CN104073236B - Self-diverting acidizing fluid and application thereof in yield-increasing acidification of oil and gas fields - Google Patents
Self-diverting acidizing fluid and application thereof in yield-increasing acidification of oil and gas fields Download PDFInfo
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- CN104073236B CN104073236B CN201310101432.7A CN201310101432A CN104073236B CN 104073236 B CN104073236 B CN 104073236B CN 201310101432 A CN201310101432 A CN 201310101432A CN 104073236 B CN104073236 B CN 104073236B
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- 239000012530 fluid Substances 0.000 title abstract description 13
- 230000020477 pH reduction Effects 0.000 title abstract 3
- 239000002280 amphoteric surfactant Substances 0.000 claims abstract description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 8
- 230000006378 damage Effects 0.000 claims description 38
- 239000002253 acid Substances 0.000 claims description 36
- 230000002209 hydrophobic effect Effects 0.000 claims description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- -1 sodium alkyl benzene Chemical class 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000001118 alkylidene group Chemical group 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 5
- 229940077388 benzenesulfonate Drugs 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 claims description 4
- 125000002252 acyl group Chemical group 0.000 claims description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 2
- 239000005642 Oleic acid Substances 0.000 claims description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 2
- JAJWGJBVLPIOOH-IZYKLYLVSA-M sodium taurocholate Chemical compound [Na+].C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(=O)NCCS([O-])(=O)=O)C)[C@@]2(C)[C@@H](O)C1 JAJWGJBVLPIOOH-IZYKLYLVSA-M 0.000 claims 1
- 239000004094 surface-active agent Substances 0.000 abstract description 14
- 150000001408 amides Chemical class 0.000 abstract description 9
- 125000001165 hydrophobic group Chemical group 0.000 abstract description 5
- 230000000638 stimulation Effects 0.000 abstract description 4
- 239000002562 thickening agent Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 46
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000011435 rock Substances 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 9
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000035699 permeability Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000006471 dimerization reaction Methods 0.000 description 4
- 238000005829 trimerization reaction Methods 0.000 description 4
- 235000016068 Berberis vulgaris Nutrition 0.000 description 3
- 241000335053 Beta vulgaris Species 0.000 description 3
- WVIDJCLBYLPMFJ-UHFFFAOYSA-N C(CCCCCCCCCCCCCCCCC)N.CCC Chemical compound C(CCCCCCCCCCCCCCCCC)N.CCC WVIDJCLBYLPMFJ-UHFFFAOYSA-N 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000010430 carbonatite Substances 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229960003237 betaine Drugs 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 238000005553 drilling Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000019197 fats Nutrition 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 208000014674 injury Diseases 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 description 1
- 241001044369 Amphion Species 0.000 description 1
- KYXHKHDZJSDWEF-LHLOQNFPSA-N CCCCCCC1=C(CCCCCC)C(\C=C\CCCCCCCC(O)=O)C(CCCCCCCC(O)=O)CC1 Chemical compound CCCCCCC1=C(CCCCCC)C(\C=C\CCCCCCCC(O)=O)C(CCCCCCCC(O)=O)CC1 KYXHKHDZJSDWEF-LHLOQNFPSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- HYAAPGPZUMZCDM-UHFFFAOYSA-N S(=O)(=O)=C[Na] Chemical compound S(=O)(=O)=C[Na] HYAAPGPZUMZCDM-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000004064 cosurfactant Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 150000001470 diamides Chemical class 0.000 description 1
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000012956 testing procedure Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 235000021081 unsaturated fats Nutrition 0.000 description 1
- 239000002888 zwitterionic surfactant 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
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/72—Eroding chemicals, e.g. acids
- C09K8/74—Eroding chemicals, e.g. acids combined with additives added for specific purposes
-
- 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
- C09K2208/30—Viscoelastic surfactants [VES]
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a self-diverting acidizing fluid and application thereof in stimulation acidification of oil and gas fields. The self-diverting acidizing fluid comprises the following components by taking the total weight of the self-diverting acidizing fluid as a reference: 0.1 to 10% of amphoteric surfactant having a plurality of hydrophilic groups and hydrophobic groups, 0.1 to 2% of anionic surfactant, and the balance of hydrochloric acid having a concentration of 3 to 28 wt%; wherein the amphoteric surfactant having a plurality of hydrophilic groups and hydrophobic groups is an amide amphoteric surfactant having two or three hydrophilic groups and hydrophobic groups. The invention also provides application of the self-diverting acidizing fluid in stimulation and acidification of an oil and gas field and a method for acidizing the oil and gas well of the oil and gas field by using the self-diverting acidizing fluid. The self-diverting acidizing fluid provided by the invention is an acidizing fluid with good performance, has obvious viscoelasticity in a solution with lower concentration, and is an excellent surfactant acidizing, fracturing and diverting thickener.
Description
Technical field
The present invention relates to a kind of low damage acidifying solution, more particularly to a kind of surface containing multiple hydrophilic radicals and hydrophobic grouping
The low damage acidifying solution of activating agent, belongs to petroleum vapour development technique field.
Background technology
The Development and Production of oil gas is that the pressure reduction on stratum makes liquid flow to well head by drilling well in oil-containing gas reservoir first.Oil
The production of gas well is generally affected by low-permeability, and low-permeability can be caused by operations such as drilling well, cleanings, or day
Right fine and close Low permeable oil and gas reservoirs.
Low permeability oil and gas field is needed to swash operation is produced, acidifying is one of conventional well stimulation, and acidifying is to make acid stream
The method that body is contacted with stratum by well bucket.Acid solution produces wormhole with rock reaction dissolving formation rock, and producing duct can
Oil gas is made to flow into withdrawal well bucket, effective placement of acid solution is highly important.Natural hydrocarbon reservoir is typically heterogeneous body multiphase.Acid
React with the rock for contacting first, the rock reaction that then acid solution will continue and contact first, and preferentially enter high permeability zones
Rather than the hyposmosis area for needing most is entered, the macropore for having reacted along smaller resistance is flowed by the acid solution that further injects,
And it is unable to the important aperture road area of diffluence.General acid solution is reacted with rock rapidly and consuming quickly, thus can not again with
Unreacted rock continuation effect, therefore acid can not be completely attached to whole formation area.
In order to effectively arrange acid solution, injection liquid is made to reach Zone Full, so that maximizing the benefits, can adopt various cloth
Steering dividing technology is put, chemical particle glue and foam are most diversion agents used in matrix acidifying, be correspondingly formed temporarily stifled and steep
Foam distributary acid technique, but foam is limited by temperature and high permeability.Oily (water) although soluble resin can be in well bore wall
Face forms filter cake, blocks high permeability zones, reduces the absorbability of high permeability zone to reach the purpose of shunting, but the change of organic resin
Particulate is very sensitive to the intrinsic fracture in stratum, and this can make organic resin reach layer position.And most of organic trees
Fat diversion agent is obtained by polymer chemistry crosslinking, is had residual injury stratum, can be caused the permanent plugging of these particles,
The injury for being difficult to recover is caused to in-place permeability, has a strong impact on acid stimulation effect.
Turn to acid to be generally made up of the hydrochloric acid crosslinking agent sensitive with gelatinizing agent, pH.When acid solution part consumes, when pH is raised
Liquid plastic.United States Patent (USP) US4695389, US7119050 is individually disclosed and is self-assembly of based on viscoelastic surfactant
Viscoplasticity glue turn to acid, main include it is N, N- dihydroxy ethyl aliphatic amine acetic acid salt, alkyl beet alkali ampholytic surface active agent.
When, before system unreacted, acid fluid system does not have plastic, viscosity keeps relatively low.And the multivalence produced after working as the reaction of acid solution and rock from
Son and pH rise the viscoelastic colloidal for obtaining thickening, due to the increase of viscosity so as to which flow resistance increases, and does not subsequently have and rock stratum
Reacted acid solution body further turns to responseless low viscosity, and the region of tight stratum makes injection liquid reach whole areas
Domain, so that maximizing the benefits.Chinese patent application 201110282979.2 provides a kind of low damage foamed acid, and the system is also
Based on Viscoelastic surfactant's system, its plastic is the viscoplasticity formed it into based on product rush after acidifying, as its viscosity is
The result of surfactant molecule association aggregation, after meeting oil, coherent condition changes, englobement low-viscosity (mobile) liquid, automatically broken glue,
And due to its be small molecule nothing residue, with the particular advantages little to formation damage.
Content of the invention
It is an object of the invention to provide a kind of new low damage acidifying solution, which is a kind of by containing multiple hydrophilic radicals
The viscoplasticity acidifying solution constituted with the amphoteric surfactant of hydrophobic grouping, in use, the viscoplasticity acidifying liquid energy is enough
Having an effect with the rock in environment makes pH value change, and then regulates and controls viscosity.
For reaching above-mentioned purpose, the invention provides a kind of low damage acidifying solution, with the gross weight of the low damage acidifying solution
On the basis of, which has following component composition：Amphoteric surfactant 0.1-10% with multiple hydrophilic radicals and hydrophobic grouping,
Anion surfactant 0.1-2%, the hydrochloric acid of balance of concentration 3-28wt%.
Low damage acidifying solution provided by the present invention has been a kind of amphion containing multiple hydrophilic radicals and hydrophobic grouping
The compound acid system of the compositions such as surfactant and cosurfactant, under relatively low surfactant concentration, acid solution with
The multivalent ion produced after rock reaction and pH rising are obtained the viscoelastic colloidal of thickening and play a part of steering.Above-mentioned
In " zwitterionic surfactants with multiple hydrophilic radicals and hydrophobic grouping ", " hydrophilic radical and hydrophobic grouping " refers to table
In one molecule of face activating agent contain hydrophilic radical, hydrophobic grouping, " multiple " refer to each group have multiple.
According to specific embodiments of the present invention, it is preferable that in above-mentioned low damage acidifying solution, adopted with multiple
The amphoteric surfactant of hydrophilic radical and hydrophobic grouping be with two or three hydrophilic radicals and two or three hydrophobic groups
The acid amides amphoteric surfactant of group.
According to specific embodiments of the present invention, it is preferable that in above-mentioned low damage acidifying solution, adopted with multiple
The amphoteric surfactant of hydrophilic radical and hydrophobic grouping has structure shown in formula I：
In Formulas I：X is 2 or 3；R1The acyl group containing x-CO- group for total carbon number 24-54；R2It is the alkylene containing 2-5 carbon
Base；R3、R4Independently be alkyl containing 1-4 carbon ,-CH2CH2COO- or-CH2CH2OH；R5For-CH2- or-CH2CH2-.
It is highly preferred that the R for being adopted1The structure having as shown in Formula II-formula IV any one：
In above-mentioned Formula II-formula IV, R6For the alkylidene that carbon chain lengths are 7, R7For the alkylidene that carbon chain lengths are 5, R8For carbon
Chain length is 8 alkylidene.
According to specific embodiments of the present invention, it is preferable that in above-mentioned low damage acidifying solution, adopted with multiple
The amphoteric surfactant of hydrophilic radical and hydrophobic grouping includes the combination of one or more in following amphoteric surfactant：
DIBT：Total carbon number be 36 the amido propyl betaine containing two hydrophilic group and two hydrophobic groupings (Formula II,
Acid amides shown in III)；
TDIBT：Total carbon number be 36 amido propyl betaine containing two hydrophilic group and two hydrophobic groupings with total
Carbon number is 54 mixture containing three hydrophilic radicals and the amido propyl betaine of three hydrophobic groupings, the content ratio of the two
For 1: 99-99: 1, it is preferable that the content of the two is respectively 80wt% and 20wt%, and (which can be the acyl shown in Formula II, III, IV
The mixture of amine, wherein, the acid amides shown in Formula II, III is isomers)；
TIBT：Total carbon number is the 54 amido propyl betaine (formula IV containing three hydrophilic radicals and three hydrophobic groupings
Shown acid amides).
According to specific embodiments of the present invention, it is preferable that in above-mentioned low damage acidifying solution, the anion table that adopted
Face activating agent includes oleic acid sulfonylmethyl sodium taurocholate (its structure is shown as a formula V) and/or sodium alkyl benzene sulfonate etc., also, institute
The alkyl for stating sodium alkyl benzene sulfonate is the straight chained alkyl containing 8-18 carbon or branched alkyl.
According to specific embodiments of the present invention, it is preferable that in above-mentioned low damage acidifying solution, with multiple hydrophilic radicals and
The amphoteric surfactant of hydrophobic grouping is prepared in accordance with the following methods：Starting acid is reacted with organic amine, then enters one
Step is synthesized with sodium chloroacetate and obtains the amphoteric surfactant with multiple hydrophilic radicals and hydrophobic grouping.
Many polyglycerol fatty acids are industrialization product, can also refer to record in United States Patent (USP) US5001260, US6187903 by
Unsaturated fat acid reaction is obtained, and structure I I, III is possible isomers.Dimer (fatty acid) yl is permissible with the reaction of the amine of mol ratio 1: 2
Diamides is generated, same principle, trimerized fatty acids can generate triamide with the amine reaction of mol ratio 1: 3.Multiamide can enter
One step forms betaine type activating agent with carboxylic radical reaction.
Above-mentioned low damage acidifying solution provided by the present invention can be by two with multiple hydrophilic radicals and hydrophobic grouping
Property surfactant and anion surfactant, mixed in hydrochloric acid prepare and obtain, its be a kind of viscoelastic surfactant from
Turn to acidifying solution.
Present invention also offers application of the above-mentioned low damage acidifying solution in oil gas field volume increase acidifying.
Present invention also offers a kind of oil gas field acidization tool, which is the oil using above-mentioned low damage acidifying solution to oil gas field
The method is acidified by gas well.
Low damage acidifying solution provided by the present invention is a kind of surfactant system, it is also possible to used as foamed self-diverting acid
Change and use.
As other general acidizing treatments, in the self-diverting acid agent provided using the present invention, can also add slow
The compositions such as erosion agent, non-emulsifier, ferrous stability, complexing agent, these compositions can be determined according to prior art.This
Bright provided low damage acidifying solution is sensitive to iron ion, it is possible to use iron reducer and complexing agent do prepad fluid and processed；
Prepad fluid can also be done with mutual solvent, prepad fluid includes small-molecular-weight fat, ether, alcohol etc..Can also phase in the low damage acidifying solution
Hold a small amount of non-emulsifier, to prevent from emulsifying the generation with sludge.
Low damage acidifying solution provided by the present invention is a kind of acidifying solution of good performance, and which has in lower concentration solutions
There is obvious viscoplasticity, be that a kind of excellent surfactant acidifying pressure break turns to thickener.
Specific embodiment
In order to be more clearly understood to the technical characteristic of the present invention, purpose and beneficial effect, the existing skill to the present invention
Art scheme carry out described further below, but it is not intended that to the present invention can practical range restriction.
Octadecyl amide propane diamine two of the embodiment 1 containing two or three hydrophilic radicals and two or three hydrophobic groupings
The synthesis of property surfactant
1st, the conjunction containing two hydrophilic group and the octadecyl amide propane diamine amphoteric surfactant of two hydrophobic groupings
Become, which comprises the following steps：
The synthesis of dimerization octadecyl amide：
Take 100g high-purity dimeric acid (the dimerization stearic acid containing ＞ 95wt%, C36) be added to N, the N- dimethyl of 38.3g-
In 1,3- propane diamine (0.38mol), mix and 160-180 DEG C of reaction 3-8 hour is heated to, distill the water that reaction is generated；
Reaction terminates when proceeding to acid number less than 6, and unnecessary N, N- dimethyl -1,3- propane diamine, acquisition binary acid acid amides is distilled off
Propane diamine intermediate (i.e. dimerization octadecyl amide)；
15.7g sodium chloroacetate (0.135mol) is added in 137ml water, Hybrid Heating is subsequently adding 50g bis- to 80 DEG C
Poly- octadecyl amide, reacts 4-6 hour at 70-80 DEG C, when the mass percentage content of NaCl reaches the 98% of theory, instead
Should finish, obtain the product of about 30% active matter content, i.e., the beet alkalescence two containing two hydrophilic group and two hydrophobic groupings
Property surfactant (DIBT), obtained by above-mentioned reaction is the mixture of the compound representated by following structure, final produces
Thing structure dimer is probably homologue：
2nd, the conjunction containing three hydrophilic radicals and the octadecyl amide propane diamine amphoteric surfactant of three hydrophobic groupings
Become, which comprises the following steps：
The synthesis of trimerization octadecyl amide：
Take common dimeric dibasic acid (the dimerization stearic acid containing 80wt%, the trimerization stearic acid of C36 and 20wt%, the mixing of C54
Thing) 100g is added to N, N- dimethyl -1 of 38.3g, and in 3- propane diamine (0.38mol), mix and be heated to 160-180 DEG C
Reaction 3-8 hour, distills the water that reaction is generated；Reaction terminates when proceeding to acid number less than 6, and unnecessary N, N- bis- is distilled off
Methyl isophthalic acid, 3- propane diamine, obtain ternary acid acid amides propane diamine intermediate (i.e. trimerization octadecyl amide)；
15.7g sodium chloroacetate (0.135mol) is added in 137ml water, Hybrid Heating is subsequently adding 50g bis- to 80 DEG C
Poly- octadecyl amide and the mixture of trimerization octadecyl amide, react 4-6 hour at 70-80 DEG C, when the quality hundred of NaCl
When dividing reach theory than content 98%, reaction is finished, and obtains the product of about 30% active matter content, that is, contain three hydrophilic radicals
With the beet of three hydrophobic groupings alkalescence amphoteric surfactant (TDIBT), the compound representated by structure shown below
Content is consistent with the content of starting acid, and when starting acid is pure a certain kind acid, obtained product is also pure a certain kind here
Compound, specifically can be prepared as needed.
Embodiment 2
On Haake RS600 flow graph, the viscosity of the low damage acidifying solution of the different compositions of test.
The code name of different chemical structures is as follows：
DIBT：The amido propyl betaine containing two hydrophilic radicals and two hydrophobic groupings of C36 is (shown in Formula II, III
Acid amides, embodiment 1 prepare)；
TDIBT：The C54's of the acyl propyl glycine betaine containing two hydrophilic of the C36 of 80wt% and 20wt% contains
The amido propyl betaine of three hydrophilic groups and three hydrophobic groups mixture (mixture of the acid amides shown in Formula II, III, IV,
Prepared by embodiment 1)；
OBT：Single-stranded stearamide base CAB (Shanghai Nuo Song Industrial Co., Ltd.)；
Anion surfactant：
OT：Oleic acid sulfonylmethyl sodium taurocholate；
ABS：Neopelex.
Concrete testing procedure：
By different amphoteric surfactantes (DIBT, TDIBT, OBT) and different anion surfactant (ABS,
OT) mixed respectively, be then dissolved in CaCl of the concentration for 24wt%2In solution, obtain simulating low damage acidifying solution and carbon
The reacted generation CaCl in sour rock stratum2Composition, its pH value is controlled to 4, in low damage acidifying solution, amphoteric surfactant
Active quantities are 1.80wt%, and the content of anion surfactant is 0.35wt%；
Under the shear rate of 1001/s, determine at 80 DEG C and formed after low damage acidifying solution is reacted with carbonatite
CaCl2Condition afterwards：Reaction equation is HCl (acid solution)+CaCO3(carbonatite) → CaCl2+CO2+H2O.Viscosity test results such as table 1
Shown.
1 viscosity test results of table (unit is mPa s)
| Mix with ABS | Mix with OT | |
| DIBT | 139 | 150 |
| TDIBT | 162 | 180 |
| OBT | 102 | 128 |
Relatively general single-stranded amphoteric surfactant can be seen that by the content of table 1, containing two, three hydrophilic radicals
Act under relatively low concentration with the amphoteric surfactant of two, three hydrophobic groupings and anion surfactant and can obtain
Obtain high viscosity colloid.
Embodiment 3
By different amphoteric surfactantes (DIBT, TDIBT, OBT) and different anion surfactant (ABS,
OT) mixed respectively, concentration is then dissolved in for, in the HCl solution of 20wt%, low damage acidifying solution being obtained, its pH value ＜ 1,
In low damage acidifying solution, the active quantities of amphoteric surfactant are 1.80wt%, and the content of anion surfactant is
0.35wt%；
Under the shear rate of 100l/s, viscosity of the low damage acidifying solution at 20 DEG C, 80 DEG C is tested respectively, concrete test
As a result as shown in table 2.
2 viscosity test results of table (unit is mPa s)
| Mix (20 DEG C) with ABS | Mix (20 DEG C) with OT | Mix (80 DEG C) with ABS | Mix (80 DEG C) with OT | |
| DIBT | 2 | 4 | 1 | 1 |
| TDIBT | 3 | 6 | 2 | 2 |
Can be seen that in acid fluid system by the viscosity test results of table 2, solution be (surfactant i.e. shown in table 2
Mixture and the mixed solution of HCl) viscosity is very low, and low damage acidifying solution and carbonatite is can be seen that according to the data in table 1
Stone reaction occurs the situation that gelling solution viscosity increases after producing salt and pH rising, this explanation is using the self-diverting acid of the present invention
Change the purpose that liquid can reach liquid steering.
Claims (6)
1. a kind of low damage acidifying solution, on the basis of the gross weight of the low damage acidifying solution, which has following component composition：Have
The amphoteric surfactant 0.1-10% of multiple hydrophilic radicals and hydrophobic grouping, anion surfactant 0.1-2%, balance of
The hydrochloric acid of concentration 3-28wt%；
Wherein, the amphoteric surfactant with multiple hydrophilic radicals and hydrophobic grouping has structure shown in formula I：
In Formulas I：X is 2 or 3；R1The acyl group containing x-CO- group for total carbon number 24-54；R2It is the alkylidene containing 2-5 carbon；
R3、R4Independently be alkyl containing 1-4 carbon；R5For-CH2- or-CH2CH2-.
2. low damage acidifying solution according to claim 1, wherein, the R1Have as shown in Formula II-formula IV any one
Structure：
In above-mentioned Formula II-formula IV, R6For the alkylidene that carbon chain lengths are 7, R7For the alkylidene that carbon chain lengths are 5, R8For carbon chain length
Spend the alkylidene for 8.
3. low damage acidifying solution according to claim 1 and 2, wherein, the anion surfactant includes oleic acid acyl
Ylmethyl sodium taurocholate and/or sodium alkyl benzene sulfonate, also, the alkyl of the sodium alkyl benzene sulfonate be containing the straight of 8-18 carbon
Alkyl group or branched alkyl.
4. low damage acidifying solution according to claim 1 and 2, wherein, described with multiple hydrophilic radicals and hydrophobic grouping
Amphoteric surfactant prepare in accordance with the following methods：
Starting acid and organic amine are reacted, be further synthesized with sodium chloroacetate obtain described with multiple hydrophilic radicals and
The amphoteric surfactant of hydrophobic grouping.
5. application of the low damage acidifying solution described in any one of claim 1-4 in oil gas field volume increase acidifying.
6. a kind of oil gas field acidization tool, is wherein the low damage acidifying solution described in usage right requirement any one of 1-4 to oil gas
The method is acidified by the Oil/gas Well in field.
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| CN107216865B (en) * | 2017-06-08 | 2020-05-22 | 中海石油伊拉克有限公司 | Self-diverting acidizing fluid and preparation method and application thereof |
| CN108467724A (en) * | 2018-03-12 | 2018-08-31 | 中国石油天然气股份有限公司 | Online shunt acid continuously injected into water injection well and preparation method thereof |
| CN110591685B (en) * | 2019-09-16 | 2022-05-10 | 西安石油大学 | In-situ self-generated microfoam steering acidizing fluid, acidizing steering method and application |
| CN116478671B (en) * | 2023-04-11 | 2024-06-11 | 西南石油大学 | Stability adjusting composition, ultralow oil-water ratio high-density oil-based drilling fluid and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102020983A (en) * | 2009-09-12 | 2011-04-20 | 中国石油化工股份有限公司 | Viscosity-variable diverting acid for improving stratigraphic acidified section |
| CN102373054A (en) * | 2010-08-12 | 2012-03-14 | 中国石油天然气股份有限公司 | Viscoelastic surfactant acidizing fluid |
| CN102504799A (en) * | 2011-11-29 | 2012-06-20 | 西南石油大学 | Acidification diverter composition |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US7119050B2 (en) * | 2001-12-21 | 2006-10-10 | Schlumberger Technology Corporation | Fluid system having controllable reversible viscosity |
| US7638468B2 (en) * | 2003-01-15 | 2009-12-29 | Bj Services Company | Surfactant based viscoelastic fluids |
-
2013
- 2013-03-27 CN CN201310101432.7A patent/CN104073236B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102020983A (en) * | 2009-09-12 | 2011-04-20 | 中国石油化工股份有限公司 | Viscosity-variable diverting acid for improving stratigraphic acidified section |
| CN102373054A (en) * | 2010-08-12 | 2012-03-14 | 中国石油天然气股份有限公司 | Viscoelastic surfactant acidizing fluid |
| CN102504799A (en) * | 2011-11-29 | 2012-06-20 | 西南石油大学 | Acidification diverter composition |
Non-Patent Citations (2)
| Title |
|---|
| 一类含酰胺基的两性双子表面活性剂的合成与性能研究;刘昱容 等;《分子科学学报》;20111231;第27卷(第6期);第387页第1.2节 * |
| 新型粘弹性表面活性自转向酸的研制及性能评价;马利成 等;《油气地质与采收率》;20070930;第14卷(第5期);第98-99页第2.1节，第100页第4节 * |
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