CN108219763A - A kind of acidizing sandstone oil reservoir slow type MH acid system and its construction technology - Google Patents
A kind of acidizing sandstone oil reservoir slow type MH acid system and its construction technology Download PDFInfo
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- CN108219763A CN108219763A CN201810055584.0A CN201810055584A CN108219763A CN 108219763 A CN108219763 A CN 108219763A CN 201810055584 A CN201810055584 A CN 201810055584A CN 108219763 A CN108219763 A CN 108219763A
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- 239000002253 acid Substances 0.000 title claims abstract description 90
- 238000010276 construction Methods 0.000 title claims description 11
- 238000005516 engineering process Methods 0.000 title claims description 10
- -1 phospho Chemical class 0.000 claims abstract description 34
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000004927 clay Substances 0.000 claims abstract description 30
- 238000005260 corrosion Methods 0.000 claims abstract description 26
- 230000007797 corrosion Effects 0.000 claims abstract description 25
- 239000003381 stabilizer Substances 0.000 claims abstract description 20
- 239000003112 inhibitor Substances 0.000 claims abstract description 16
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 15
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- VPTUPAVOBUEXMZ-UHFFFAOYSA-N (1-hydroxy-2-phosphonoethyl)phosphonic acid Chemical compound OP(=O)(O)C(O)CP(O)(O)=O VPTUPAVOBUEXMZ-UHFFFAOYSA-N 0.000 claims description 5
- 229940120146 EDTMP Drugs 0.000 claims description 5
- 150000003863 ammonium salts Chemical class 0.000 claims description 5
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 claims description 5
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 4
- 239000003125 aqueous solvent Substances 0.000 claims description 4
- 239000007859 condensation product Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 150000001412 amines Chemical class 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 230000001934 delay Effects 0.000 claims 1
- 230000003628 erosive effect Effects 0.000 claims 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 16
- 230000020477 pH reduction Effects 0.000 abstract description 15
- 230000035699 permeability Effects 0.000 abstract description 13
- 230000009466 transformation Effects 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 6
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 31
- 239000000243 solution Substances 0.000 description 15
- 239000011435 rock Substances 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 235000015165 citric acid Nutrition 0.000 description 9
- 239000010410 layer Substances 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 6
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000000752 ionisation method Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- 208000027418 Wounds and injury Diseases 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 208000014674 injury Diseases 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical compound Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000000116 mitigating effect Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- JKTORXLUQLQJCM-UHFFFAOYSA-N 4-phosphonobutylphosphonic acid Chemical compound OP(O)(=O)CCCCP(O)(O)=O JKTORXLUQLQJCM-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 244000248349 Citrus limon Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910017665 NH4HF2 Inorganic materials 0.000 description 1
- QNGLQQLZIAMTEE-UHFFFAOYSA-L P([O-])([O-])=O.[Si+4].[Al+3] Chemical compound P([O-])([O-])=O.[Si+4].[Al+3] QNGLQQLZIAMTEE-UHFFFAOYSA-L 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- 241000255964 Pieridae Species 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- SEOVTRFCIGRIMH-UHFFFAOYSA-N indole-3-acetic acid Chemical group C1=CC=C2C(CC(=O)O)=CNC2=C1 SEOVTRFCIGRIMH-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000004375 physisorption Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000010457 zeolite 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
- C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
- C09K8/528—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning inorganic depositions, e.g. sulfates or carbonates
-
- 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
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
-
- 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
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/12—Swell inhibition, i.e. using additives to drilling or well treatment fluids for inhibiting clay or shale swelling or disintegrating
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mining & Mineral Resources (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Fluid Mechanics (AREA)
- Physics & Mathematics (AREA)
- Geochemistry & Mineralogy (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Abstract
The invention discloses the water of 45~55% organic phospho acid, 5~10% sulfamic acid, 5~10% hydrogen fluoride amine, 2~4% high-temperature corrosion inhibitor, 1~3% citric acid, 10~18% formaldehyde, 0.5~1% clay stabilizer and surplus that a kind of acidizing sandstone oil reservoir includes being calculated in mass percent with slow type MH acid system；Corresponding acidizing treatment then adds in part sulfamic acid, organic phospho acid, high-temperature corrosion inhibitor, citric acid, formaldehyde and clay stabilizer using first mixing, then certain interval of time remix add in remaining sulfamic acid and ammonium acid fluoride method is added portionwise；The acidizing sandstone oil reservoir injures sandstone oil reservoir skeleton with slow type MH acid system small, it is good to be acidified plugging removal effect, it is compared to the mud acid that tradition uses, its drill core permeability rate increase multiple ratio is 3~4 times, in-place permeability is effectively increased, realizes and acidification transformation is carried out to complex lithology sandstone oil reservoir deep.
Description
Technical field
The present invention relates to oil gas field stimulation technology field, more particularly to a kind of acidizing sandstone oil reservoir more hydrogen of slow type
Acid system and its construction technology.
Background technology
Sandstone reservoir grease well acidizing mainly by injecting the acid fluid systems such as HF acid, HCl acid and HFB acid to stratum, makes
Acid solution with many silicoides include quartz and clay reaction, release near wellbore zone tamper (such as iron oxide, ferrous sulfide,
Clay etc.) renwing stratum permeability；The part rock of nearly well band is also can dissolve, the throat of expandable pores structure improves stratum and oozes
Saturating rate.But it improves permeability and depends on many factors, if acid type selection or acid treatment process are improper, cannot not only increase production, even
The chemical precipitation and other reasons that can be also generated in acidization cause oil and gas reservoir pore plugging and the underproduction.
However, the conventional acidulation liquid system including regular mud acid, hydrochloric acid etc. is applied to show during sandstone acidizing
Go out following deficiency：1) reaction speed is fast, and acid just occurs immediately upon reaction when being contacted with rock or clay, causes penetration range short, acid
Liquid is difficult to enter into complex lithology deep and is transformed；2) secondary precipitation, the chlorite contained in mineral and mixing are easily formed
Clay is by after mud acid corrosion, it will generates a large amount of iron colloidal precipitation, the iron hydroxide of precipitation can block hole, easily cause stratum
Permeability is low；And zeolite and feldspar in reservoir etc., although can be generated dissolution pore after sour corrosion, acid solution can excessively cause rock
The disintegration of skeleton particle blocks hole and oil reservoir is damaged；3) high volatility, not environmentally, hydrochloric acid and mud acid both acid are easily
Volatilization, especially when Hainan is when torrid areas operation, performance it is particularly evident, high volatility not only be pungent and to human body and environment
It endangers larger, belongs to the acids chemicals of public security department's control.
Therefore, in order to efficiently solve the above problem, the effect of complicated sandstone oil reservoir deep transformation is improved, should be studied
A kind of acid fluid system for being adapted to sandstone oil reservoir transformation of environment-friendly type, in-place permeability is improved after being transformed.
Invention content
The object of the present invention is to provide one kind to overcome drawbacks described above, realizes and complex lithology sandstone oil reservoir deep is acidified
The slow type MH acid system of the acidizing sandstone oil reservoir of transformation.
It is realized it is a further object of the present invention to provide a kind of using the slow type MH acid system of above-mentioned acidizing sandstone oil reservoir
The corresponding construction technology of acidification transformation is carried out to complex lithology sandstone oil reservoir deep.
For this purpose, technical solution of the present invention is as follows：
A kind of slow type MH acid system of acidizing sandstone oil reservoir, including be calculated in mass percent 45~55% it is organic
Phosphonic acids, 5~10% sulfamic acid, 5~10% hydrogen fluoride amine, 2~4% high-temperature corrosion inhibitor, 1~3% citric acid, 10
The water of~18% formaldehyde, 0.5~1% clay stabilizer and surplus；Wherein, the organic phospho acid is aminotrimethylene phosphine
Sour (ATMP), hydroxy ethylene diphosphonic acid (HEDP), ethylenediamine tetramethylene phosphonic acid (EDTMP) or diethylenetriamine pentamethylene
Phosphonic acids (DETPMP).
Wherein, organic phospho acid plays the role of two in the system, and one prevents calcium ion from forming carbon to provide hydrogen ion
Second sour calcium is to play corrosion inhibition；In addition, ensure its chemical stabilization containing a large amount of C-P keys in the molecule of organic phospho acid
Property is good, and facile hydrolysis, high temperature resistant can not keep stable property in sandstone.The structural formula of sulfamic acid is：NH2SO3H,
Aqueous solution has the highly acid equal with hydrochloric acid, sulfuric acid etc., has the characteristics of not volatile, odorless, minimum to human toxicity.
The structural formula of hydrogen fluoride amine is：NH4HF2, it is used for identical with organic phospho acid, in the early stage for providing hydrogen ion, plays acidification sand
Rock prevents calcium ion from forming the effect of calcium carbonate.Citric acid is used as ferrous stability in the system.Formaldehyde then primarily serves
Sterilization and corrosion-resistant effect.Clay stabilizer is then used to after entering stratum adsorb in surface of clay, prevents water sensitivity mineral aquation
Expansion and dispersion are migrated and the injury caused by oil-gas Layer
It is preferred that the high-temperature corrosion inhibitor is the condensation product of acetophenone-metaformaldehyde-cyclohexylamine, nonylphenol polyoxyethylene ether,
The mixture of methanol and propilolic alcohol, four weight ratios are 10:2:6:1.
It is preferred that the clay stabilizer is organic ammonium salt and the mixture of ammonium chloride, the two weight ratio is 3:7；Wherein, have
Machine ammonium salt is 1 by molar ratio:2.5~3 ethylenediamine is generated with acetic acid reaction.
A kind of construction technology of the slow type MH acid system of acidizing sandstone oil reservoir, wherein, acidizing sandstone oil reservoir is with slowly
The formula of type MH acid system is as described above；Accordingly, which is walked with slow type MH acid system Specific construction
It is rapid as follows：The sulfamic acid of suitable aqueous solvent and half quality is added in agitator tank first, is continued after stirring evenly to stirring
It mixes and organic phospho acid, high-temperature corrosion inhibitor, citric acid, formaldehyde and clay stabilizer is added in tank, continue stirring to after mixing, incite somebody to action
Gained mixed solution is delivered to underground by casing；After 2~8h is spaced, hydrogen fluoride amine, remaining half are added in into agitator tank
The sulfamic acid of quality and suitable aqueous solvent, underground is delivered to after stirring evenly by mixed solution by casing.
In the construction technology, acidizing sandstone oil reservoir with the component that slow type MH acid system includes is divided into and is sent into twice
Underground makes acid solution real its role is to which the acid solution into lithology sandstone is enable to keep hydrionic presence under longer time
Penetration range of the border in lithology sandstone layer increases, that is, achievees the purpose that deep acidizing is transformed.
Wherein, be delivered in the blending ingredients of underground at first, sulfamic acid and part organic phospho acid first provide hydrogen from
Calcium carbonate and quartz components in son dissolving rock, penetrate rock stratum and form crack；Since iron-bearing mineral content is high in stratum, pass through
The effect iron-bearing mineral of acid solution will dissociate Fe3+Ion will generate Fe (OH) when residual sour pH value rises to 23Secondary precipitation, shape
Into secondary injury, acidizing effect is influenced, therefore complexing of the stabilizer realization to iron ion is used as by the citric acid of addition；Inhibition
Agent avoids Fe for preventing corrosion of the acid solution to pipeline and equipment3+Into formation influence acidizing effect；Clay stabilizer is then used for
It adsorbs in surface of clay, prevents water sensitivity mineral hydration swelling and dispersion migration and injured caused by oil-gas Layer.
Continue to convey second batch blending ingredients after 2~8h of interval, be sent into the sulfamic acid of the other half quality on stratum to rock
While hydrogen ion in rock layers is supplemented, villiaumite (i.e. hydrogen fluoride amine) reacts generation hydrofluoric acid with remaining organic phospho acid,
Sandstone skeleton structure and clay mineral are dissolved, increases reservoir permeability.
Specifically, organic phospho acid, i.e. aminotrimethylenephosphonic acid (ATMP), hydroxy ethylene diphosphonic acid (HEDP), second
Diamines tetramethylene phosphonic acid (EDTMP) and diethylenetriamine penta (DETPMP) are MH acid, can be occurred
Step-ionization reacts, and Step-ionization goes out hydrogen ion, since organic phospho acid reacts generation hydrofluoric acid with villiaumite (i.e. hydrogen fluoride amine)
Process can promote the progress of ionization reaction simultaneously, therefore after organic phospho acid encounters hydrogen fluoride amine, Step-ionization goes out hydrogen ion,
And generation hydrofluoric acid HF is reacted with villiaumite, HF and the sandstone reservoir of generation react, gradually penetrate sandstone deep formation, penetrate
It is good to complete acidification reservoir reconstruction effect for distance.
It is illustrated by taking diethylenetriamine penta as an example, Step-ionization process is shown below：
H5R——→H++H4R- pK1=1.0
H4R-——→H++H3R2- pK2=2.5
H3R2-——→H++H2R3- pK3=7.0
H2R3-——→H++H R4- pK4=11.4
H R4-——→H++R5- pK5＞ 12.0
It is not difficult to find out from above formula, since diethylenetriamine penta is pentabasic acid, including five steps electricity
From process, wherein according to the dissociation constant provided, it is main ionization process that first three step, which is ionization, due to adding for later stage hydrogen fluoride amine
Enter, be promoted above-mentioned ionization process, ionize out more hydrogen ions；Therefore, because the ionization process of MH acid is substep
It carries out, and the presence of sulfamic acid simultaneously suitably inhibits the ionization rate of MH acid early period, avoids ionization rate mistake
Soon, it realizes that hydrionic remaining time extends, is conducive to the extension of its penetration range in lithology sandstone layer, it is final to obtain deeply
The effect of degree transformation sandstone layer.
Moreover, it is also resided in the advantages of MH acid can adsorb on a rock surface；In addition to physisorption with
Outside, when MH acid is reacted with clay, at " thin layer " of surface of clay generation aluminium silicon phosphonate, belong to film forming effect, prevent viscous
Soil and acid liquid reaction reduce the solubility of clay, so as to reduce corrosiveness of the acid solution to reservoir skeleton；Meanwhile to rock
The later Ca of corrosion2+、Al3+、Fe2+、Fe3+With very strong complexing power, prevent these ions and fluorine ion, fluosilicic acid root from
Son forms villiaumite precipitation, fluosilicate precipitates and blocks duct, and chelating effect can occurs in it under very low concentrations in addition, make
These ions remain solution state, that is, " threshold effect " occur；Due to inhibiting and precipitation seed is prevented to generate, improve
Permeability and acidification effect.
In conclusion the acidizing sandstone oil reservoir injures sandstone oil reservoir skeleton with slow type MH acid system small, acidification solution
Stifled effect is good, is compared to the mud acid that tradition uses, drill core permeability rate increase multiple ratio is 2~4 times, effectively increases stratum
Permeability is realized and carries out acidification transformation to complex lithology sandstone oil reservoir deep；And the system is in protection rock matrix and inhibition
While clay swelling, the pollution of near wellbore zone is released.In addition, the acidizing sandstone oil reservoir is formed with slow type MH acid system
Each component easily obtains, at low cost, and construction technology is simple, has good popularizing application prospect.
Specific embodiment
With reference to specific embodiment, the present invention is described further, but following embodiments absolutely not to the present invention have appoint
What is limited.
Embodiment 1
The slow type MH acid system of a kind of acidizing sandstone oil reservoir, including 50 parts of DETPMP, 8 parts of amino in parts by weight
Sulfonic acid, 5 parts of hydrogen fluoride amine, 3 parts of high-temperature corrosion inhibitors, 1 part of citric acid, 17 parts of formaldehyde, 1 part of clay stabilizer and 15 parts of water.
Embodiment 2
The slow type MH acid system of a kind of acidizing sandstone oil reservoir, including 48 parts of ATMP, 9 parts of amino sulphurs in parts by weight
Acid, 6 parts of hydrogen fluoride amine, 3.5 parts of high-temperature corrosion inhibitors, 2 parts of citric acids, 15 parts of formaldehyde, 0.5 part of clay stabilizer and 16 parts of water.
Embodiment 3
The slow type MH acid system of a kind of acidizing sandstone oil reservoir, including 45 parts of ATMP, 10 parts of amino in parts by weight
Sulfonic acid, 8.5 parts of hydrogen fluoride amine, 4 parts of high-temperature corrosion inhibitors, 2 parts of citric acids, 13 parts of formaldehyde, 0.5 part of clay stabilizer and 17 parts of water.
Embodiment 4
The slow type MH acid system of a kind of acidizing sandstone oil reservoir, including 52 parts of DETPMP, 7 parts of amino in parts by weight
Sulfonic acid, 5.5 parts of hydrogen fluoride amine, 2.5 parts of high-temperature corrosion inhibitors, 1 part of citric acid, 18 parts of formaldehyde, 1 part of clay stabilizer and 13 parts of water.
Embodiment 5
The slow type MH acid system of a kind of acidizing sandstone oil reservoir, including 55 parts of EDTMP, 5 parts of amino in parts by weight
Sulfonic acid, 7.5 parts of hydrogen fluoride amine, 2 parts of high-temperature corrosion inhibitors, 3 parts of citric acids, 10 parts of formaldehyde, 0.5 part of clay stabilizer and 17 parts of water.
In above-described embodiment 1~5, in addition to high-temperature corrosion inhibitor and clay stabilizer, other components are bought from commercial product.
Wherein, the preparation method of high-temperature corrosion inhibitor is：It is 1 first by molar ratio:1:0.8 acetophenone, metaformaldehyde and cyclohexylamine three
It kind of monomer and accounts for the hydrochloric acid (37.5wt.%) of monomer gross mass 3.5% and adds in reaction kettle and be warming up to 95 DEG C of reaction 8h, obtain
The condensation product of acetophenone-metaformaldehyde-cyclohexylamine；Then it is 10 by weight ratio:2:6:1 acetophenone-metaformaldehyde-cyclohexylamine
Condensation product, nonylphenol polyoxyethylene ether, methanol and propilolic alcohol mixed to get to high-temperature corrosion inhibitor.Clay stabilizer
Preparation method is：It is first 1 in molar ratio by ethylenediamine and acetic acid:2.5~3 reaction generation organic ammonium salts, then with weight ratio
It is 3:7 are mixed with ammonium chloride, and gained mixture can be used as clay stabilizer use.
Acidizing treatment simulation further is carried out with slow type MH acid system to the acidizing sandstone oil reservoir of Examples 1 to 5, with
Its corresponding acidizing effect is evaluated.
Mimicry acidifying is tested：The core simulation sandstone that 6 pieces of ingredients are identical is taken, and is respectively put into 6 large beakers, to 6
The mix acid liquor by evenly mixing that Examples 1 to 5 provides is separately added into beaker, injects mud acid solution in the 6th beaker
(12wt.%HCl+3wt.%HF) as a comparison case.The acid solution injected in each beaker there was not core completely.Core is impregnated
It takes out, dries after 48h in acid solution, impregnate forward and backward weight by weighing, calculate Examples 1 to 5 and come relative to comparative example
Say acid solution to the acidification of rock core as a result, i.e. core permeability increase multiple, specific formula for calculation are：A=(m1-m2)/(m1’-
m2'), wherein, a increases multiple, m for core permeability1For the core initial quality of Examples 1 to 5, m2For Examples 1 to 5
Quality of the core after immersion, m1' be comparative example core initial quality, m2' it is matter of the core of comparative example after immersion
Amount.
In addition, also to the acidizing sandstone oil reservoir of Examples 1 to 5 with slow type MH acid system under normal pressure to J55 steel discs
Corrosion rate tested, test the corrosion mitigating effect of the system.
Test result is as follows shown in table 1.
Table 1：
As can be seen from the above table, the mud acid body which is used with slow type MH acid system relative to tradition
The core permeability of system can effectively increase at least 3 times or more, to the corrosion rate ＞ 0.708g/m of J55 steel discs2.h, there is acid
The advantages of quick property formation damage is small, and acidification plugging removal effect is good, corrosion mitigating effect is good；Simultaneously as acid solution used in the system exists
Not volatile during use, each additive is nontoxic or less toxic, small to human body and environmental injury.In actual use, it is sour
Compatibility is good between each additive of liquid and between water flooding.
The one embodiment applied below for the practical acidification of the slow type MH acid system of the acidizing sandstone oil reservoir.
Embodiment 6
Flower xx well locations are in Hainan Fushan oil field, and small fault block is more, lithology is complex, and reservoir permeability is low, reservoir and non-storage
Layer is interlaced, and interlayer relation is complicated, and reservoir sensitivity is strong.It is quick that the acid-sensitive evaluation result of the block belongs to strong acid, and Lin Jing is conventional
Soil acid acidizing reaches expected effect of increasing production unobvious after acidification.Therefore, it determines to carry out acid to the well using multi-hydrogen acid system
Neutralizing is stifled.Wherein, acidification liquid system includes 50 parts by weight organic phospho acids, 10 parts by weight sulfamic acids, 5 parts by weight ammonium acid fluorides, 1
Parts by weight clay stabilizer, 3 parts by weight of lemon acid, 2 parts by weight high-temperature corrosion inhibitors, 13 parts by weight of formaldehyde and 16 parts by weight are originally
Water；Displacement fluid is done with+2% clay stabilizer of clear water.
Construction results compare：Well day oil-producing 3.06t/d before acidification, well day oil-producing 15.34t/d after acidification, volume increase 5
Times, it is seen that using the acidizing sandstone oil reservoir with slow type MH acid system carry out acidification de-plugging achieve highly significant volume increase imitate
Fruit.
Claims (4)
1. a kind of slow type MH acid system of acidizing sandstone oil reservoir, which is characterized in that including be calculated in mass percent 45~
55% organic phospho acid, 5~10% sulfamic acid, 5~10% hydrogen fluoride amine, 2~4% high-temperature corrosion inhibitor, 1~3%
Citric acid, 10~18% formaldehyde, 0.5~1% clay stabilizer and surplus water；Wherein, the organic phospho acid is ammonia
Base trimethylene phosphonic, hydroxy ethylene diphosphonic acid, ethylenediamine tetramethylene phosphonic acid or diethylenetriamine penta.
2. the slow type MH acid system of acidizing sandstone oil reservoir according to claim 1, which is characterized in that the high temperature delays
Mixture of the erosion agent for the condensation product of acetophenone-metaformaldehyde-cyclohexylamine, nonylphenol polyoxyethylene ether, methanol and propilolic alcohol, four
Person's weight ratio is 10:2:6:1.
3. the slow type MH acid system of acidizing sandstone oil reservoir according to claim 1, which is characterized in that the clay is steady
Agent is determined for organic ammonium salt and the mixture of ammonium chloride, and the two weight ratio is 3:7；Wherein, organic ammonium salt is 1 by molar ratio:2.5~
3 ethylenediamine is generated with acetic acid reaction.
4. a kind of acidizing sandstone oil reservoir according to claim 1 construction technology of slow type MH acid system, feature
It is, construction procedure is as follows：The sulfamic acid of suitable aqueous solvent and half quality is added in agitator tank first, is stirred evenly
After continue to add in organic phospho acid, high-temperature corrosion inhibitor, citric acid, formaldehyde and clay stabilizer into agitator tank, continue stirring to mixed
After closing uniformly, gained mixed solution is delivered to underground by casing；After 2~8h is spaced, hydrogen fluoride is added in into agitator tank
Amine, the sulfamic acid of remaining half quality and suitable aqueous solvent, well is delivered to after stirring evenly by mixed solution by casing
Under.
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| CN109777389A (en) * | 2019-03-04 | 2019-05-21 | 北京国海能源技术研究院 | A kind of MH acid system and preparation method thereof suitable for reservoir blockages relieving acidification |
| CN113046050A (en) * | 2021-03-17 | 2021-06-29 | 中国海洋石油集团有限公司 | Efficient slow-speed acidizing working fluid and preparation method thereof |
| CN113563864A (en) * | 2020-04-29 | 2021-10-29 | 中国石油天然气股份有限公司 | Sandstone reservoir retarded acid, application and production increase transformation method of sandstone reservoir |
| CN114427400A (en) * | 2020-09-21 | 2022-05-03 | 中国石油化工股份有限公司 | Method for improving development effect of biological limestone oil reservoir by utilizing acid-producing microorganisms |
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