively low strength. In the injection process, the flow velocity of the near wellbore zone is high, the shearing effect is strong, the viscosity of the system is low, and the injection is easy; when the system enters the deep part of the oil reservoir, the flow speed is reduced, the shearing action is weakened, the system begins to form a large amount of gel, the viscosity is rapidly increased, and the plugging action is started to be generated.
However, with the fluctuation of price of fossil-based raw materials and the higher demand for biodegradability of oilfield chemicals during field application in the oilfield, the most widely used Al 3+ The crosslinker/HPAM system has been difficult to gradually meet environmental requirements; meanwhile, the plugging system has the problems of poor temperature resistance and insufficient colloid strength, and the performance is required to be improved. Therefore, the aluminum gel system which is low in cost, excellent in product performance and meets the environmental protection requirement is developed, and has important significance for sustainable development of water shutoff profile control technology.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides a lignin-based water shutoff and profile control system, and a preparation method and application thereof. The water shutoff and profile control system can be controlled to form gel (18 h-8 d) within a wider oil reservoir temperature (35-115 ℃) range, the plugging rate is more than 98.3%, the breakthrough pressure gradient is more than 4.5MPa/m, the temperature resistance is improved, and the strength is higher; the system has the characteristics of high viscosity, high blocking strength, high applicable temperature and the like, effectively reduces the production cost of the water blocking profile control system, meets the requirements of site construction on performance, economy and environmental protection, and has higher practicability.
In order to achieve the above object, a first aspect of the present invention provides a water shutoff and profile control system, the preparation raw materials of the water shutoff and profile control system include: hydrolyzed lignin amide, hydrolyzed polyacrylamide, aluminum-based cross-linking agents and additives.
The second aspect of the invention provides a method for preparing a lignin-based water shutoff and profile control system, which comprises the following steps: in the presence of a solvent, carrying out contact reaction on hydrolyzed lignin amide, hydrolyzed polyacrylamide, a cross-linking agent and an additive to obtain the water shutoff profile control system.
The third aspect of the invention provides a lignin-based water shutoff and profile control system prepared by the preparation method.
The fourth aspect of the invention provides the application of the lignin-based water shutoff profile control system in oil extraction in an oil field.
According to the technical scheme, the water shutoff and profile control system provided by the invention realizes replacement of petrochemical raw materials by biological materials, and can be controlled to be gel (18 h-8 d) within a wider oil reservoir temperature (35-115 ℃) range, the plugging rate is more than 98.3%, the breakthrough pressure gradient is more than 4.5MPa/m, the temperature resistance is improved, and the strength is higher; the system has the characteristics of high viscosity, high blocking strength, high applicable temperature and the like, effectively reduces the production cost of the water blocking profile control system, meets the requirements of site construction on performance, economy and environmental protection, and has higher practicability.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In a first aspect, the present invention provides a lignin-based water shutoff and profile control system, the preparation raw materials of the water shutoff and profile control system include: hydrolyzed lignin amide, hydrolyzed polyacrylamide, aluminum-based cross-linking agents and additives.
Lignin is a complex natural polymer, and a three-dimensional network structure of hetero-branched chains is formed by bonding phenylpropyl groups through ether (C-O-C) or carbon-carbon bonds (C-C). Lignin is second only to cellulose in natural world, and is the second largest natural organic matter. The industrial lignin has rich sources and low cost, and can be used as a raw material for producing oilfield chemicals. The industrial lignin products have different structures due to different sources and separation methods, mainly contain active groups such as aryl, phenolic hydroxyl, alcoholic hydroxyl, carbonyl, methoxy, carboxyl and conjugated double bonds, and can carry out various chemical reactions such as oxidation, reduction, hydrolysis, alcoholysis, photolysis, acylation, sulfonation, alkylation, halogenation, nitration, condensation, graft copolymerization and the like.
The inventor of the invention unexpectedly discovers in the research that the hydrolyzed lignin amide is obtained by amination, acylation and hydrolytic modification of lignin, and the hydrolyzed lignin amide is matched with hydrolyzed polyacrylamide, an aluminum-based cross-linking agent and an additive to be used for preparing an aluminum gel system, so that the performance of the plugging agent is finally improved. Presumably, the reason for this is that lignin crosslinking sites are increased and lignin crosslinking activity is improved by subjecting lignin to amination and acylation modification. In addition, lignin amide is matched with other components of the water shutoff and profile control system, can be controllably formed into gel (18 h-8 d) within a wider oil reservoir temperature (35-115 ℃) range, has a plugging rate of more than 98.3 percent and a breakthrough pressure gradient of more than 4.5MPa/m, improves the temperature resistance and has higher strength; the system has the characteristics of high viscosity, high blocking strength, high applicable temperature and the like, effectively reduces the production cost of the water blocking profile control system, meets the requirements of site construction on performance, economy and environmental protection, and has higher practicability.
Preferably, the hydrolyzed lignin amide is prepared by the following method: in the solution, the lignin is subjected to amination reaction with organic amine, acylation reaction with acyl chloride and hydrolysis reaction with a hydrolysis agent in sequence to obtain the hydrolyzed lignin amide.
In the present invention, the lignin, the organic amine and the acyl chloride are all commercially available, and preferably the lignin is contained in an effective amount of 80 to 99.9%.
In the present invention, the lignin may be various lignin conventionally used, preferably, the lignin is selected from at least one of alkali lignin, enzymatic lignin, chlorinated lignin, steam exploded lignin, lignin sulfonate and sulfur lignin, more preferably enzymatic lignin, which is commercially available, for example, from Shandong Biotechnology Co., ltd.
In the present invention, the organic amine may be various organic amines conventionally used, preferably, the organic amine is selected from at least one of dimethylamine, ethylenediamine, trimethylamine, triethylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, putrescine, cadaverine, spermidine and spermine, more preferably diethylenetriamine and/or tetraethylenepentamine.
In the present invention, the amount of the organic amine may be selected within a wide range, and in order to further improve the performance of the water shutoff profile control system, it is preferable that the mass ratio of the organic amine to the lignin is 0.05-4.5:1, for example, 0.05:1, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2:1, 2.1:1, 2.2:1, 2.3:1, 2.4:1, 2.5:1, 3:1, 3.5:1, 4:1.
In the present invention, the conditions of the amination reaction may be changed within a wide range as long as the lignin can be effectively aminated, and in order to further improve the performance of the water shutoff profile control system, the temperature is preferably 60 to 75 ℃ (for example, may be 60 ℃, 65 ℃, 70 ℃, 75 ℃) for 1.5 to 4 hours (for example, may be 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours), and the pH is 10 to 11.5 (for example, may be 10, 10.5, 11, 11.5).
In a preferred embodiment of the present invention, the amination reaction is carried out in the presence of an aldehyde; the aldehyde is preferably a C1-C5 aldehyde, for example, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, more preferably formaldehyde. With the preferred embodiment, the performance of the prepared water shutoff profile control system can be further improved.
Preferably, the mass ratio of aldehyde to lignin is 0.02-1.5:1, e.g. may be 0.02:1, 0.05:1, 0.1:1, 0.3:1, 0.5:1, 0.7:1, 0.9:1, 1.1:1, 1.3:1, 1.35:1, 1.4:1, 1.45:1, 1.5:1.
In the present invention, the acid chloride may be various acid chlorides conventionally used, preferably, the acid chloride is selected from at least one of acetyl chloride, benzoyl chloride, oxalyl chloride, chloroacetyl chloride, trichloroacetyl chloride, fatty acid chloride, stearoyl chloride, linolenoyl chloride, oleic acid chloride and palmitoyl chloride, more preferably oleic acid chloride and/or palmitoyl chloride.
In the present invention, the amount of the acid chloride may be selected within a wide range, and in order to further improve the performance of the water shutoff profile control system, it is preferable that the mass ratio of the acid chloride to the lignin amine is 0.5-2.5:1 (for example, may be 0.5:1, 0.8:1, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.8:1, 2:1, 2.2:1, 2.5:1).
In the present invention, the conditions of the acylation reaction may be changed within a wide range as long as the lignin can be effectively acylated to obtain lignin amide, and in order to further improve the performance of the water shutoff profile control system, the temperature is preferably 55 to 65 ℃ (for example, may be 55 ℃, 60 ℃, 65 ℃), the time is 1 to 4 hours (for example, may be 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours), and the pH is 8 to 9.5 (for example, may be 8, 8.5, 9, 9.5).
In the present invention, the hydrolyzing agent may be any substance capable of hydrolyzing the resulting lignin amide, preferably, the hydrolyzing agent is a base, more preferably, the hydrolyzing agent is at least one selected from the group consisting of sodium hydroxide, sodium carbonate, sodium bicarbonate and potassium hydroxide.
In the present invention, the amount of the hydrolysis agent may be selected within a wide range, and in order to further improve the performance of the water shutoff profile control system, it is preferable that the mass ratio of the hydrolysis agent to the lignin amide is 0.0001 to 0.8:1, preferably 0.01-0.05:1, the concentration of the hydrolysing agent being 15-50wt%.
In the present invention, the conditions of the hydrolysis reaction may be changed within a wide range as long as the hydrolysis of the aminated and acylated lignin is possible, and in order to further improve the performance of the water shutoff profile control system, the temperature is preferably 60 to 80 ℃ (for example, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃) and the time is 2 to 12 hours (for example, 2 hours, 2.5 hours, 3 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours may be mentioned).
The inventor finds in the study that better effect can be obtained when the hydrolyzed lignin amide obtained under the conditions of amination with temperature of 60-75 ℃ for 1.5-4h and pH value of 10-11.5, acylation with temperature of 55-65 ℃ for 1-4h and pH value of 8-9.5 and hydrolysis with temperature of 60-80 ℃ for 2-12h is used in a water shutoff profile control system.
In the present invention, the solution is preferably an aqueous solution.
In the present invention, the method of adjusting the pH is a method commonly used in the art, and preferably, the pH adjustment is performed by adding an alkaline substance. The alkaline substance can be sodium hydroxide solution, potassium hydroxide solution, sodium carbonate solution and the like.
In a preferred embodiment of the invention: the preparation method of the hydrolyzed lignin amide comprises the steps of preparing lignin into lignin aqueous solution, and then adding organic amine under stirring for amination reaction to obtain solid-phase lignin amine; preparing solid-phase lignin amine into lignin amine aqueous solution, and then adding acyl chloride under stirring to carry out acylation reaction; finally, adding a hydrolytic agent to carry out hydrolysis reaction to obtain the hydrolyzed lignin amide.
Preferably, the lignin concentration in the aqueous lignin solution is 3-50wt%, for example, may be 3wt%, 5wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%.
Preferably, the organic amine is added to the aqueous lignin solution by means of dropwise addition.
Preferably, the concentration of lignin amine in the aqueous lignin amine solution is 3-30wt%.
Preferably, the acid chloride is added dropwise to the aqueous lignin amine solution.
Preferably, the solid-phase lignin amine is obtained by the following steps: and after the amination reaction is finished, regulating the pH value to separate out a product, and then washing and drying to obtain an intermediate product lignin amine.
In a particularly preferred embodiment of the invention, the hydrolyzed lignin amide is prepared by the following process:
(1) Dissolving lignin and alkali in water, and stirring to prepare lignin solution;
(2) Then adding organic amine, regulating pH, adding formaldehyde under stirring, heating and refluxing for reaction, regulating pH to be neutral after the reaction is finished, separating out a product, and washing and drying to obtain an intermediate lignin amine;
(3) Dissolving intermediate lignin amine in water, regulating pH, adding acyl chloride under stirring, continuing to react, and performing suction filtration, washing, drying and grinding to obtain lignin amide products;
(4) And mixing lignin amide with the hydrolysate for hydrolysis reaction, and drying and grinding after the reaction to obtain a hydrolysis lignin amide product.
Preferably, the hydrolyzed lignin amide is prepared by the following method:
(1) At room temperature, dissolving lignin and NaOH in water to prepare lignin solution; wherein the concentration of lignin in the lignin solution is 3-50wt% and the concentration of NaOH in the lignin solution is 0.001-8.0wt%;
(2) Then dripping organic amine, regulating the pH to 10-11.5, dripping formaldehyde under stirring, heating and refluxing for reaction, regulating the pH to be nearly neutral after the reaction is finished, separating out a product, and washing and drying to obtain an intermediate lignin amine; wherein the mass ratio of the organic amine, formaldehyde and lignin is 0.05-4.5:0.02-1.5:1, the reaction temperature is 60-75 ℃ and the reaction time is 1.5-4h;
(3) Dissolving intermediate lignin amine in water to prepare a concentration of 3-30wt%, regulating and maintaining the pH to 8-9.5, dripping acyl chloride under stirring, heating to 55-65 ℃ for continuous reaction for 1-4h, and carrying out suction filtration, washing, drying and grinding to obtain lignin amide products; wherein the mass ratio of the acyl chloride to the lignin amine is 0.5-2.5:1;
(4) Mixing lignin amide and sodium hydroxide solution according to a certain proportion, hydrolyzing, sealing, placing at 60-80 ℃ for reaction for 2-12h, drying and grinding after the reaction to obtain a hydrolyzed lignin amide product; wherein the mass ratio of the hydrolytic agent to the lignin amide is 0.0001-0.8:1, the concentration of the hydrolytic agent is 15-50wt%.
In the present invention, there is no particular limitation on the content of each component, and in order to further obtain a better effect, for example, to enable the profile control agent to achieve controllable crosslinking at a higher gel forming temperature and to have a better gel strength, preferably, the content of the hydrolyzed lignin amide is 0.1 to 4.5wt% (for example, may be 0.1wt%, 0.5wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt%, 4wt%, 4.5wt%, preferably 0.4 to 2 wt%); the content of the hydrolyzed polyacrylamide is 0.01 to 1.5wt% (for example, may be 0.01wt%, 0.05wt%, 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1wt%, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt%, 1.5wt%, preferably 0.01 to 0.5 wt%); the crosslinking agent is present in an amount of 0.05 to 2wt% (e.g., may be 0.05wt%, 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1wt%, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt%, 1.5wt%, 1.6wt%, 1.7wt%, 1.8wt%, 1.9wt%, 2wt%, preferably 0.2 to 1.2 wt%); the content of the additive is 0.03 to 0.6wt% (for example, may be 0.03wt%, 0.05wt%, 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, preferably 0.05 to 0.4 wt%).
In the present invention, the hydrolyzed polyacrylamide (the polyacrylamide generally refers to anionic polyacrylamide) may be any hydrolyzed polyacrylamide, preferably, in order to further improve the performance of the prepared water shutoff and profile control system, the hydrolyzed polyacrylamide preferably has a degree of hydrolysis of 15-30%, which is commercially available, for example, from Shandong Bao Mohs Biochemical Co., ltd.
In the present invention, the weight average molecular weight of the hydrolyzed polyacrylamide is preferably 800 to 3000 ten thousand.
In the present invention, preferably, the crosslinking agent is an aluminum crosslinking agent selected from at least one of aluminum citrate and aluminum polymer; in the present invention, the aluminum citrate is commercially available, for example, from Ningbo chemical raw materials Co.
Wherein the polyaluminum is ACH full name Aluminum Chlorohydrate, chinese name aluminum hydroxychloride, also called polyaluminum or aluminum hydroxychloride, and has a molecular formula of Al 2 (OH) 5 Cl·2H 2 O。
In the present invention, the additive is commercially available; preferably, the additive is selected from at least one of sodium thiosulfate, sodium sulfite, sodium bisulfite, sodium dithionite, metaphenylene diamine, isoascorbic acid and thiourea.
It will be clear to those skilled in the art that the preparation raw materials of the lignin-based water shutoff profile control system of the present invention further comprise a pH adjustor and water. In a preferred embodiment of the invention, the preparation raw materials of the water shutoff and profile control system consist of hydrolyzed lignin amide, hydrolyzed polyacrylamide, an aluminum-based crosslinking agent, an additive, a pH regulator and water. It can be clear that due to the purity problem of the raw materials used, part of impurities are inevitably present in each raw material, so that it can be understood that the raw materials for preparing the water shutoff and profile control system consist of hydrolyzed lignin amide, hydrolyzed polyacrylamide, aluminum-based cross-linking agent, additives, pH regulator, water and impurities carried by each raw material.
In the present invention, the pH adjustor may be an acid or an alkali substance commonly used in the art for adjusting pH; preferably, the pH regulator is at least one selected from the group consisting of dilute hydrochloric acid, dilute sulfuric acid, sodium hydroxide, sodium carbonate, sodium bicarbonate, sodium acetate and aqueous ammonia.
In the present invention, the water used in the preparation of the lignin-based water shutoff and profile control system is not particularly limited, and may be river, lake, atmospheric water, sea water, groundwater, artificial water, oilfield produced water, etc., preferably water having a mineralization degree of less than 30000mg/L and a divalent ion of less than 3000 mg/L.
In a second aspect, the invention provides a method for preparing a lignin-based water shutoff and profile control system, which comprises the following steps: in the presence of a solvent, carrying out contact reaction on hydrolyzed lignin amide, hydrolyzed polyacrylamide, a cross-linking agent and an additive to obtain the water shutoff profile control system.
The preparation, selection and amounts of the hydrolyzed lignin amide, hydrolyzed polyacrylamide, cross-linking agent and additives in the present invention have been described in detail in the first aspect above, and in order to avoid unnecessary repetition, the description thereof will not be repeated here.
According to a preferred embodiment of the invention, the preparation method of the lignin-based water shutoff and profile control system comprises the following steps:
(1) Adding hydrolyzed lignin amide and hydrolyzed polyacrylamide into water under stirring until the hydrolyzed lignin amide and hydrolyzed polyacrylamide are uniformly dissolved;
(2) And adding a cross-linking agent, an additive and a pH regulator for contact reaction to obtain the water shutoff profile control system.
In the invention, the adding sequence of the crosslinking agent, the additive and the pH regulator is not particularly limited, so as to realize uniform mixing and obtain the water shutoff profile control system.
In the present invention, the pH adjustor is preferably used in such an amount that the pH of the reaction system does not cause Al 3+ Precipitation is sufficient, and may be, for example, 5.5 to 6.5.
In the present invention, preferably, the temperature and time of the contact reaction are not particularly required as long as the materials can be uniformly mixed.
The third aspect of the invention provides a lignin-based water shutoff and profile control system prepared by the preparation method.
The fourth aspect of the invention provides the application of the lignin-based water shutoff profile control system in oil extraction in an oil field.
Compared with the prior art, the invention has the following advantages:
the water shutoff profile control system can be controlled to be gel (18 h-8 d) within a wider oil reservoir temperature (35-115 ℃) range, the plugging rate is more than 98.3%, the breakthrough pressure gradient is more than 4.5MPa/m, the temperature resistance is improved, and the water shutoff profile control system has higher strength; the system has the characteristics of high viscosity, high blocking strength, high applicable temperature and the like, effectively reduces the production cost of the water blocking and profile control system, meets the requirements of on-site construction on performance, economy and environmental protection, has higher practicability, and can be applied to water blocking and profile control in the oil extraction process of an oil field.
The present invention will be described in detail by examples. In the following examples and comparative examples,
the complex viscosity was tested using a rotational rheometer (available from sameidie technologies, inc. RS 6000).
The enzymatic lignin was purchased from Shandong Longli Biotechnology Co., ltd, and the lignin content was more than 80% by weight.
The crosslinking agent aluminum citrate is purchased from Ningbo chemical raw material Co., ltd, and the concentration of aluminum is 2000mg/kg.
Diethylenetriamine, tetraethylenepentamine, oleic acid chloride and palmitoyl chloride were purchased from carbofuran technologies.
Core plugging capability test:
an artificial core (sand filling pipe) with the diameter of 25mm and the length of 65mm is taken, the initial permeability is measured by using 10% NaCl solution, the plugging agent solution is injected in the forward direction or the reverse direction to form gel by the solution under the gel forming strip of the preparation example/comparative example, the gel is washed in the forward direction by using the 10% NaCl solution, and the breakthrough pressure and the permeability after plugging are measured.
The breakthrough pressure gradient is calculated from the breakthrough pressure and the core size.
Preparation example 1
This preparation example is used to illustrate the preparation of hydrolyzed lignin amide L1
(1) At room temperature, 10g lignin and 1.62g NaOH were dissolved in water to prepare a 15wt% lignin solution.
(2) Then 12.5g of diethylenetriamine is dripped into the mixture, the pH value is regulated to 10.5, 14.1g of formaldehyde is dripped into the mixture under stirring, the mixture is heated and refluxed for 2.5 hours, the pH value is regulated to be nearly neutral after the reaction is finished, the product is separated out, and the intermediate lignin amine is obtained through washing and drying.
(3) 6g of lignin amine is taken and dissolved in water, the pH value is regulated and kept to 8.5, 7.53g of oleic acid acyl chloride is dripped under stirring, then the temperature is raised to 60 ℃ for continuous reaction for 3 hours, and after the reaction, the lignin amide is obtained through suction filtration, washing, drying and grinding.
(4) 6.5g of lignin amide is taken, added into water to be swelled, then is mixed with 0.21g of 30wt percent NaOH solution, the mixture is sealed and placed at 60 ℃ to continue the reaction for 8 hours, and after the reaction, the mixture is dried and ground, thus obtaining the hydrolysis lignin amide product L1.
Preparation example 2
This preparation example is used to illustrate the preparation of hydrolyzed lignin amide L2
The procedure of preparation 1 was followed, except that 12.5g of diethylenetriamine was replaced with 19.4g of tetraethylenepentamine and 7.53g of oleic acid chloride was replaced with 6.8g of palmitoyl chloride, to obtain hydrolyzed lignin amide product L2.
Preparation example 3
This preparation example is used to illustrate the preparation of hydrolyzed lignin amide L3
The procedure of preparation 1 was followed, except that formaldehyde was not added in step (2), to obtain hydrolyzed lignin amide product L3.
Example 1
The embodiment is used for explaining the water shutoff and profile control system provided by the invention
12.1g of hydrolyzed lignin amide L1 and 1.6g of hydrolyzed polyacrylamide (weight average molecular weight of 1500 ten thousand, degree of hydrolysis of 25%, purchased from Shandong Bao Mo Biochemical Co., ltd.) are dissolved in formulated water (divalent ion lower than 3000 mg/L) with a degree of mineralization of 13000mg/L, and stirred at a rotation speed of 500r/min until it is uniformly dissolved; then 1.11g of sodium bisulphite and 2g of aluminum citrate are added, and the pH value of the system is adjusted so as not to lead Al 3+ Precipitating, wherein the total mass of the system is 1kg, stirring uniformly to obtain a water shutoff profile control system, and pluggingThe water profile control system starts to gel after 1d at 98 ℃, the compound viscosity reaches 51710 mPa.s after the crosslinking reaction is finished, the plugging rate is 99.3%, and the breakthrough pressure gradient is 4.95MPa/m.
Example 2
The embodiment is used for explaining the water shutoff and profile control system provided by the invention
Dissolving 4g of hydrolyzed lignin amide L1 and 5g of hydrolyzed polyacrylamide (with a weight average molecular weight of 1000 ten thousand and a degree of hydrolysis of 23%, purchased from Shandong Bao Mo biochemical Co., ltd.) in water with a mineralization degree of 15000mg/L, and stirring at a rotation speed of 500r/min until the water is uniformly dissolved; then 4g of sodium bisulphite and 8g of aluminum citrate are added, and the pH value of the system is adjusted so as not to lead Al 3+ And (3) precipitating, wherein the total mass of the system is 1kg, and uniformly mixing to obtain a water shutoff and profile control system, wherein the water shutoff and profile control system starts to form gel after 18 hours at 98 ℃, the compound viscosity reaches 59080 mPa.s after the crosslinking reaction is finished, the core plugging rate is 99.8%, and the breakthrough pressure gradient is 5.46MPa/m.
Example 3
The embodiment is used for explaining the water shutoff and profile control system provided by the invention
20g of hydrolyzed lignin amide L1 and 0.1g of hydrolyzed polyacrylamide (with a weight average molecular weight of 2000 ten thousand and a degree of hydrolysis of 20 percent, purchased from Shandong Bao Mo Biochemical Co., ltd.) are dissolved in preparation water with a mineralization degree of 18000mg/L, and stirred at a rotation speed of 500r/min until the mixture is uniformly dissolved; then 0.5g of sodium bisulphite and 12g of aluminum citrate are added, and the pH value of the system is adjusted so as not to lead Al 3+ Precipitating, wherein the total mass of the system is 1kg, and obtaining a water shutoff and profile control system, wherein the water shutoff and profile control system starts to form gel after 2.5d at 98 ℃, the compound viscosity reaches 59680 mPa.s after the crosslinking reaction is finished, the core plugging rate is 99.6%, and the breakthrough pressure gradient is 5.79MPa/m.
Example 4
The embodiment is used for explaining the water shutoff and profile control system provided by the invention
The preparation of the water shutoff and profile control system was carried out in the manner of example 1, except that the hydrolyzed polyacrylamide had a weight average molecular weight of 800 ten thousand, the water shutoff and profile control system began to gel after 29 hours at 98℃and the complex viscosity reached 42350 mPas after the crosslinking reaction, the core plugging rate was 98.9%, and the breakthrough pressure gradient was 4.81MPa/m.
Example 5
The embodiment is used for explaining the water shutoff and profile control system provided by the invention
The preparation of the water shutoff profile control system was performed as in example 1, except that hydrolyzed lignin amide L1 was replaced with hydrolyzed lignin amide L2. The water shutoff and profile control system starts to gel after 31 hours at 98 ℃, the compound viscosity reaches 49810 mPa.s after the crosslinking reaction is finished, the core shutoff rate is 98.9%, and the breakthrough pressure gradient is 4.61MPa/m.
Example 6
The embodiment is used for explaining the water shutoff and profile control system provided by the invention
The preparation of the water shutoff profile control system was performed as in example 1, except that hydrolyzed lignin amide L1 was replaced with hydrolyzed lignin amide L3. The water shutoff and profile control system starts to gel after 62 hours at 98 ℃, the compound viscosity reaches 40120 mPa.s after the crosslinking reaction is finished, the core plugging rate is 98.3%, and the breakthrough pressure gradient is 4.5MPa/m.
Example 7
The embodiment is used for explaining the water shutoff and profile control system provided by the invention
12.4g of hydrolyzed lignin amide L2 and 1.9g of hydrolyzed polyacrylamide (weight average molecular weight of 1500 ten thousand, degree of hydrolysis of 25%, purchased from Shandong Bao Mo Biochemical Co., ltd.) are dissolved in the preparation water with mineralization of 18000mg/L, and stirred at a rotation speed of 500r/min until the mixture is uniformly dissolved; then 1.39g of thiourea and 1.62g of aluminum citrate are added, and the pH value of the system is adjusted so as not to lead Al 3+ Precipitating, wherein the total mass of the system is 1kg, and obtaining a water shutoff and profile control system, wherein the water shutoff and profile control system starts to gel after 20 hours at 115 ℃, the compound viscosity reaches 58980 mPa.s after the crosslinking reaction is finished, the core plugging rate is 99.1%, and the breakthrough pressure gradient is 4.83MPa/m.
Example 8
The embodiment is used for explaining the water shutoff and profile control system provided by the invention
10.9g of hydrolyzed lignin amide L1 and 2.4g of hydrolyzed polyacrylamide (weight average molecular weight 1500 ten thousand,hydrolysis degree of 25%, purchased from Shandong Bao Mo Biochemical Co., ltd.) is dissolved in the prepared water with mineralization degree of 10000mg/L, and stirred at a rotation speed of 500r/min until the water is uniformly dissolved; then 1.45g of thiourea and 1.1g of aluminum citrate are added, and the pH value of the system is adjusted so as not to lead Al 3+ Precipitating, wherein the total mass of the system is 1kg, and obtaining a water shutoff and profile control system, wherein the water shutoff and profile control system starts to form gel after 4.5d at 60 ℃, the compound viscosity reaches 49850 mPa.s after the crosslinking reaction is finished, the core plugging rate is 98.4%, and the breakthrough pressure gradient is 4.6MPa/m.
Example 9
The embodiment is used for explaining the water shutoff and profile control system provided by the invention
10.5g of hydrolyzed lignin amide L2 and 3.5g of hydrolyzed polyacrylamide (weight average molecular weight is 1500 ten thousand, degree of hydrolysis is 25%, purchased from Shandong Bao Mo biochemical Co., ltd.) are dissolved in the prepared water with the mineralization degree of 20000mg/L, and stirred at the rotation speed of 500r/min until the solution is uniformly dissolved; then 1.39g of sodium bisulphite and 1.51g of aluminum citrate are added, and the pH value of the system is adjusted so as not to lead Al 3+ And (3) precipitating, wherein the total mass of the system is 1kg, so as to obtain a water shutoff and profile control system, the water shutoff and profile control system starts to form gel after 2.5d at 75 ℃, the compound viscosity reaches 54330 mPa.s after the crosslinking reaction is finished, the plugging rate is 98.8%, and the breakthrough pressure gradient is 4.74MPa/m.
Comparative example 1
This comparative example is used to illustrate a reference water shutoff profile control system
The preparation of the water shutoff and profile control system was carried out in the manner of example 1, except that the hydrolyzed lignin amide L1 was replaced with lignin amide, the obtained water shutoff and profile control system began to gel after 19 hours at 98℃and the compound viscosity reached 11040 mPa.s after the crosslinking reaction was completed, the plugging rate was 94.1% and the breakthrough pressure gradient was 1.64MPa/m.
Comparative example 2
This comparative example is used to illustrate a reference water shutoff profile control system
The preparation of the water shutoff and profile control system was carried out in the manner of example 7, except that the hydrolyzed lignin amide L2 was replaced with lignin amide, the obtained water shutoff and profile control system began to gel after 16 hours at 115℃and the compound viscosity reached 13100 mPas after the crosslinking reaction was completed, the plugging rate was 95.4%, and the breakthrough pressure gradient was 2.21MPa/m.
Comparative example 3
This comparative example is used to illustrate a reference water shutoff profile control system
The preparation of the water shutoff and profile control system was carried out in the manner of example 8, except that the hydrolyzed lignin amide L1 was replaced with lignin amide, the resulting water shutoff and profile control system began to gel after 30d at 60℃and the complex viscosity reached 9050 mPa.s after the crosslinking reaction was completed, the plugging rate was 92.3% and the breakthrough pressure gradient was 1.89MPa/m.
Comparative example 4
This comparative example is used to illustrate a reference water shutoff profile control system
The preparation of the water shutoff and profile control system was carried out in the manner of example 9, except that the hydrolyzed lignin amide L2 was replaced with lignin amide, the resulting water shutoff and profile control system began to gel after 27 hours at 75℃and the complex viscosity reached 11050 mPa.s after the crosslinking reaction was completed, the plugging rate was 94.1% and the breakthrough pressure gradient was 2.02MPa/m.
Comparative example 5
This comparative example is used to illustrate a reference water shutoff profile control system
The preparation of the water shutoff and profile control system was carried out in the manner of example 1, except that the hydrolyzed polyacrylamide was replaced with polyacrylamide, the obtained water shutoff and profile control system began to gel after 15d at 98 ℃, the complex viscosity reached 12690mpa·s after the crosslinking reaction was completed, the core plugging rate was 89.2%, and the breakthrough pressure gradient was 1.25mPa/m.
As can be seen from the comparison examples and comparative examples, the invention provides a novel lignin modified product and a preparation method thereof, and creatively applies the lignin modified product to the water shutoff and profile control process of an oil field, and increases lignin crosslinking sites, improves lignin crosslinking activity and finally improves the performance of the plugging agent through lignin amination, acylation and hydrolysis modification. The water shutoff profile control system provided by the invention can be controllably gelled in a wider oil reservoir temperature range, the shutoff rate is more than 98.3%, the breakthrough pressure gradient is more than 4.5MPa/m, the temperature resistance is improved, and the intensity is higher; the system has the characteristics of high viscosity, high blocking strength, high applicable temperature and the like, effectively reduces the production cost of the water blocking profile control system, meets the requirements of site construction on performance, economy and environmental protection, and has higher practicability.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (22)
1. The lignin-based water shutoff and profile control agent is characterized in that the preparation raw materials of the water shutoff and profile control agent comprise: hydrolyzed lignin amide, hydrolyzed polyacrylamide, aluminum-based crosslinking agent and additives; wherein the additive is at least one of sodium thiosulfate, sodium sulfite, sodium bisulfite, sodium dithionite, m-phenylenediamine, isoascorbic acid and thiourea;
wherein, the consumption of the hydrolyzed lignin amide is 0.1 to 4.5 and wt percent based on the total weight of the raw materials of the water shutoff profile control agent; the dosage of the hydrolyzed polyacrylamide is 0.01-1.5 wt%; the dosage of the aluminum-based cross-linking agent is 0.05-2 wt%; the dosage of the additive is 0.03-0.6 wt%;
wherein, lignin in the hydrolytic lignin amide is selected from at least one of alkali lignin, enzymolysis lignin and steam explosion lignin.
2. The water shutoff profile control agent of claim 1, wherein the method of preparing the hydrolyzed lignin amide comprises: in the solution, the lignin is subjected to amination reaction with organic amine, acylation reaction with acyl chloride and hydrolysis reaction with a hydrolysis agent in sequence to obtain the hydrolyzed lignin amide.
3. The water shutoff profile control agent of claim 2, wherein the organic amine is selected from dimethylamine,At least one of ethylenediamine, trimethylamine, triethylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, putrescine, cadaverine, spermidine and spermine; and/or the mass ratio of the organic amine to the lignin is 0.05-4.5:1; and/or, the amination reaction conditions include: at a temperature of 60-75 DEG C o C. The time is 1.5-4h, and the pH value is 10-11.5.
4. The water shut-off profile control agent of claim 2, wherein the amination reaction is performed in the presence of an aldehyde.
5. The water shut-off profile control agent of claim 4, wherein the aldehyde is a C1-C5 aldehyde.
6. The water shutoff profile control agent of claim 2, wherein the acyl chloride is selected from at least one of acetyl chloride, benzoyl chloride, oxalyl chloride, chloroacetyl chloride, trichloroacetyl chloride, stearoyl chloride, linolenoyl chloride, oleic acid acyl chloride, and palmitoyl chloride; and/or, carrying out amination reaction on lignin and organic amine to obtain lignin amine, wherein the mass ratio of acyl chloride to lignin amine is 0.5-2.5:1; and/or, the conditions of the acylation reaction include: at a temperature of 55-65 DEG C o C. The time is 1-4h, and the pH value is 8-9.5.
7. The water shutoff profile control agent of claim 2, wherein the hydrolysis agent is a base; and/or, the hydrolysis reaction conditions include: at a temperature of 60-80 DEG C o C. The time is 2-12h.
8. The water shutoff profile control agent of any of claims 1-7, wherein the hydrolyzed polyacrylamide has a degree of hydrolysis of 15-30%; and/or
The weight average molecular weight of the hydrolyzed polyacrylamide is 800-3000 ten thousand.
9. The water shutoff profile control agent of any of claims 1-7, wherein the aluminum-based cross-linking agent is aluminum citrate and/or aluminum polymer.
10. The water shutoff profile control agent according to claim 1, wherein the amount of the hydrolyzed lignin amide is 0.4-2wt% based on the total weight of the raw materials of the water shutoff profile control agent; the dosage of the hydrolyzed polyacrylamide is 0.01-0.5 wt%; the dosage of the aluminum-based cross-linking agent is 0.2-1.2 wt%; the dosage of the additive is 0.05-0.4. 0.4wt percent.
11. The preparation method of the lignin-based water shutoff profile control agent is characterized by comprising the following steps: in the presence of a solvent, carrying out contact reaction on hydrolyzed lignin amide, hydrolyzed polyacrylamide, an aluminum-based cross-linking agent and an additive to obtain the water shutoff profile control agent; wherein the additive is at least one of sodium thiosulfate, sodium sulfite, sodium bisulfite, sodium dithionite, m-phenylenediamine, isoascorbic acid and thiourea;
wherein, the consumption of the hydrolyzed lignin amide is 0.1 to 4.5 and wt percent based on the total weight of the raw materials of the water shutoff profile control agent; the dosage of the hydrolyzed polyacrylamide is 0.01-1.5 wt%; the dosage of the aluminum-based cross-linking agent is 0.05-2 wt%; the dosage of the additive is 0.03-0.6 wt%;
wherein, lignin in the hydrolytic lignin amide is selected from at least one of alkali lignin, enzymolysis lignin and steam explosion lignin.
12. The method of claim 11, wherein the method of preparing hydrolyzed lignin amide comprises: in the solution, the lignin is subjected to amination reaction with organic amine, acylation reaction with acyl chloride and hydrolysis reaction with a hydrolysis agent in sequence to obtain the hydrolyzed lignin amide.
13. The production method according to claim 12, wherein the organic amine is at least one selected from dimethylamine, ethylenediamine, trimethylamine, triethylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, putrescine, cadaverine, spermidine and spermine; and/or, the organic amineThe mass ratio of the lignin to the lignin is 0.05-4.5:1; and/or, the amination reaction conditions include: at a temperature of 60-75 DEG C o C. The time is 1.5-4h, and the pH value is 10-11.5.
14. The method of claim 12, wherein the amination reaction is performed in the presence of an aldehyde.
15. The method of claim 14, wherein the aldehyde is a C1-C5 aldehyde.
16. The production method according to claim 12, wherein the acyl chloride is at least one selected from acetyl chloride, benzoyl chloride, oxalyl chloride, chloroacetyl chloride, trichloroacetyl chloride, stearoyl chloride, linolenoyl chloride, oleic acid acyl chloride and palmitoyl chloride; and/or, carrying out amination reaction on lignin and organic amine to obtain lignin amine, wherein the mass ratio of acyl chloride to lignin amine is 0.5-2.5:1; and/or, the conditions of the acylation reaction include: at a temperature of 55-65 DEG C o C. The time is 1-4h, and the pH value is 8-9.5.
17. The method of claim 12, wherein the hydrolyzing agent is a base; and/or, the hydrolysis reaction conditions include: at a temperature of 60-80 DEG C o C. The time is 2-12h.
18. The production method according to any one of claims 11 to 17, wherein the hydrolyzed polyacrylamide has a degree of hydrolysis of 15 to 30%; and/or
The weight average molecular weight of the hydrolyzed polyacrylamide is 800-3000 ten thousand.
19. The method of any one of claims 11-17, wherein the aluminum-based cross-linking agent is aluminum citrate and/or aluminum polymer.
20. The preparation method of claim 11, wherein the amount of the hydrolyzed lignin amide is 0.4-2wt% based on the total weight of the water shutoff profile control agent; the dosage of the hydrolyzed polyacrylamide is 0.01-0.5 wt%; the dosage of the aluminum-based cross-linking agent is 0.2-1.2 wt%; the dosage of the additive is 0.05-0.4. 0.4wt percent.
21. The lignin-based water shutoff profile control agent prepared by the preparation method of any one of claims 11-20.
22. Use of the lignin-based water shutoff profile control agent of any of claims 1-10 and 21 in oil recovery in an oilfield.
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CN202011552715.XA CN114672291B (en) | 2020-12-24 | 2020-12-24 | Lignin-based water shutoff and profile control system and preparation method and application thereof |
JP2023539130A JP2024500525A (en) | 2020-12-24 | 2021-10-27 | Blocking agent for oil field extraction, its preparation method and use |
US18/257,923 US20240052232A1 (en) | 2020-12-24 | 2021-10-27 | Plugging agent for oil extraction in oilfield and a preparation method therefor and application thereof |
PCT/CN2021/126751 WO2022134839A1 (en) | 2020-12-24 | 2021-10-27 | Plugging agent for oil extraction in oilfield and a preparation method therefor and application thereof |
EP21908840.8A EP4261265A4 (en) | 2020-12-24 | 2021-10-27 | SEALING AGENT FOR OIL EXTRACTION IN AN OIL FIELD AND PRODUCTION METHOD AND APPLICATION THEREOF |
ZA2023/07292A ZA202307292B (en) | 2020-12-24 | 2023-07-21 | Plugging agent for oil extraction in oilfield and a preparation method therefor and application thereof |
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