CN109423266B - Amphoteric ion starch microsphere and preparation method and application thereof - Google Patents
Amphoteric ion starch microsphere and preparation method and application thereof Download PDFInfo
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- CN109423266B CN109423266B CN201710720863.XA CN201710720863A CN109423266B CN 109423266 B CN109423266 B CN 109423266B CN 201710720863 A CN201710720863 A CN 201710720863A CN 109423266 B CN109423266 B CN 109423266B
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- starch
- parts
- zwitterionic
- inorganic salt
- salt
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- 229920002472 Starch Polymers 0.000 title claims abstract description 165
- 235000019698 starch Nutrition 0.000 title claims abstract description 160
- 239000008107 starch Substances 0.000 title claims abstract description 160
- 239000004005 microsphere Substances 0.000 title claims abstract description 102
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 95
- 239000002245 particle Substances 0.000 claims abstract description 77
- 239000012266 salt solution Substances 0.000 claims abstract description 38
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002888 zwitterionic surfactant Substances 0.000 claims abstract description 29
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000008367 deionised water Substances 0.000 claims abstract description 24
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 22
- 239000003999 initiator Substances 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000009826 distribution Methods 0.000 claims description 50
- 239000000243 solution Substances 0.000 claims description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 31
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 21
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 20
- 238000005303 weighing Methods 0.000 claims description 19
- 229920001592 potato starch Polymers 0.000 claims description 15
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 11
- 239000011780 sodium chloride Substances 0.000 claims description 10
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- 229920002261 Corn starch Polymers 0.000 claims description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 8
- 150000003863 ammonium salts Chemical class 0.000 claims description 8
- 159000000007 calcium salts Chemical class 0.000 claims description 8
- 239000008120 corn starch Substances 0.000 claims description 8
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 8
- 159000000003 magnesium salts Chemical class 0.000 claims description 8
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 8
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 8
- 159000000000 sodium salts Chemical class 0.000 claims description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 8
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 8
- 240000003183 Manihot esculenta Species 0.000 claims description 7
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 claims description 7
- 240000004922 Vigna radiata Species 0.000 claims description 6
- 235000010721 Vigna radiata var radiata Nutrition 0.000 claims description 6
- 235000011469 Vigna radiata var sublobata Nutrition 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 5
- VTCNIIJVSUFNQZ-UHFFFAOYSA-N CCCCCCCCC(CCCCC[N+](C)(C)CCS([O-])(=O)=O)N Chemical class CCCCCCCCC(CCCCC[N+](C)(C)CCS([O-])(=O)=O)N VTCNIIJVSUFNQZ-UHFFFAOYSA-N 0.000 claims description 5
- KADLKJHGMWDSKR-UHFFFAOYSA-N CCCCCCCCCC(CC[N+](C)(C)CCCS([O-])(=O)=O)O Chemical class CCCCCCCCCC(CC[N+](C)(C)CCCS([O-])(=O)=O)O KADLKJHGMWDSKR-UHFFFAOYSA-N 0.000 claims description 5
- JWRZDDGWGBUEEX-UHFFFAOYSA-N CCCCCCCCCCCCCCCC[N+](C)(C)CCS([O-])(=O)=O Chemical class CCCCCCCCCCCCCCCC[N+](C)(C)CCS([O-])(=O)=O JWRZDDGWGBUEEX-UHFFFAOYSA-N 0.000 claims description 5
- 244000017020 Ipomoea batatas Species 0.000 claims description 5
- 235000002678 Ipomoea batatas Nutrition 0.000 claims description 5
- 239000001110 calcium chloride Substances 0.000 claims description 5
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 5
- IZWSFJTYBVKZNK-UHFFFAOYSA-N lauryl sulfobetaine Chemical class CCCCCCCCCCCC[N+](C)(C)CCCS([O-])(=O)=O IZWSFJTYBVKZNK-UHFFFAOYSA-N 0.000 claims description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 5
- 229940100445 wheat starch Drugs 0.000 claims description 5
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 4
- AERFECJVKFIHED-UHFFFAOYSA-N 4-ethenylpyridin-1-ium;propane-1-sulfonate Chemical compound CCCS([O-])(=O)=O.C=CC1=CC=[NH+]C=C1 AERFECJVKFIHED-UHFFFAOYSA-N 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- 240000002853 Nelumbo nucifera Species 0.000 claims description 4
- 235000006508 Nelumbo nucifera Nutrition 0.000 claims description 4
- 239000004111 Potassium silicate Substances 0.000 claims description 4
- 239000004115 Sodium Silicate Substances 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 4
- 240000001085 Trapa natans Species 0.000 claims description 4
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- 229910001622 calcium bromide Inorganic materials 0.000 claims description 4
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 4
- 235000019797 dipotassium phosphate Nutrition 0.000 claims description 4
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 4
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 4
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 4
- 235000019800 disodium phosphate Nutrition 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 claims description 4
- 229910001623 magnesium bromide Inorganic materials 0.000 claims description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 4
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 4
- 239000011736 potassium bicarbonate Substances 0.000 claims description 4
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 4
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 235000011181 potassium carbonates Nutrition 0.000 claims description 4
- 239000001103 potassium chloride Substances 0.000 claims description 4
- 235000011164 potassium chloride Nutrition 0.000 claims description 4
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 4
- 235000010333 potassium nitrate Nutrition 0.000 claims description 4
- 239000004323 potassium nitrate Substances 0.000 claims description 4
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 4
- 235000011009 potassium phosphates Nutrition 0.000 claims description 4
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 4
- 235000019353 potassium silicate Nutrition 0.000 claims description 4
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 4
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 4
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 claims description 4
- 235000011151 potassium sulphates Nutrition 0.000 claims description 4
- 235000019252 potassium sulphite Nutrition 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 235000009165 saligot Nutrition 0.000 claims description 4
- 235000017550 sodium carbonate Nutrition 0.000 claims description 4
- 239000004317 sodium nitrate Substances 0.000 claims description 4
- 235000010344 sodium nitrate Nutrition 0.000 claims description 4
- 239000001488 sodium phosphate Substances 0.000 claims description 4
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 4
- 235000011008 sodium phosphates Nutrition 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- 235000019794 sodium silicate Nutrition 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- 235000010265 sodium sulphite Nutrition 0.000 claims description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 4
- 235000003283 Pachira macrocarpa Nutrition 0.000 claims description 3
- 235000014364 Trapa natans Nutrition 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- AMRAXBIKUIPCMJ-UHFFFAOYSA-N N,N-dimethyloctadecane-1-sulfonamide Chemical class CCCCCCCCCCCCCCCCCCS(=O)(=O)N(C)C AMRAXBIKUIPCMJ-UHFFFAOYSA-N 0.000 claims 2
- 239000002981 blocking agent Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 20
- 239000007789 gas Substances 0.000 description 17
- 238000005553 drilling Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- 239000012530 fluid Substances 0.000 description 12
- 238000001914 filtration Methods 0.000 description 7
- 239000004576 sand Substances 0.000 description 7
- UNIGAQKUMBZWBV-UHFFFAOYSA-N 4-[dodecyl(dimethyl)azaniumyl]butane-1-sulfonate Chemical class CCCCCCCCCCCC[N+](C)(C)CCCCS([O-])(=O)=O UNIGAQKUMBZWBV-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- ISZZVWZCCZYJAF-UHFFFAOYSA-N 4-[dimethyl(octadecyl)azaniumyl]butane-1-sulfonate Chemical class CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCS([O-])(=O)=O ISZZVWZCCZYJAF-UHFFFAOYSA-N 0.000 description 3
- 240000008042 Zea mays Species 0.000 description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 235000005822 corn Nutrition 0.000 description 2
- -1 diallyl propanesulfonate Chemical compound 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920012128 methyl methacrylate acrylonitrile butadiene styrene Polymers 0.000 description 2
- GBCKRQRXNXQQPW-UHFFFAOYSA-N n,n-dimethylprop-2-en-1-amine Chemical compound CN(C)CC=C GBCKRQRXNXQQPW-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- JRGMLMBWXYVJCA-UHFFFAOYSA-N C[N+](C)(CCCCCCCCCCCCCCCCO)CCCS([O-])(=O)=O Chemical class C[N+](C)(CCCCCCCCCCCCCCCCO)CCCS([O-])(=O)=O JRGMLMBWXYVJCA-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 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
- C09K8/516—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls characterised by their form or by the form of their components, e.g. encapsulated material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/003—Crosslinking of starch
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/08—Ethers
- C08B31/12—Ethers having alkyl or cycloalkyl radicals substituted by heteroatoms, e.g. hydroxyalkyl or carboxyalkyl starch
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biochemistry (AREA)
- Mining & Mineral Resources (AREA)
- Geology (AREA)
- Fluid Mechanics (AREA)
- Environmental & Geological Engineering (AREA)
- Physics & Mathematics (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a zwitterionic starch microsphere and a preparation method and application thereof, wherein the zwitterionic starch microsphere comprises the following raw materials: 100 parts of deionized water, 1-20 parts of starch, 10-50 parts of triethanolamine, 0.105-14.6 parts of epoxy chloropropane, 0.1-20 parts of zwitterionic monomer, 0.001-0.2 part of initiator, 0.05-10 parts of zwitterionic surfactant and 0.5-200 parts of inorganic salt solution, wherein the inorganic salt solute accounts for 0.025-50 parts. The particle size of the starch microspheres is 0.1-500 mu m, and the starch microspheres have uniformly distributed polydispersity. The prepared zwitter-ion starch microspheres are polydisperse starch microspheres with uniformly distributed particle sizes.
Description
Technical Field
The invention belongs to the technical field of microspheres, and particularly relates to a zwitterionic starch microsphere and a preparation method and application thereof.
Background
The shielding temporary plugging protection oil-gas layer drilling technology (shielding temporary plugging technology for short) is mainly used for solving the problem that a multi-pressure layer system stratum of an open hole well section protects an oil-gas layer, namely two adverse factors (pressure difference and drilling fluid solid-phase particles) which damage the oil-gas layer in the process of drilling into the oil-gas layer are utilized to convert the adverse factors into the advantageous factors for protecting the oil-gas layer, and the purpose of reducing the damage of the drilling fluid, cement paste, the pressure difference and the bubble invasion time to the oil-gas layer is achieved.
The basic idea of the shielding temporary plugging protection oil-gas reservoir drilling technology is that when an oil-gas reservoir is drilled, the pressure difference formed between the pressure of a drilling fluid liquid column and the pressure of the oil-gas reservoir forces solid particles of types and sizes artificially added in the drilling fluid to enter the pore throat of the oil-gas reservoir in a very short time, a plugging zone is quickly, shallowly and effectively formed near a well wall, the drilling fluid is prevented from continuously invading the oil-gas reservoir, and the damage of the drilling fluid to the oil-gas reservoir is reduced. Its thickness must be much less than the perforation depth in order to unblock through the perforations when the completion is put into production. After drilling is completed, if the open hole is completed, the blocking zone can be eliminated by means of acidification and the like, so that the original permeability of an oil-gas layer is recovered, and the oil-gas well is ensured to have better yield.
The microsphere compound is a more common temporary plugging agent for protecting oil and gas reservoirs at present, wherein the starch microsphere is also widely researched. The prior art has more researches on monodisperse or polydisperse starch microspheres, and patents CN201010546156.1 and CN201410236878.5 describe two preparation methods of monodisperse starch microspheres. CN201510151917.6 describes a preparation method of nano-scale polydisperse starch microspheres. CN201510175382.6 provides a method for preparing polymer microspheres with particle size gradient characteristics. There are few reports on uniformly distributed polydisperse starch microspheres.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the zwitter-ion starch microsphere and the preparation method and the application thereof.
The invention provides a zwitterionic starch microsphere, which comprises the following raw materials in parts by weight: 100 parts of deionized water, 1-20 parts of starch, 10-50 parts of triethanolamine, 0.105-14.6 parts of epoxy chloropropane, 0.1-20 parts of zwitterionic monomer, 0.001-0.2 part of initiator, 0.05-10 parts of zwitterionic surfactant and 0.5-200 parts of inorganic salt solution, wherein the inorganic salt solute accounts for 0.025-50 parts.
In the zwitterionic starch microspheres, the zwitterionic starch microspheres comprise the following raw materials in parts by weight: 100 parts of deionized water, 5-15 parts of starch, 20-40 parts of triethanolamine, 1.04-7.8 parts of epoxy chloropropane, 5-15 parts of zwitterionic monomer, 0.02-0.105 part of initiator, 1-6 parts of zwitterionic surfactant and 50-150 parts of inorganic salt solution, wherein the inorganic salt solute accounts for 0.5-30 parts.
In the zwitterionic starch microspheres, the controllable range of the particle size of the starch microspheres is 0.1-500 mu m, the particle size of the starch microspheres is in a particle size concentrated distribution interval (wherein the particle size concentrated distribution interval is defined as a continuous interval with the proportion of particle size distribution being more than or equal to 90% except particle size boundaries at two ends), and the particle size is concentrated from the view point of a particle size distribution diagramThe distribution interval is an area with the particle size distribution being approximately in a straight line, and the area with the obvious inflection point at the two ends is not included), the particle size distribution in the particle size concentration distribution interval has the following characteristics: evenly dividing the particle size concentrated distribution interval into n intervals, wherein the ratio of the microspheres in each interval is as follows:
wherein n is an integer greater than 1.
In the zwitterionic starch microsphere, the zwitterionic monomer can be one or more of DMAPS (methacryloyloxyethyl-N, N-dimethyl propanesulfonate), DAPS (N, N-dimethyl allylamine propanesulfonate), VPPS (4-vinylpyridine propanesulfonate), MAPS (N-methyl diallyl propanesulfonate) and MABS (N-methyl diallyl butanesulfonate).
In the zwitterionic starch microspheres, the starch is one or more of mung bean starch, cassava starch, sweet potato starch, wheat starch, water caltrop starch, lotus root starch and corn starch, and preferably corn starch and/or potato starch.
In the zwitterionic starch microsphere, the initiator can be any one of potassium persulfate, sodium persulfate and ammonium persulfate.
In the zwitterionic starch microsphere, the zwitterionic surfactant has the following structure:
wherein: n is an integer between 2 and 6, preferably n is 3 or 4; r is a carbon chain having 1 to 18 carbon atoms, preferably 12 to 18 carbon atoms. The carbon chain is a saturated carbon chain and can be a straight chain or a branched chain. The carbon chain (excluding the terminal carbon) may contain substituted hydroxyl, amino or carboxyl groups, and the same carbon may be monosubstituted. The zwitterionic surfactant can be dimethyl dodecyl sulfopropyl ammonium salt, dimethyl hexadecyl sulfoethyl ammonium salt, dimethyl octadecyl sulfobutyl ammonium salt, dimethyl (3-hydroxy dodecyl) sulfopropyl ammonium salt and dimethyl (6-Aminotetradecyl) sulfoethylammonium salt.
In the zwitterionic starch microspheres, the inorganic salt is soluble inorganic salt, the inorganic salt is one or more of sodium salt, potassium salt, ammonium salt, calcium salt and magnesium salt, and when the inorganic salt is sodium salt, the inorganic salt is specifically one or more of sodium chloride, sodium bromide, sodium sulfate, sodium sulfite, sodium carbonate, sodium bicarbonate, sodium nitrate, sodium phosphate, sodium hydrogen phosphate and sodium silicate; when the inorganic salt is potassium salt, the inorganic salt is one or more of potassium chloride, potassium bromide, potassium sulfate, potassium sulfite, potassium carbonate, potassium bicarbonate, potassium nitrate, potassium phosphate, potassium hydrogen phosphate and potassium silicate; when the inorganic salt is ammonium salt, the inorganic salt is one or more of ammonium chloride, ammonium bromide and ammonium nitrate; when the inorganic salt is a calcium salt, it is specifically calcium chloride or calcium bromide; when the inorganic salt is a magnesium salt, the inorganic salt is specifically one or more of magnesium chloride, magnesium bromide, magnesium sulfate and magnesium nitrate.
The second aspect of the invention provides a preparation method of zwitterionic starch microspheres, which comprises the following steps:
(1) weighing a certain amount of starch, adding the starch into water, adding a certain amount of triethanolamine, fully and uniformly mixing at 20-80 ℃, and adding epoxy chloropropane for reaction;
(2) adding a zwitterionic monomer into the solution obtained in the step (1), fully dissolving and uniformly mixing, adding an initiator, and reacting for 3-6 h at the temperature of 60-80 ℃;
(3) adding a zwitterionic surfactant into the feed liquid obtained in the step (2), and uniformly mixing;
(4) and (3) slowly adding an inorganic salt solution and epoxy chloropropane into the feed liquid obtained in the step (3) at a constant speed at the temperature of 30-60 ℃, and continuing to react after the inorganic salt solution and the epoxy chloropropane are added to obtain the starch microspheres.
In the method, the starch in the step (1) is one or more of mung bean starch, cassava starch, sweet potato starch, wheat starch, water chestnut starch, lotus root starch and corn starch, and preferably corn starch and/or potato starch.
In the method, the temperature in the step (1) is 30-60 ℃. The reaction time in the step (1) is 0.5-4 h, preferably 1-3 h.
In the method of the present invention, the initiator in the step (2) may be any one of potassium persulfate, sodium persulfate, and ammonium persulfate; the part of the initiator is 0.001-0.2 part, preferably 0.02-0.105 part.
In the method of the present invention, the zwitterionic monomer in step (2) may be one or more selected from DMAPS (methacryloyloxyethyl-N, N-dimethylpropanesulfonate), DAPS (N, N-dimethylallylamine propanesulfonate), VPPS (4-vinylpyridine propanesulfonate), MAPS (N-methyldiallylpropyl propanesulfonate) and MABS (N-methyldiallylbutylsulfonate).
In the method of the present invention, the zwitterionic surfactant described in step (3) has the following structure:
wherein: n is an integer between 2 and 6, preferably n is 3 or 4; r is a carbon chain having 1 to 18 carbon atoms, preferably 12 to 18 carbon atoms. The carbon chain is a saturated carbon chain and can be a straight chain or a branched chain. The carbon chain (excluding the terminal carbon) may contain substituted hydroxyl, amino or carboxyl groups, and the same carbon may be monosubstituted. The zwitterionic surfactant can be one or more of dimethyl dodecyl sulfopropyl ammonium salt, dimethyl hexadecyl sulfoethyl ammonium salt, dimethyl octadecyl sulfobutyl ammonium salt, dimethyl (3-hydroxyl dodecyl) sulfopropyl ammonium salt and dimethyl (6-amino tetradecyl) sulfoethyl ammonium salt.
In the method, the inorganic salt in the step (4) is soluble inorganic salt, the inorganic salt is one or more of sodium salt, potassium salt, ammonium salt, calcium salt and magnesium salt, and when the inorganic salt is sodium salt, the inorganic salt is specifically one or more of sodium chloride, sodium bromide, sodium sulfate, sodium sulfite, sodium carbonate, sodium bicarbonate, sodium nitrate, sodium phosphate, sodium hydrogen phosphate and sodium silicate; when the inorganic salt is potassium salt, the inorganic salt is one or more of potassium chloride, potassium bromide, potassium sulfate, potassium sulfite, potassium carbonate, potassium bicarbonate, potassium nitrate, potassium phosphate, potassium hydrogen phosphate and potassium silicate; when the inorganic salt is ammonium salt, the inorganic salt is one or more of ammonium chloride, ammonium bromide and ammonium nitrate; when the inorganic salt is a calcium salt, it is specifically calcium chloride or calcium bromide; when the inorganic salt is a magnesium salt, the inorganic salt is specifically one or more of magnesium chloride, magnesium bromide, magnesium sulfate and magnesium nitrate.
In the method, the amounts of the deionized water, the starch, the triethanolamine, the epichlorohydrin, the zwitterionic monomer, the initiator, the zwitterionic surfactant and the inorganic salt solution are respectively as follows in parts by weight: 100 parts of deionized water, 1-20 parts of starch, 10-50 parts of triethanolamine, 0.105-14.6 parts of epoxy chloropropane, 0.1-20 parts of zwitterionic monomer, 0.001-0.2 part of initiator, 0.05-10 parts of zwitterionic surfactant and 0.5-200 parts of inorganic salt solution (wherein inorganic salt solute accounts for 0.025-50 parts); preferably 100 parts of deionized water, 5-15 parts of starch, 20-40 parts of triethanolamine, 1.04-7.8 parts of epoxy chloropropane, 5-15 parts of zwitterionic monomer, 0.02-0.105 part of initiator, 1-6 parts of zwitterionic surfactant and 50-150 parts of inorganic salt solution (wherein inorganic salt solute accounts for 0.5-30 parts).
In the method, the epoxy chloropropane in the step (1) is 0.005-0.6 part, preferably 0.04-3 parts.
In the method, the epoxy chloropropane in the step (4) is 0.1-14 parts, preferably 1-7.5 parts.
In the method of the present invention, the slow and uniform adding in the step (4) may be any method capable of realizing uniform solvent adding in the field, such as a dropwise adding method.
The third aspect of the invention also provides application of the zwitterionic starch microspheres in temporary plugging agent for protecting oil and gas reservoirs. The starch microspheres are used as a component in a drilling fluid system to play a role in shielding and temporary plugging. The addition amount of 0.5-5 wt% can achieve good effect. The drilling fluid added with the microspheres has good plugging capability, can effectively plug pores or microcracks to form compact mud cakes, prevents a large amount of filtrate from permeating into a stratum, and reduces the filtration loss.
Compared with the prior art, the zwitterionic starch microsphere and the preparation method thereof have the following advantages:
1. the zwitterionic starch microspheres are polydisperse microspheres with uniformly distributed particle sizes, and are different from monodisperse and polydisperse starch microspheres prepared by the prior art. When the starch microspheres are applied to the field of temporary plugging agents for protecting oil and gas reservoirs, due to the fact that geological structures are different, the porosity span of the reservoirs is large, and if the microspheres with monodisperse particle sizes are used, the requirement on broad spectrum is difficult to meet, and the using effect cannot meet the industrial requirement. In addition, the existing polydisperse microspheres are normally distributed, the effective range of the particle size is narrow, and the effect is obviously limited. The uniformly distributed polydisperse starch microspheres provided by the technology can well solve the problems, namely, in any particle size interval, the microspheres have equivalent proportion, high microsphere content and obvious temporary plugging effect, and can meet the requirement of broad spectrum.
2. In the preparation method of the zwitterionic starch microspheres, the structures of the straight chain part and the branched chain part in the starch are equivalent in size and have similar molecular sizes under the combined action of the triethanolamine and the epichlorohydrin, so that the prepared microspheres are easier to control, and the particle size distribution is uniform. Then the starch is subjected to copolymerization modification by using a zwitterionic monomer so as to have amphiphilicity. In the process of crosslinking starch into microspheres, by using a zwitterionic surfactant and simultaneously slowly adding inorganic salt and epichlorohydrin at a constant speed, under the combined action of the zwitterionic surfactant and the epichlorohydrin, the particle size of the prepared starch microspheres is linearly changed, and then the polydisperse starch microspheres with uniformly distributed particle sizes are prepared.
3. In the preparation method of the zwitterionic starch microspheres, due to the addition of the zwitterionic monomer, the salt resistance, temperature resistance and other properties of the microspheres are remarkably improved.
Detailed Description
The zwitterionic starch microspheres of the present invention and their preparation and use are further described below by way of specific examples, which are not intended to be limiting.
The particle size of the zwitterionic starch microspheres in the embodiment of the invention is measured by a Malvern 3000 particle size analyzer, and the measuring method is wet measurement.
The particle size range (a μm-b μm) in all the examples and comparative examples below means a.ltoreq.D < b.
Example 1
Weighing 13 parts of potato starch, adding into 100 parts of deionized water, adding 10 parts of triethanolamine, and fully dissolving at 75 ℃. Then 0.013 part of epoxy chloropropane is added, and the mixture is mixed and reacted for 2.5 h. 7 parts of DMAPS are weighed and added into the starch solution, and the mixture is fully dissolved and mixed. 0.03 part of potassium persulfate was added thereto at 65 ℃ and reacted for 5 hours. 5 parts of dimethyldodecylsulfobutylammonium salt are added and mixed thoroughly. Weighing 38 parts of NaCl to prepare 170 parts of inorganic salt solution, dripping the inorganic salt solution and 1.5 parts of epichlorohydrin into the starch solution at the same time at 40 ℃, and dripping the solution at a constant speed for 6 hours. And continuously reacting for 2 hours after the dropwise adding is finished to obtain the uniformly distributed polydisperse starch microspheres. The starch microspheres have a particle size concentration distribution interval of 10-170 micrometers (94.2% of particle sizes are in the interval), and the particle size distribution in the particle size concentration distribution interval has the following characteristics: (10 μm-50 μm): 24.9 percent; (50 μm-90 μm): 25.6 percent; (90 μm-130 μm): 25.1 percent; (130 μm-170 μm): 24.4 percent.
Example 2
5 parts of potato starch are weighed into 100 parts of deionized water, 22 parts of triethanolamine are added, and the mixture is fully dissolved at room temperature. Then 0.04 epichlorohydrin is added, and the mixture is mixed and reacted for 2 hours. 6 parts of MAPS are weighed and added into the starch solution, and fully dissolved and mixed. 0.07 part of ammonium persulfate was added at 70 ℃ and reacted for 4 hours. 1 part of dimethylhexadecylsulfoethylammonium salt is added and mixed thoroughly. Weighing 0.5 part of CaCl2Preparing 33 parts of inorganic salt solution, dripping the inorganic salt solution and 7.5 parts of epoxy chloropropane into the starch solution at the same time at the temperature of 60 ℃, and dripping the solution at a constant speed for 8 hours. And continuously reacting for 2 hours after the dropwise adding is finished to obtain the uniformly distributed polydisperse starch microspheres. The particle size concentration distribution interval of the starch microspheres is 120-400 mu m (97.1% of particle size is in the interval), and the starch microspheres are prepared by the methodThe particle size distribution in the particle size concentrated distribution interval has the following characteristics: (120 μm-190 μm): 26 percent; (190 μm-260 μm): 24.5 percent; (260 μm-330 μm): 25.1 percent; (330 μm-400 μm): 24.4 percent.
Example 3
Weighing 20 parts of cassava starch, adding the cassava starch into 100 parts of deionized water, adding 20 parts of triethanolamine, and fully dissolving at 40 ℃. Then 0.3 part of epoxy chloropropane is added, and the mixture is mixed and reacted for 1 hour. 13 parts of DAPS are weighed out and added to the starch solution, and the mixture is thoroughly dissolved and mixed. 0.105 part of sodium persulfate was added thereto at 80 ℃ and reacted for 3 hours. 10 parts of dimethyloctadecyl sulfobutylammonium salt are added and mixed well. Weighing 16 parts of MgCl2150 parts of inorganic salt solution is prepared, and is dripped into the starch solution at 40 ℃ together with 14 parts of epichlorohydrin for 10 hours at uniform speed. And continuously reacting for 2 hours after the dropwise adding is finished to obtain the uniformly distributed polydisperse starch microspheres. The concentrated particle size distribution interval of the starch microspheres is 50-300 mu m (95.4% of particle size is in the interval), and the particle size distribution in the concentrated particle size distribution interval has the following characteristics: (50 μm-100 μm): 19.5 percent; (100 μm-150 μm): 18.7 percent; (150 μm-200 μm): 21 percent; (200 μm-250 μm): 20.0 percent; (250 μm-300 μm): 20.8 percent.
Example 4
Weighing 15 parts of mung bean starch, adding into 100 parts of deionized water, adding 40 parts of triethanolamine, and fully dissolving at 60 ℃. Then 0.6 part of epoxy chloropropane is added, and the mixture is reacted for 1.5 hours after being mixed. 20 parts of VPPS are weighed and added into the starch solution, and fully dissolved and mixed. 0.2 part of potassium persulfate was added thereto at 75 ℃ and reacted for 5 hours. 4.5 parts of dimethyl (3-hydroxydodecyl) sulfopropyl ammonium salt are added and mixed thoroughly. Weighing 30 parts of K2SO4Preparing 135 parts of inorganic salt solution, dripping the inorganic salt solution and 9.5 parts of epoxy chloropropane into the starch solution at the same time at the temperature of 30 ℃, and dripping the solution at a constant speed for 7 hours. And continuously reacting for 2 hours after the dropwise adding is finished to obtain the uniformly distributed polydisperse starch microspheres. The starch microspheres have a particle size concentration distribution interval of 150-500 microns (96.2% of particle sizes are in the interval), and the particle size distribution in the particle size concentration distribution interval has the following characteristics: (150 μm-200 μm): 13.5 percent; (200 μm-250 μm)）：14.2%；（250μm-300μm）：15.4%；（300μm-350μm）：14.7%；（350μm-400μm）：13.9%；（400μm-450μm）：14.7%；（450μm-500μm）：13.6%。
Example 5
Weighing 1 part of sweet potato starch, adding into 100 parts of deionized water, adding 50 parts of triethanolamine, and fully dissolving at 50 ℃. Then 0.15 part of epoxy chloropropane is added, and the mixture is reacted for 2.5 hours after being mixed. 0.1 part of MAPS was weighed into the starch solution and mixed well. 0.001 part of ammonium persulfate was added at 65 ℃ and reacted for 4 hours. 0.05 part of dimethyl (6-aminotetradecyl) sulfoethylammonium salt is added and mixed well. 0.025 part of NaCl is weighed to prepare 0.5 part of inorganic salt solution, and the inorganic salt solution and 0.1 part of epichlorohydrin are simultaneously dripped into the starch solution at the temperature of 55 ℃, and the dripping time is 9 hours at uniform speed. And continuously reacting for 2 hours after the dropwise adding is finished to obtain the uniformly distributed polydisperse starch microspheres. The concentrated particle size distribution interval of the starch microspheres is 0.1-3.7 microns (95.0% of particle size is in the interval), and the particle size distribution in the concentrated particle size distribution interval has the following characteristics: (0.1 μm-0.7 μm): 16.5 percent; (0.7 μm-1.3 μm): 15.9 percent; (1.3 μm-1.9 μm): 17.2 percent; (1.9 μm-2.5 μm): 17.5 percent; (2.5 μm-3.1 μm): 16.4 percent; (3.1 μm-3.7 μm): 16.5 percent.
Example 6
17 parts of starch (corn: mung bean =2: 1) are weighed into 100 parts of deionized water, 30 parts of triethanolamine are added, and the mixture is dissolved sufficiently at 72 ℃. Then 0.28 part of epoxy chloropropane is added, and the mixture is reacted for 0.5h after being mixed. 11.5 parts DMAPS were weighed into the starch solution and mixed well. 0.009 part of potassium persulfate was added thereto at 68 ℃ and reacted for 5 hours. 7 parts of dimethyldodecylsulfobutylammonium salt are added and mixed well. Weighing 45 parts of inorganic salt (NaCl: CaCl)2=1: 1) is prepared into 50 portions of inorganic salt solution, and the inorganic salt solution and 12 portions of epichlorohydrin are simultaneously dripped into the starch solution at 57 ℃, and the dripping time is 4.5h at uniform speed. And continuously reacting for 2 hours after the dropwise adding is finished to obtain the uniformly distributed polydisperse starch microspheres. The starch microspheres have a particle size concentration distribution interval of 70-270 micrometers (91.2% of particle sizes are in the interval), and the particle size distribution in the particle size concentration distribution interval has the following characteristics: (70. mum-110μm）：20.7%；（110μm-150μm）：20.6%；（150μm-190μm）：20.1%；（190μm-230μm）：19.8%；（230μm-270μm）：18.8%。
Example 7
6 parts of starch (cassava: corn =3: 1) are weighed into 100 parts of deionized water, 14 parts of triethanolamine are added, and the mixture is dissolved sufficiently at 65 ℃. Then 0.025 parts of epoxy chloropropane is added, and the mixture is mixed and reacted for 1.6 h. 2 parts of DMAPS are weighed and added into the starch solution, and the mixture is fully dissolved and mixed. 0.022 part of ammonium persulfate was added thereto at 72 ℃ and reacted for 4 hours. 0.8 part of dimethylhydroxyhexadecylsulfopropyl ammonium salt is added and mixed well. Weighing 10 parts of KNO3Preparing 64 parts of inorganic salt solution, dripping the inorganic salt solution and 7 parts of epichlorohydrin into the starch solution at the same time at 45 ℃, and dripping the solution at a constant speed for 6 hours. And continuously reacting for 2 hours after the dropwise adding is finished to obtain the uniformly distributed polydisperse starch microspheres. The particle size concentrated distribution interval of the starch microspheres is 20-260 mu m (93.7% of particle size is in the interval), and the particle size distribution in the particle size concentrated distribution interval has the following characteristics: (20 μm-60 μm): 16.6 percent; (60 μm-100 μm): 17.8 percent; (100 μm-140 μm): 15.9 percent; (140 μm-180 μm): 17.5 percent; (180 μm-220 μm): 17.0 percent; (220 μm-260 μm): 15.2 percent.
Example 8
Weighing 18 parts of wheat starch, adding into 100 parts of deionized water, adding 24 parts of triethanolamine, and fully dissolving at 45 ℃. Then 0.013 part of epoxy chloropropane is added, and the mixture is mixed and reacted for 2.75 hours. 3.5 parts of monomer (DMAPS: MAPS =1: 1) were weighed into the starch solution and mixed well. 0.01 part of an initiator (sodium persulfate: potassium persulfate =1: 1) was added at 67.5 ℃ and reacted for 6 hours. 5.5 parts of dimethyldodecylsulfopropyl ammonium salt are added and mixed thoroughly. Weighing 7 parts of Na2CO3130 parts of inorganic salt solution is prepared, and is dripped into the starch solution at 42 ℃ together with 2 parts of epichlorohydrin, and the dripping time is 6.5h at uniform speed. And continuously reacting for 2 hours after the dropwise adding is finished to obtain the uniformly distributed polydisperse starch microspheres. The particle size concentration distribution interval of the starch microspheres is 0.1-4.9 microns (95.6% of the particle size is in the interval), and the particle size distribution in the particle size concentration distribution interval is as followsIs characterized in that: (0.1 μm-0.9 μm): 16.8 percent; (0.9 μm-1.7 μm): 17.6 percent; (1.7 μm-2.5 μm): 16.8 percent; (2.5 μm-3.3 μm): 15.9 percent; (3.3 μm-4.1 μm): 17.4 percent; (4.1 μm-4.9 μm): 15.5 percent.
Comparative example 1
Adding 13 parts of potato starch into 100 parts of deionized water, fully dissolving for 30min at 75 ℃, and then cooling for later use. 7 parts of DMAPS are weighed and added into the starch solution, and the mixture is fully dissolved and mixed. 0.03 part of potassium persulfate was added thereto at 65 ℃ and reacted for 5 hours. 5 parts of dimethyldodecylsulfobutylammonium salt are added, and fully dissolved and mixed. 1.5 parts of epichlorohydrin is weighed and added into a starch solution, and the continuous reaction time is 6 hours at 40 ℃. Obtaining the uniformly distributed polydisperse starch microspheres. The starch microspheres have a particle size concentration distribution interval of 120-400 microns (92.2% of particle sizes are in the interval), and the particle size distribution in the particle size concentration distribution interval has the following characteristics: (120 μm-170 μm): 13.4 percent; (170 μm-350 μm): 75.4 percent; (350 μm-400 μm): 11.2 percent.
Comparative example 2
Adding 13 parts of potato starch into 100 parts of deionized water, adding 10 parts of triethanolamine, and fully dissolving at 75 ℃.7 parts of DMAPS are weighed and added into the starch solution, and the mixture is fully dissolved and mixed. 0.03 part of potassium persulfate was added thereto at 65 ℃ and reacted for 5 hours. Then, 5 parts of dimethyldodecylsulfobutylammonium salt was added and mixed well. Weighing 38 parts of NaCl to prepare 170 parts of inorganic salt solution, dripping the inorganic salt solution and 1.5 parts of epichlorohydrin into the starch solution at the same time at 40 ℃, and dripping the solution at a constant speed for 6 hours. And continuously reacting for 2 hours after the dropwise adding is finished to obtain the uniformly distributed polydisperse starch microspheres. The starch microspheres have a particle size concentration distribution interval of 20-180 micrometers (91.8% of particle sizes are in the interval), and the particle size distribution in the particle size concentration distribution interval has the following characteristics: (20 μm-60 μm): 32.8 percent; (60 μm-100 μm): 17.5 percent; (100 μm-140 μm): 19.2 percent; (140 μm-180 μm): 30.5 percent.
Comparative example 3
Weighing 13 parts of potato starch, adding into 100 parts of deionized water, adding 10 parts of triethanolamine, and fully dissolving at 75 ℃. Then 0.013 part of epoxy chloropropane is added, and the mixture is mixed and reacted for 2.5 h. 7 parts of DMAPS are weighed and added into the starch solution, and the mixture is fully dissolved and mixed. 0.03 part of potassium persulfate was added thereto at 65 ℃ and reacted for 5 hours. 5 parts of dimethyldodecylsulfobutylammonium salt are added and mixed thoroughly. Weighing 38 parts of NaCl to prepare 170 parts of inorganic salt solution, simultaneously adding the inorganic salt solution and 1.5 parts of epichlorohydrin into the starch solution at one time at 40 ℃, and continuously reacting for 6 hours to obtain the uniformly distributed polydisperse starch microspheres. The starch microspheres have a particle size concentration distribution interval of 10-190 micrometers (96.2% of particle sizes are in the interval), and the particle size distribution in the particle size concentration distribution interval has the following characteristics: (10 μm-55 μm): 9.9 percent; (55 μm-100 μm): 37.2 percent; (100 μm-145 μm): 42.1 percent; (145 μm-190 μm): 10.8 percent.
Comparative example 4
13 parts of potato starch are weighed into 100 parts of deionized water and dissolved thoroughly at 75 ℃. Then 0.013 part of epoxy chloropropane is added, and the mixture is mixed and reacted for 2.5 h. 7 parts of DMAPS are weighed and added into the starch solution, and the mixture is fully dissolved and mixed. 0.03 part of potassium persulfate was added thereto at 65 ℃ and reacted for 5 hours. 5 parts of dimethyldodecylsulfobutylammonium salt are added and mixed thoroughly. Weighing 38 parts of NaCl to prepare 170 parts of inorganic salt solution, dripping the inorganic salt solution and 1.5 parts of epichlorohydrin into the starch solution at the same time at 40 ℃, and dripping the solution at a constant speed for 6 hours. And continuously reacting for 2 hours after the dropwise adding is finished to obtain the uniformly distributed polydisperse starch microspheres. The starch microspheres have a particle size concentration distribution interval of 5-205 μm (94.2% of particle size is in the interval), and the particle size distribution in the particle size concentration distribution interval has the following characteristics: (5 μm-55 μm): 36.3 percent; (55 μm-105 μm): 22.1 percent; (105 μm-155 μm): 19.9 percent; (155 μm-205 μm): 21.7 percent.
Evaluation of application of the zwitterionic starch microspheres as temporary plugging agents, namely sand bed plugging experiments, and evaluation is carried out by selecting samples in examples and comparative examples. An experimental instrument: a drilling fluid sand bed filtration loss instrument, a stirrer and an oven. Experimental materials: log 860 well slurry (density 1.19 g/cm)3) Examples, comparative examples and 20-40 mesh sand samples.
The experimental steps are as follows:
1. slurry preparation: formulated slurry +3% of example sample or comparative sample;
2. manufacturing a sand bed: adding 20-40 mesh sand into the cylinder by 350cm3Shaking up;
3. adding prepared experimental slurry (400-500 mL), fixing on an instrument frame and sealing an upper channel and a lower channel;
4. and opening an air source, adjusting the pressure to 0.69mPa, simultaneously opening an upper switch and a lower switch, and measuring the condition that the drilling fluid invades the sand bed in the half-hour process.
The experimental results are as follows:
the filtrate loss FL is 30min after the formula is added1And the drilling fluid is basically stable after invading the sand bed to the depth D. After a stable mud cake is formed, the pressure is released, the drilling fluid is poured out, clear water is added to the position of 400mL, and the filtration loss FL after 30min of pressurization (0.69 mPa) measurement is carried out2The results are shown in Table 1.
TABLE 1 results of the experiment
| Sample (I) | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| Filtration loss FL1/ml | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 2 | 0 | 3 | 0 |
| Depth D/cm3 | 135 | 170 | 190 | 200 | 220 | 205 | 145 | 205 | 350 (full immersion) | 310 | 350 (full immersion) | 330 |
| Filtration loss FL2/ml | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 65 | 15 | 73 | 22 |
From the above results, it can be seen that the clear water shows good plugging effect without filtration loss at 0.69mPa pressure for 30min when the samples of examples 1-8 are used, while the clear water shows poor plugging effect with filtration loss of 73ml at maximum at 0.69mPa pressure for 30min when the samples of comparative examples 1-4 are used.
Claims (34)
1. The zwitterionic starch microspheres are prepared from the following raw materials in parts by weight: 100 parts of deionized water, 1-20 parts of starch, 10-50 parts of triethanolamine, 0.105-14.6 parts of epoxy chloropropane, 0.1-20 parts of zwitterionic monomer, 0.001-0.2 part of initiator, 0.05-10 parts of zwitterionic surfactant and 0.5-200 parts of inorganic salt solution, wherein the inorganic salt solute accounts for 0.025-50 parts; the preparation method of the zwitterionic starch microspheres comprises the following steps:
(1) weighing starch, adding the starch into water, adding triethanolamine, fully and uniformly mixing at 20-80 ℃, and adding epoxy chloropropane for reaction;
(2) adding a zwitterionic monomer into the solution obtained in the step (1), fully dissolving and uniformly mixing, adding an initiator, and reacting for 3-6 h at the temperature of 60-80 ℃;
(3) adding a zwitterionic surfactant into the feed liquid obtained in the step (2), and uniformly mixing;
(4) and (3) slowly adding an inorganic salt solution and epoxy chloropropane into the feed liquid obtained in the step (3) at a constant speed at the temperature of 30-60 ℃, and continuing to react after the inorganic salt solution and the epoxy chloropropane are added to obtain the starch microspheres.
2. The zwitterionic starch microsphere of claim 1, wherein the zwitterionic starch microsphere comprises the following components in parts by weight: 100 parts of deionized water, 5-15 parts of starch, 20-40 parts of triethanolamine, 1.04-7.8 parts of epoxy chloropropane, 5-15 parts of zwitterionic monomer, 0.02-0.105 part of initiator, 1-6 parts of zwitterionic surfactant and 50-150 parts of inorganic salt solution, wherein the inorganic salt solute accounts for 0.5-30 parts.
3. The zwitterionic starch microsphere of claim 1, wherein the controllable range of particle size of the starch microsphere is 0.1-500 μm.
4. The zwitterionic starch microsphere of claim 1, wherein said starch microsphere has a uniform polydispersity in size distribution over a concentrated size distribution interval, said concentrated size distribution interval characterized by: evenly dividing the particle size concentrated distribution interval into n intervals, wherein the ratio of the microspheres in each interval is as follows:
wherein n is an integer greater than 1.
5. The zwitterionic starch microsphere of claim 1, wherein the starch is one or more of mung bean starch, tapioca starch, sweet potato starch, wheat starch, water chestnut starch, lotus root starch and corn starch.
6. The zwitterionic starch microsphere of claim 1, wherein said starch is corn starch and/or potato starch.
7. The zwitterionic starch microsphere of claim 1, wherein said zwitterionic surfactant has the following structure:
wherein: n is an integer between 2 and 6, R is a carbon chain with the carbon number of 1 to 18, and the carbon chain is a saturated carbon chain and is a straight chain or a branched chain.
8. The zwitterionic starch microsphere of claim 1, wherein said zwitterionic surfactant has the following structure:
wherein: n is 3 or 4; r is a carbon chain with 12-18 carbon atoms, and the carbon chain is a saturated carbon chain and is a straight chain or a branched chain.
9. The zwitterionic starch microsphere of claim 7, wherein said zwitterionic surfactant has a substituted hydroxyl, amino or carboxyl group on the carbon chain except for the terminal carbon, and is monosubstituted on the same carbon.
10. The zwitterionic starch microsphere of claim 1, wherein the zwitterionic surfactant is one or more of dimethyldodecylsulfopropyl ammonium salt, dimethylhexadecylsulfoethyl ammonium salt, dimethyloctadecylsulfonylammonium salt, dimethyl (3-hydroxydodecyl) sulfopropyl ammonium salt, and dimethyl (6-aminotetradecyl) sulfoethyl ammonium salt.
11. The zwitterionic starch microsphere of claim 1, wherein said inorganic salt is a soluble inorganic salt.
12. The zwitterionic starch microsphere of claim 1, wherein said inorganic salt is one or more of sodium salt, potassium salt, ammonium salt, calcium salt, magnesium salt, and when said inorganic salt is sodium salt, one or more of sodium chloride, sodium bromide, sodium sulfate, sodium sulfite, sodium carbonate, sodium bicarbonate, sodium nitrate, sodium phosphate, sodium hydrogen phosphate, sodium silicate; when the inorganic salt is potassium salt, the inorganic salt is one or more of potassium chloride, potassium bromide, potassium sulfate, potassium sulfite, potassium carbonate, potassium bicarbonate, potassium nitrate, potassium phosphate, potassium hydrogen phosphate and potassium silicate; when the inorganic salt is ammonium salt, the inorganic salt is one or more of ammonium chloride, ammonium bromide and ammonium nitrate; when the inorganic salt is a calcium salt, calcium chloride or calcium bromide; when the inorganic salt is a magnesium salt, the inorganic salt is one or more of magnesium chloride, magnesium bromide, magnesium sulfate and magnesium nitrate.
13. The zwitterionic starch microsphere of claim 1 or 2, wherein the zwitterionic monomer is one or more of methacryloyloxyethyl-N, N-dimethylpropanesulfonate, N-dimethylallylamine propanesulfonate, 4-vinylpyridine propanesulfonate, N-methyldiallylpropane propanesulfonate, and N-methyldiallylbutylsulfonate.
14. A method of preparing zwitterionic starch microspheres as claimed in any one of claims 1 to 13, said method comprising:
(1) weighing starch, adding the starch into water, adding triethanolamine, fully and uniformly mixing at 20-80 ℃, and adding epoxy chloropropane for reaction;
(2) adding a zwitterionic monomer into the solution obtained in the step (1), fully dissolving and uniformly mixing, adding an initiator, and reacting for 3-6 h at the temperature of 60-80 ℃;
(3) adding a zwitterionic surfactant into the feed liquid obtained in the step (2), and uniformly mixing;
(4) and (3) slowly adding an inorganic salt solution and epoxy chloropropane into the feed liquid obtained in the step (3) at a constant speed at the temperature of 30-60 ℃, and continuing to react after the inorganic salt solution and the epoxy chloropropane are added to obtain the starch microspheres.
15. The preparation method according to claim 14, wherein the starch in the step (1) is one or more of mung bean starch, tapioca starch, sweet potato starch, wheat starch, water chestnut starch, lotus root starch and corn starch.
16. The method according to claim 14 or 15, wherein the starch in the step (1) is corn starch and/or potato starch.
17. The method according to claim 14, wherein the temperature in the step (1) is 30 to 60 ℃.
18. The method according to claim 14, wherein the reaction time in the step (1) is 0.5 to 4 hours.
19. The method according to claim 14, wherein the reaction time in the step (1) is 1 to 3 hours.
20. The production method according to claim 14, wherein the initiator in the step (2) is any one of potassium persulfate, sodium persulfate and ammonium persulfate.
21. The method according to claim 14, wherein the zwitterionic monomer in step (2) is one or more of methacryloyloxyethyl-N, N-dimethylpropanesulfonate, N-dimethylallylamine propanesulfonate, 4-vinylpyridine propanesulfonate, N-methyldiallylpropane propanesulfonate and N-methyldiallylbutylsulfonate.
22. The method according to claim 14, wherein the zwitterionic surfactant in step (3) has the following structure:
wherein: n is an integer between 2 and 6, R is a carbon chain with the carbon number of 1 to 18, and the carbon chain is a saturated carbon chain and is a straight chain or a branched chain.
23. The method according to claim 14, wherein the zwitterionic surfactant in step (3) has the following structure:
wherein: n is 3 or 4; r is a carbon chain with 12-18 carbon atoms, and the carbon chain is a saturated carbon chain and is a straight chain or a branched chain.
24. The method according to claim 22 or 23, wherein the zwitterionic surfactant has a hydroxyl, amino or carboxyl group substituted on the carbon chain except for the terminal group, and the same carbon is monosubstituted.
25. The method according to any one of claims 14, 22 and 23, wherein the zwitterionic surfactant is one or more of dimethyldodecylsulfopropyl ammonium salt, dimethylhexadecylsulfoethyl ammonium salt, dimethyloctadecylsulfonyl ammonium salt, dimethyl (3-hydroxydodecyl) sulfopropyl ammonium salt and dimethyl (6-aminotetradecyl) sulfoethyl ammonium salt.
26. The method according to claim 14, wherein the inorganic salt in the step (4) is a soluble inorganic salt.
27. The preparation method according to claim 14 or 26, wherein the inorganic salt in the step (4) is one or more of sodium salt, potassium salt, ammonium salt, calcium salt and magnesium salt, and when the inorganic salt is sodium salt, one or more of sodium chloride, sodium bromide, sodium sulfate, sodium sulfite, sodium carbonate, sodium bicarbonate, sodium nitrate, sodium phosphate, sodium hydrogen phosphate and sodium silicate; when the inorganic salt is potassium salt, the inorganic salt is one or more of potassium chloride, potassium bromide, potassium sulfate, potassium sulfite, potassium carbonate, potassium bicarbonate, potassium nitrate, potassium phosphate, potassium hydrogen phosphate and potassium silicate; when the inorganic salt is ammonium salt, the inorganic salt is one or more of ammonium chloride, ammonium bromide and ammonium nitrate; when the inorganic salt is a calcium salt, calcium chloride or calcium bromide; when the inorganic salt is a magnesium salt, the inorganic salt is one or more of magnesium chloride, magnesium bromide, magnesium sulfate and magnesium nitrate.
28. The preparation method of claim 14, wherein the deionized water, the starch, the triethanolamine, the epichlorohydrin, the zwitterionic monomer, the initiator, the zwitterionic surfactant and the inorganic salt solution are respectively used in the following amounts by weight: 100 parts of deionized water, 1-20 parts of starch, 10-50 parts of triethanolamine, 0.105-14.6 parts of epoxy chloropropane, 0.1-20 parts of zwitterionic monomer, 0.001-0.2 part of initiator, 0.05-10 parts of zwitterionic surfactant and 0.5-200 parts of inorganic salt solution, wherein the inorganic salt solute accounts for 0.025-50 parts.
29. The preparation method according to claim 14 or 28, wherein the deionized water, the starch, the triethanolamine, the epichlorohydrin, the zwitterionic monomer, the initiator, the zwitterionic surfactant and the inorganic salt solution are respectively used in the following amounts in parts by weight: 100 parts of deionized water, 5-15 parts of starch, 20-40 parts of triethanolamine, 1.04-7.8 parts of epoxy chloropropane, 5-15 parts of zwitterionic monomer, 0.02-0.105 part of initiator, 1-6 parts of zwitterionic surfactant and 50-150 parts of inorganic salt solution, wherein the inorganic salt solute accounts for 0.5-30 parts.
30. The process according to claim 14, wherein the amount of epichlorohydrin in the step (1) is 0.005 to 0.6 parts.
31. The production process according to claim 14 or 30, wherein the amount of the epichlorohydrin in the step (1) is 0.04 to 3 parts.
32. The process according to claim 14, wherein the amount of epichlorohydrin in the step (4) is 0.1 to 14 parts.
33. The production process according to claim 14 or 32, wherein the amount of the epichlorohydrin in the step (4) is 1 to 7.5 parts.
34. Use of zwitterionic starch microspheres according to any one of claims 1 to 13 in a reservoir protection temporary blocking agent.
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| PCT/CN2018/101771 WO2019037743A1 (en) | 2017-08-22 | 2018-08-22 | Starch-containing microsphere and preparation method therefor and application thereof |
| EP18847661.8A EP3670540B1 (en) | 2017-08-22 | 2018-08-22 | Starch-containing microsphere and preparation method therefor and application thereof |
| CA3073777A CA3073777C (en) | 2017-08-22 | 2018-08-22 | Starch-containing microsphere and preparation method and use thereof |
| US16/641,504 US20210032373A1 (en) | 2017-08-22 | 2018-08-22 | Starch-containing microsphere and preparation method and use thereof |
| US17/658,173 US11891458B2 (en) | 2017-08-22 | 2022-04-06 | Starch-containing microsphere and preparation method and use thereof |
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