CN104073236A - Self-diverting acidifying liquid and applications thereof in production increase acidification of oil and gas fields - Google Patents
Self-diverting acidifying liquid and applications thereof in production increase acidification of oil and gas fields Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/30—Viscoelastic surfactants [VES]
Abstract
The invention relates to a self-diverting acidifying liquid and applications thereof in production increase acidification of oil and gas fields. Based on the total weight of the self-diverting acidifying liquid, the self-diverting acidifying liquid comprises 0.1-10% of an ampholytic surfactant having a plurality of hydrophilic groups and hydrophobic groups, and 0.1-2% of an anionic surfactant, with the balance being hydrochloric acid having a concentration of 3-28 wt%, wherein the ampholytic surfactant having a plurality of the hydrophilic groups and the hydrophobic groups is an amide ampholytic surfactant having two or three hydrophilic groups and hydrophobic groups. The invention also provides the applications of the self-diverting acidifying liquid in production increase acidification of oil and gas fields, and a method of acidifying oil-gas wells in the oil and gas fields by using the self-diverting acidifying liquid. The self-diverting acidifying liquid has good properties and has obvious viscoelasticity in a solution having a relatively low concentration. The self-diverting acidifying liquid is a good surfactant acidifying cracking diverting thickener.
Description
Technical field
The present invention relates to a kind of self-diverting acid liquid, relate in particular to a kind of self-diverting acid liquid of the tensio-active agent containing multiple hydrophilic radicals and hydrophobic grouping, belong to petroleum vapour development technique field.
Background technology
The Development and Production of oil gas be first by drilling well in oil-containing gas reservoir, the pressure reduction on stratum makes liquid flow to well head.The production of Oil/gas Well is subject to the impact of low permeability conventionally, and low permeability can be caused by the operation such as drilling well, cleaning, or natural fine and close low-permeability oil gas reservoir.
Need to swash product operation for low-permeability oil gas field, acidifying is one of conventional well stimulation, and acidifying is to make acidic fluid pass through the method that well bucket contacts with stratum.Acid solution is reacted with rock and is dissolved formation rock generation wormhole, produces duct and can make oil gas flow into withdrawal well bucket, and effective placement of acid solution is very important.Natural oil gas reservoir normally heterogeneous body is heterogeneous.Acid and the rock reaction first contacting, then acid solution is by the rock reaction continuing and first contact, and preferentially enter into high permeability zones instead of enter the hyposmosis district needing most, the acid solution that a nearly step is injected flows edge compared with the macropore having reacted of slight drag, and can not the important area, aperture road of diffluence.General acid solution is reacted and very fast consuming rapidly with rock, thereby can not be again and unreacted rock continuation effect, and therefore acid can not contact completely with whole formation area.
In order effectively to arrange acid solution, make filling liquid reach all zones, so that maximizing the benefits, can adopt various layouts to turn to dividing technology, chemical particle glue and foam are in matrix acidifying, to use maximum diverting agents, corresponding formation is stifled and foam distributary acid technique temporarily, but foam is subject to the restriction of temperature and high permeability.Oil (water) is although soluble resin can form filter cake at well wall, stop up high permeability zones, reduce the receptivity of most permeable zone to reach the object of shunting, but the chemical particle of organic resin is very responsive to the natural fracture in stratum, this can make organic resin can not reach layer position.And most of organic resin diversion agents are cross-linked acquisition by polymer chemistry, there is residual injury stratum, can cause the permanent plugging of these particles, zone permeability is caused and is difficult to the injury that recovers, have a strong impact on acid stimulation effect.
Turn to acid conventionally to be formed by the linking agent of hydrochloric acid and gelatinizing agent, pH sensitivity.When acid solution part consumes, liquid plastic in the time that pH raises.US Patent No. 4695389, US7119050 disclose respectively the visco-elasticity glue forming based on viscoelastic surfactant self-assembly and have turned to acid, mainly comprise it being 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, and it is lower that viscosity keeps.And the polyvalent ion producing after acid solution is reacted with rock and pH rising obtain the viscoelastic colloidal of thickening, due to the increase of viscosity, its resistance to flow is increased, follow-up do not have with the reacted acid solution body in rock stratum and then turn to responseless low viscosity, the region of tight stratum, make filling liquid reach all zones, so that maximizing the benefits.It is a kind of from turning to foamed acid that Chinese patent application 201110282979.2 provides, this system is also based on visco-elasticity surfactivity system, its plastic is to impel the visco-elasticity of its formation based on acidifying after product, because its viscosity is the result that surfactant molecule association is assembled, to meet after oil, state of aggregation changes, englobement low-viscosity (mobile) liquid, automatically broken glue, and due to its be small molecules without residue, there is the particular advantages little to formation damage.
Summary of the invention
The object of the present invention is to provide a kind of novel self-diverting acid liquid, it is a kind of visco-elasticity acidifying liquid being made up of the amphoterics that contains multiple hydrophilic radicals and hydrophobic grouping, in use, this visco-elasticity acidifying liquid can with environment in rock have an effect pH value changed, and then regulation and control viscosity.
For achieving the above object, the invention provides a kind of self-diverting acid liquid, taking the gross weight of this self-diverting acid liquid as benchmark, it has following one-tenth and is grouped into: the amphoterics 0.1-10% with multiple hydrophilic radicals and hydrophobic grouping, anion surfactant 0.1-2%, surplus is the hydrochloric acid of concentration 3-28wt%.
Self-diverting acid liquid provided by the present invention has been a kind of compound acid system of composition such as zwitterionics and cosurfactant etc. containing multiple hydrophilic radicals and hydrophobic grouping, under lower surfactant concentration, the viscoelastic colloidal that the polyvalent ion that acid solution produces after reacting with rock and pH rising can obtain thickening plays the effect turning to.In above-mentioned " thering is the zwitterionics of multiple hydrophilic radicals and hydrophobic grouping ", " hydrophilic radical and hydrophobic grouping " refers in a molecule of tensio-active agent and contains hydrophilic radical, hydrophobic grouping, and " multiple " refer to each group to be had multiple.
According to specific embodiment of the invention scheme, preferably, in above-mentioned self-diverting acid liquid, the amphoterics with multiple hydrophilic radicals and hydrophobic grouping adopting is the acid amides amphoterics with two or three hydrophilic radicals and two or three hydrophobic groupings.
According to specific embodiment of the invention scheme, preferably, in above-mentioned self-diverting acid liquid, the amphoterics with multiple hydrophilic radicals and hydrophobic grouping adopting has suc as formula the structure shown in I:
In formula I: x is 2 or 3; R
1for the acyl group containing x-CO-group of total carbon number 24-54; R
2for the alkylidene group containing 2-5 carbon; R
3, R
4be independently respectively alkyl ,-CH containing 1-4 carbon
2cH
2cOO-or-CH
2cH
2oH; R
5for-CH
2-or-CH
2cH
2-.More preferably, the R adopting
1have suc as formula the structure shown in any in II-formula IV:
In above-mentioned formula II-formula IV, R
6for carbon chain lengths be 7 alkylidene group, R
7for carbon chain lengths be 5 alkylidene group, R
8for the carbon chain lengths alkylidene group that is 8.
According to specific embodiment of the invention scheme, preferably, in above-mentioned self-diverting acid liquid, the amphoterics with multiple hydrophilic radicals and hydrophobic grouping adopting comprises one or more the combination in following amphoterics:
DIBT: the amido propyl betaine (acid amides shown in formula II, III) that what total carbon number was 36 contain two hydrophilic group and two hydrophobic groupings;
TDIBT: the mixture of what total carbon number was 36 the amido propyl betaine that contains two hydrophilic group and two hydrophobic groupings and the amido propyl betaine that contains three hydrophilic radicals and three hydrophobic groupings that always carbon number is 54, the content ratio of the two is 1: 99-99: 1, preferably, the content of the two is respectively 80wt% and 20wt%, and (it can be the mixture of the acid amides shown in formula II, III, IV, wherein, the acid amides shown in formula II, III is isomer);
TIBT: the amido propyl betaine that contains three hydrophilic radicals and three hydrophobic groupings (acid amides shown in formula IV) that total carbon number is 54.
According to specific embodiment of the invention scheme; preferably; in above-mentioned self-diverting acid liquid; the anion surfactant adopting comprises oleic acid acyl group N-methyltaurine sodium (its structure is suc as formula shown in V) and/or sodium alkyl benzene sulfonate etc.; and the alkyl of described sodium alkyl benzene sulfonate is straight chained alkyl or the branched-chain alkyl that contains 8-18 carbon.
According to specific embodiment of the invention scheme, preferably, in above-mentioned self-diverting acid liquid, the amphoterics with multiple hydrophilic radicals and hydrophobic grouping prepares in accordance with the following methods: starting acid is reacted with organic amine, more further react the amphoterics described in synthetic obtaining with multiple hydrophilic radicals and hydrophobic grouping with sodium chloroacetate.
Poly lipid acid is industrialization product, also can be obtained by unsaturated fatty acids acid-respons with reference to the record in US Patent No. 5001260, US6187903, and structure I I, III are possible isomer.Dimer (fatty acid) yl and the mol ratio amine of 1: 2 reacts and can generate diamide, same principle, and three polyglycerol fatty acids and the mol ratio amine of 1: 3 reacts and can generate triamide.Multiamide can further form betaine type promoting agent with carboxylic radical reaction.
Above-mentioned self-diverting acid liquid provided by the present invention can be that amphoterics and anion surfactant, the mixed in hydrochloric acid preparation with multiple hydrophilic radicals and hydrophobic grouping are obtained, and it is a kind of viscoelastic surfactant self-diverting acid liquid.
The present invention also provides the application of above-mentioned self-diverting acid liquid in oil-gas field volume increase acidifying.
The present invention also provides a kind of oil-gas field souring method, and it is the method that uses above-mentioned self-diverting acid liquid the Oil/gas Well of oil-gas field to be carried out to acidifying.
Self-diverting acid liquid provided by the present invention is a kind of surfactant system, also can be used as foam self-diverting acidization and uses.
The same with other general acidizing treatment, in the time using self-diverting acid agent provided by the invention, can also add the compositions such as inhibiter, non-emulsifier, Fe stabilizer, complexing agent, these compositions can be determined according to prior art.Self-diverting acid liquid provided by the present invention, to iron ion sensitivity, can use iron reducer and complexing agent to do spearhead and process; Also can do spearhead with mutual solvent, spearhead comprises small molecules amount fat, ether, alcohol etc.All right compatible a small amount of non-emulsifier in this self-diverting acid liquid, to prevent the generation of emulsification and sludge.
Self-diverting acid liquid provided by the present invention is a kind of well behaved acidizing fluid, and it has obvious visco-elasticity in lower concentration solutions, is that a kind of good tensio-active agent acidifying pressure break turns to thickening material.
Embodiment
Understand for technical characterictic of the present invention, object and beneficial effect being had more clearly, existing technical scheme of the present invention is carried out to following detailed description, but can not be interpreted as restriction that can practical range of the present invention.
Embodiment 1 is synthetic containing the octadecyl acid amides propylene diamine amphoterics of two or three hydrophilic radicals and two or three hydrophobic groupings
1, synthetic containing the octadecyl acid amides propylene diamine amphoterics of two hydrophilic group and two hydrophobic groupings, it comprises the following steps:
Synthesizing of dimerization octadecyl acid amides:
Get 100g high-purity dimeric acid (containing the dimerization stearic acid of > 95wt%, C36) join the N of 38.3g, N-dimethyl-1, in 3-propylene diamine (0.38mol), mix and be heated to 160-180 DEG C of reaction 3-8 hour, distill the water that reaction generates; Reaction proceeds to acid number and is less than at 6 o'clock and finishes, and unnecessary N is removed in distillation, N-dimethyl-1, and 3-propylene diamine, obtains diprotic acid acid amides propylene diamine intermediate (being dimerization octadecyl acid amides);
15.7g sodium chloroacetate (0.135mol) is joined in 137ml water, Hybrid Heating to 80 DEG C, then add 50g dimerization octadecyl acid amides, at 70-80 DEG C of reaction 4-6 hour, in the time that the mass percentage content of NaCl reaches theoretical 98%, react complete, obtain the product of approximately 30% active matter content, contain the beet alkalescence amphoterics (DIBT) of two hydrophilic group and two hydrophobic groupings, what obtain by above-mentioned reaction is the mixture of the compound of structure representative below, and final product structure dimer may be homologue:
2, synthetic containing the octadecyl acid amides propylene diamine amphoterics of three hydrophilic radicals and three hydrophobic groupings, it comprises the following steps:
Synthesizing of trimerization octadecyl acid amides:
Get common dimeracid (containing the trimerization stearic acid of dimerization stearic acid, C36 and the 20wt% of 80wt%, the mixture of C54) 100g and join the N of 38.3g, N-dimethyl-1, in 3-propylene diamine (0.38mol), mix and be heated to 160-180 DEG C of reaction 3-8 hour, distill the water that reaction generates; Reaction proceeds to acid number and is less than at 6 o'clock and finishes, and unnecessary N is removed in distillation, N-dimethyl-1, and 3-propylene diamine, obtains triprotic acid acid amides propylene diamine intermediate (being trimerization octadecyl acid amides);
15.7g sodium chloroacetate (0.135mol) is joined in 137ml water, Hybrid Heating to 80 DEG C, then add the mixture of 50g dimerization octadecyl acid amides and trimerization octadecyl acid amides, at 70-80 DEG C of reaction 4-6 hour, in the time that the mass percentage content of NaCl reaches theoretical 98%, react complete, obtain the product of approximately 30% active matter content, contain the beet alkalescence amphoterics (TDIBT) of three hydrophilic radicals and three hydrophobic groupings, the content of compound and the content of starting acid of the structure representative are below consistent, when starting acid is pure a certain acid, here the product that obtained is also pure a certain compound, specifically can prepare as required.
Embodiment 2
On Haake RS600 rheometer, the viscosity of the self-diverting acid liquid of the different compositions of test.
The code name of different chemical structures is as follows:
The amido propyl betaine that contains two hydrophilic radicals and two hydrophobic groupings (acid amides shown in formula II, III, prepared by embodiment 1) of DIBT:C36;
The mixture (mixture of the acid amides shown in formula II, III, IV, prepared by embodiment 1) of the amido propyl betaine that contains three hydrophilic groups and three hydrophobic groups of the acyl propyl trimethyl-glycine that contains two hydrophilic of the C36 of TDIBT:80wt% and the C54 of 20wt%;
OBT: strand stearoyl amido CAB (Shanghai Nuo Song Industrial Co., Ltd.);
Anion surfactant:
OT: oleic acid acyl group N-methyltaurine sodium;
ABS: Sodium dodecylbenzene sulfonate.
Concrete test procedure:
Different amphoterics (DIBT, TDIBT, OBT) is mixed respectively from different anion surfactants (ABS, OT), be then dissolved in the CaCl that concentration is 24wt%
2in solution, obtain simulating the reacted generation of self-diverting acid liquid and carbonic acid rock stratum CaCl
2composition, it is 4 that its pH value is controlled, in self-diverting acid liquid, the active quantities of amphoterics is 1.80wt%, the content of anion surfactant is 0.35wt%;
Under the velocity of shear of 1001/s, at 80 DEG C, measure and after self-diverting acid liquid reacts with carbonatite, form CaCl
2after condition: reaction formula is HCl (acid solution)+CaCO
3(carbonatite) → CaCl
2+ CO
2+ H
2o.Viscosity test result is as shown in table 1.
Table 1 viscosity test result (unit is mPas)
| ? | Mix with ABS | Mix with OT |
| DIBT | 139 | 150 |
| TDIBT | 162 | 180 |
| OBT | 102 | 128 |
Content by table 1 can be found out, relatively general strand amphoterics, acts under lower concentration and can obtain high viscosity colloid containing the amphoterics of two, three hydrophilic radicals and two, three hydrophobic groupings and anion surfactant.
Embodiment 3
Different amphoterics (DIBT, TDIBT, OBT) is mixed respectively from different anion surfactants (ABS, OT), then being dissolved in concentration is in the HCl solution of 20wt%, obtain self-diverting acid liquid, its pH value < 1, in self-diverting acid liquid, the active quantities of amphoterics is 1.80wt%, and the content of anion surfactant is 0.35wt%;
Under the velocity of shear of 100l/s, test respectively the viscosity of self-diverting acid liquid at 20 DEG C, 80 DEG C, concrete test result is as shown in table 2.
Table 2 viscosity test result (unit is mPas)
| ? | 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 |
Viscosity test result by table 2 can be found out, in acid fluid system, solution (i.e. the mixture of the tensio-active agent shown in table 2 and the mixing solutions of HCl) viscosity is very low, and can find out according to the data in table 1, self-diverting acid liquid reacts the situation that there will be gelling solution viscosity to increase after salt and pH raise that produces with carbonic acid rock, this explanation adopt self-diverting acid liquid of the present invention can reach liquid rotating to object.
Claims (8)
1. a self-diverting acid liquid, taking the gross weight of this self-diverting acid liquid as benchmark, it has following one-tenth and is grouped into: there is the amphoterics 0.1-10% of multiple hydrophilic radicals and hydrophobic grouping, and anion surfactant 0.1-2%, surplus is the hydrochloric acid of concentration 3-28wt%;
The amphoterics wherein, with multiple hydrophilic radicals and hydrophobic grouping is the acid amides amphoterics with two or three hydrophilic radicals and two or three hydrophobic groupings.
2. self-diverting acid liquid according to claim 1, wherein, described in there is multiple hydrophilic radicals and hydrophobic grouping amphoterics have suc as formula the structure shown in I:
In formula I: x is 2 or 3; R
1for the acyl group containing x-CO-group of total carbon number 24-54; R
2for the alkylidene group containing 2-5 carbon; R
3, R
4be independently respectively alkyl ,-CH containing 1-4 carbon
2cH
2cOO-or-CH
2cH
2oH; R
5for-CH
2-or-CH
2cH
2-.
3. self-diverting acid liquid according to claim 2, wherein, described R
1have suc as formula the structure shown in any in II-formula IV:
In above-mentioned formula II-formula IV, R
6for carbon chain lengths be 7 alkylidene group, R
7for carbon chain lengths be 5 alkylidene group, R
8for the carbon chain lengths alkylidene group that is 8.
4. according to the self-diverting acid liquid described in claim 1-3 any one, wherein, described in there is multiple hydrophilic radicals and hydrophobic grouping amphoterics comprise one or more the combination in following amphoterics:
The amido propyl betaine that what total carbon number was 36 contain two hydrophilic group and two hydrophobic groupings;
The mixture of what total carbon number was 36 the amido propyl betaine that contains two hydrophilic group and two hydrophobic groupings and the amido propyl betaine that contains three hydrophilic radicals and three hydrophobic groupings that always carbon number is 54, the content ratio of the two is 99: 1 to 1: 99;
The amido propyl betaine that contains three hydrophilic radicals and three hydrophobic groupings that total carbon number is 54.
5. according to the self-diverting acid liquid described in claim 1-4 any one; wherein; described anion surfactant comprises oleic acid acyl group N-methyltaurine sodium and/or sodium alkyl benzene sulfonate, and the alkyl of described sodium alkyl benzene sulfonate is straight chained alkyl or the branched-chain alkyl that contains 8-18 carbon.
6. according to the self-diverting acid liquid described in claim 1-4 any one, wherein, described in there is multiple hydrophilic radicals and hydrophobic grouping amphoterics prepare in accordance with the following methods:
Starting acid is reacted with organic amine, more further react the amphoterics described in synthetic obtaining with multiple hydrophilic radicals and hydrophobic grouping with sodium chloroacetate.
7. the application of the self-diverting acid liquid described in claim 1-6 any one in oil-gas field volume increase acidifying.
8. an oil-gas field souring method is wherein the method that right to use requires the self-diverting acid liquid described in 1-6 any one the Oil/gas Well of oil-gas field to be carried out to acidifying.
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| CN104927832A (en) * | 2014-10-30 | 2015-09-23 | 中国石油大学(华东) | Self-diverting acid for acidifying modification of heterogeneous reservoir |
| CN107216865A (en) * | 2017-06-08 | 2017-09-29 | 中海石油伊拉克有限公司 | A kind of low damage acidifying solution and its preparation method and application |
| CN108467724A (en) * | 2018-03-12 | 2018-08-31 | 中国石油天然气股份有限公司 | A kind of online shunting acid and preparation method thereof that water injection well is continuously injected into |
| CN110591685A (en) * | 2019-09-16 | 2019-12-20 | 西安石油大学 | In-situ self-generated microfoam steering acidizing fluid, acidizing steering method and application |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104927832A (en) * | 2014-10-30 | 2015-09-23 | 中国石油大学(华东) | Self-diverting acid for acidifying modification of heterogeneous reservoir |
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| CN107216865A (en) * | 2017-06-08 | 2017-09-29 | 中海石油伊拉克有限公司 | A kind of low damage acidifying solution and its preparation method and application |
| CN108467724A (en) * | 2018-03-12 | 2018-08-31 | 中国石油天然气股份有限公司 | A kind of online shunting acid and preparation method thereof that water injection well is continuously injected into |
| US10961442B2 (en) | 2018-03-12 | 2021-03-30 | Petrochina Company Limited | On-line diverting acid for continuous injection into water injection wells and a preparation method thereof |
| CN110591685A (en) * | 2019-09-16 | 2019-12-20 | 西安石油大学 | In-situ self-generated microfoam steering acidizing fluid, acidizing steering method and application |
| 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 |
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| Publication number | Publication date |
|---|---|
| CN104073236B (en) | 2017-03-08 |
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