CN107325806A - A kind of visco-elastic surfactant acid liquid system of the quaternary ammonium alkyl of base containing erucic acid salt surfactant - Google Patents
A kind of visco-elastic surfactant acid liquid system of the quaternary ammonium alkyl of base containing erucic acid salt surfactant Download PDFInfo
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- 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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- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/24—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfuric acids
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- 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
- C09K8/602—Compositions for stimulating production by acting on the underground formation containing surfactants
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Abstract
The present invention is intended to provide a kind of cost is relatively low, visco-elastic surfactant acid liquid system with high temperature high voltage resistant performance.In order to solve the above technical problems, the present invention is achieved through the following technical solutions：A kind of visco-elastic surfactant acid liquid system of the quaternary ammonium alkyl of base containing erucic acid salt surfactant, including erucic acid base quaternary ammonium alkyl salt surfactant, the acid solution being made up of at least one inorganic acid or organic acid, ferrous stability and corrosion inhibiter.Erucic acid base quaternary ammonium alkyl salt surfactant is low molecule viscoelastic surfactant, and no residue does not form filter cake, small to formation contaminant, can improve effective flow conductivity of crack.It is not required to gel breaker (meet oil or water breaks glue) and broken glue is thoroughly, the raffinate easily row of returning.Frictional resistance is low, only the 30~40% of water, and operational discharge capacity range of choice is big, and the requirement of different process transformation can be achieved.Good filtrate reducing characteristic and retardative property, can increase considerably acid-etched fracture length.
Description
Technical field
It is used for HTHP stratum the present invention relates to oil gas field acid fracturing stimulation work technical field, more particularly to one kind
The visco-elastic surfactant acid liquid system of the quaternary ammonium alkyl salt surfactant of base containing erucic acid of acid fracturing stimulation work.
Background technology
Acid fracturing be higher than under formation fracture pressure with acid solution as fracturing fluid, be not added with the pressure break of proppant.
During acid fracturing by acid solution corrosion by the wall corrosion in crack into rough surface, so as to after termination of pumping release, split
Slotted wall face will not be closed completely, and with higher flow conductivity, to recovering and improving capacity of oilwell, effect is obvious.
Acidifying can effectively release the pollution and blocking of near wellbore zone oil reservoir, and raising pit shaft is logical near wellbore zone reservoir
Property, increase oil well productivity.The flowing of acid solution follows minimum impedance concept, and to preferentially enter permeability preferable for acid solution in acidization
Reservoir.In the stronger reservoir of anisotropism, most of acid solution, which enters middle and high permeable formation, only small part acid solution, not to be had even
There is acid solution to enter less permeable layer, this is not only difficult to reservoir homogeneous acidification, increases the purpose of oil well productivity, and storage can be made on the contrary
The anisotropism of layer is further enhanced, and increases exploitation difficulty.
The content of the invention
The present invention is intended to provide a kind of cost is relatively low, the alkyl quaternary ammonium salts of base containing erucic acid surface with high temperature high voltage resistant performance
The visco-elastic surfactant acid liquid system of activating agent.
In order to solve the above technical problems, the present invention is achieved through the following technical solutions：
A kind of visco-elastic surfactant acid liquid system of the quaternary ammonium alkyl of base containing erucic acid salt surfactant, including：
(1) erucic acid base quaternary ammonium alkyl salt surfactant；
(2) acid solution being made up of at least one inorganic acid or organic acid；
(3) ferrous stability；
(4) corrosion inhibiter.
Further, the structure formula (I) of erucic acid base quaternary ammonium alkyl salt surfactant is：
Further, the preparation process of the erucic acid base quaternary ammonium alkyl salt surfactant is：
A, erucyl amide synthesis：
By N, N- dimethyl -1,3- propane diamine and erucic acid are put into reactor, are added catalyst, are warming up to 100 DEG C -130
DEG C, 3-5h is reacted, 170-190 DEG C is then to slowly warm up to, the heating-up time is 1.9-2.1h, final reaction 17-19h, obtains mustard
Sour acid amides；Reaction is such as formula (II)：
B, erucic acid base quaternary ammonium alkyl salt surfactant synthesis：
Under the conditions of 60-80 DEG C, the erucyl amide obtained by step a is used into dimethyl sulfate methylation of ester, erucic acid base is obtained
Quaternary ammonium alkyl salt surfactant.Reaction is such as formula (III)：
Further, the pH in reactor, and pH are adjusted using sodium hydroxide in step b>7.
Further, catalyst described in step a is phosphorous acid.
Further, the mol ratio of N, N- dimethyl -1,3- propane diamine and erucic acid is 1:1；Erucyl amide and dimethyl suflfate
Mol ratio is 1:1.
Further, acid solution includes any one in hydrochloric acid, mud acid, MH acid, hydrofluoric acid, fluoboric acid, nitric acid and acetic acid
Or it is several.
Further, erucic acid base quaternary ammonium alkyl salt surfactant accounts for 0.2- in visco-elastic surfactant acid liquid system according to quality
8%.
Further, ferrous stability accounts for 1-3% in visco-elastic surfactant acid liquid system according to quality.
Further, corrosion inhibiter accounts for 1-6% in visco-elastic surfactant acid liquid system according to quality.
Compared with prior art it is an advantage of the invention that：
1) erucic acid base quaternary ammonium alkyl salt surfactant is low molecule viscoelastic surfactant, and no residue does not form filter
Cake, it is small to formation contaminant, effective flow conductivity of crack can be improved.
2) it is not required to gel breaker (meet oil or water breaks glue) and broken glue is thoroughly, the raffinate easily row of returning.
3) frictional resistance is low, only the 30~40% of water, and operational discharge capacity range of choice is big, and wanting for different process transformation can be achieved
Ask.
4) good filtrate reducing characteristic and retardative property, can increase considerably acid-etched fracture length.
5) liquid dosage is simple, and scene does not need excessive equipment, it is not necessary to which crosslinking agent, gel breaker, constructing operation are simple.
4) the visco-elastic surfactant acid liquid system construction operation obtained by the present invention is convenient, can meet well depth more than 6000m, temperature surpasses
Cross the acid fracturing operation on 200 DEG C of HTHP stratum.
Embodiment
A kind of visco-elastic surfactant acid liquid system of the quaternary ammonium alkyl of base containing erucic acid salt surfactant, including：
(1) erucic acid base quaternary ammonium alkyl salt surfactant；Erucic acid base quaternary ammonium alkyl salt surfactant is in visco-elastic surfactant acid
In liquid system 0.2-8% is accounted for according to quality.
(2) acid solution being made up of at least one inorganic acid or organic acid；Acid solution includes hydrochloric acid, mud acid, MH acid, hydrogen fluorine
Any one or a few in acid, fluoboric acid, nitric acid and acetic acid.
(3) ferrous stability；Ferrous stability accounts for 1-3% in visco-elastic surfactant acid liquid system according to quality.Iron from
The Main Ingredients and Appearance of sub- stabilizer is organic acid and its salt.With the effect for preventing Fe3+ depositing damages stratum, ferrous stability
Can be from complexing, the reprecipitation for reducing, disperseing prevention Fe3+ in terms of three.
(4) corrosion inhibiter；Corrosion inhibiter accounts for 1-6% in visco-elastic surfactant acid liquid system according to quality.
Wherein, the structure formula (I) of erucic acid base quaternary ammonium alkyl salt surfactant is：
The preparation process of erucic acid base quaternary ammonium alkyl salt surfactant is：
A, erucyl amide synthesis：
By N, N- dimethyl -1,3- propane diamine and erucic acid are put into reactor, N, N- dimethyl -1,3- propane diamine and erucic acid
Mol ratio be 1:1 (weight ratio about 720：230) catalyst phosphorous acid, is added, 100 DEG C -130 DEG C are warming up to, 3-5h is reacted, with
After be to slowly warm up to 170-190 DEG C, the heating-up time is 1.9-2.1h, final reaction 17-19h, obtains erucyl amide；Specific reaction
Formula such as formula (II)：
B, new erucic acid base quaternary ammonium alkyl salt surfactant synthesis：Under the conditions of 60-80 DEG C, by obtained by step a
Erucyl amide uses dimethyl sulfate methylation of ester, and erucyl amide and dimethyl suflfate mol ratio are 1:1 (weight ratio about 920：
250) erucic acid base quaternary ammonium alkyl salt surfactant, is obtained.PH in reactor, and pH are adjusted using sodium hydroxide>7.Specifically
Reaction equation such as formula (III)：
Acid filling friction pressure can be greatly lowered in the present invention, delay acid-rock reaction speed；Acid liquid loss can be greatly lowered
Speed, the advantages of improving acid etching EFFECTIVE RANGE and acidizing effect.Cracked furthermore it is also possible to take sand branch during acid fracturing
Seam, improves fracture condudtiviy.System viscosity when with liquid is relatively low, when viscoelastic surfactant enters In Carbonate Rock
When, with the progress of acid-rock reaction, acid concentration constantly declines, and the pH value rise and the concentration increase of chlorion of solution make viscoplasticity
Viscoelastic surfactant long rod-like molecules in fluid are transformed into the vermiculate glues for mutually twining and being woven in together, and viscosity drastically increases
Greatly, at this moment high viscosity fluid just temporarily serves the effect of barrier, and remaining low-permeability process layer is given divided fluid stream.Cleaning
The automatic viscosity for changing acid solution of acid is turned to, it is achieved thereby that the uniform cloth of heterogeneous reservoir (long net horizontal section or long open hole well section)
Acid, has reached the purpose of reservoir homogeneous acidification.Visco-elastic surfactant acid system has that turning function is good, slow, filtrate loss controllability is good, into
This is low, to stratum fanout free region the features such as.
With reference to experiment, the present invention will be further described：
Experiment one：
The visco-elastic surfactant acid liquid system of the quaternary ammonium alkyl salt surfactant of base containing erucic acid, visco-elastic surfactant acid liquid system is according to matter
It is steady that amount includes 20%HCL, 6%VES (new erucic acid base quaternary ammonium alkyl salt surfactant), 4.5% corrosion inhibiter and 2% iron ion
Determine agent, remaining is water.
The sour viscosity for the visco-elastic surfactant acid prepared according to aforementioned proportion is 35mPa.s, then adds calcium carbonate powder and cleaning
Acid reaction is turned to, when reaction to concentration of hydrochloric acid is less than 10%, visco-elastic surfactant acid viscosity is 115mPa.s；Continue plus Paris white
End is reacted with visco-elastic surfactant acid, and when reaction to concentration of hydrochloric acid is 5%, visco-elastic surfactant acid viscosity is 125mPa.s, finally when anti-
When should be less than 1% to concentration of hydrochloric acid, visco-elastic surfactant acid viscosity is reduced to 8mPa.s.
Experiment two：
In X1 well field experiments：Depth of reservoirs：Nearly 6000m, temperature：190℃.
The visco-elastic surfactant acid liquid system of the quaternary ammonium alkyl salt surfactant of base containing erucic acid, according to quality include 15%HCL,
5%VES, 4.5% corrosion inhibiter and 2% ferrous stability, remaining is water.
When using identical infusion discharge capacity during construction, infusion guanidine gum fracturing fluid is than infusion visco-elastic surfactant acid liquid system
When pressure it is about high 8~10 MPas, illustrate that the sour frictional ratio guanidine gum fracturing fluid of cleaning is low by 15% or so.The well is cleaned to turn to sour acid fracturing
Volume increase is more than 30 times of guanidine gum fracturing fluid after transformation.
Experiment three：
In X2 well field experiments：Depth of reservoirs：Nearly 3000m, temperature：90℃.
The visco-elastic surfactant acid liquid system of the quaternary ammonium alkyl salt surfactant of base containing erucic acid, according to quality include 25%HCL,
5%VES, 3% corrosion inhibiter and 1% ferrous stability, remaining is water.
The process of the well construction, as acid solution is gradually reacted with formation rock, in the case where discharge capacity is stable, construction pump pressure
There is up-trend；Illustrate as the progress of acid-rock reaction, the reduction of acid strength, acid liquid viscosity increases automatically, cleaning acid solution rises
The effect turned to has been arrived, has been conducive to the uniform transformation of heterogeneous reservoir, the ability of the potential volume increase of reservoir can be given full play to.The Bowl
After acidfracturing treatment, increase production 23 times.
In summary, the visco-elastic surfactant acid liquid system of the quaternary ammonium alkyl salt surfactant of base containing erucic acid of the invention has excellent
Delay acid-rock reaction speed ability and turning function, can effectively prevent acid solution to hypertonic part occur fingering, improve acid
Operating distance is lost, and the migration of the clay minerals illite etc. can be suppressed, permanently effective fracture condudtiviy is kept.Also simultaneously
With excellent heatproof, anti-shearing and low friction performance, well depth can be met more than 6000m, HTHP of the temperature more than 200 DEG C
The acid fracturing operation of layer.Field experiment shows the visco-elastic surfactant acid system acid with the quaternary ammonium alkyl salt surfactant of base containing erucic acid
Pressing element has significant effect of increasing production.The visco-elastic surfactant acid system of the quaternary ammonium alkyl salt surfactant of base containing erucic acid is tested at the scene
With application more than 100 Kou Bowl, significant effect of increasing production is achieved.
The specific embodiment of the present invention is the foregoing is only, but the technical characteristic of the present invention is not limited thereto, Ren Heben
The technical staff in field is in the field of the invention, and the change or modification made all are covered among the scope of the claims of the present invention.
Claims (10)
1. a kind of visco-elastic surfactant acid liquid system of the quaternary ammonium alkyl of base containing erucic acid salt surfactant, it is characterised in that including：
(1) erucic acid base quaternary ammonium alkyl salt surfactant；
(2) acid solution being made up of at least one inorganic acid or organic acid；
(3) ferrous stability；
(4) corrosion inhibiter.
2. a kind of visco-elastic surfactant acid liquid system of the quaternary ammonium alkyl of base containing erucic acid salt surfactant according to claim 1,
Characterized in that, the structure formula (I) of erucic acid base quaternary ammonium alkyl salt surfactant is：
3. a kind of visco-elastic surfactant acid liquid system of the quaternary ammonium alkyl of base containing erucic acid salt surfactant according to claim 2,
Characterized in that, the preparation process of the erucic acid base quaternary ammonium alkyl salt surfactant is：
A, erucyl amide synthesis：
By N, N- dimethyl -1,3- propane diamine and erucic acid are put into reactor, are added catalyst, are warming up to 100 DEG C -130 DEG C, instead
3-5h is answered, 170-190 DEG C is then to slowly warm up to, the heating-up time is 1.9-2.1h, final reaction 17-19h, obtains erucic acid acyl
Amine；Reaction is such as formula (II)：
B, new erucic acid base quaternary ammonium alkyl salt surfactant synthesis：
Under the conditions of 60-80 DEG C, the erucyl amide obtained by step a is used into dimethyl sulfate methylation of ester, erucic acid base alkyl is obtained
Quaternary surfactant；Reaction is such as formula (III)：
4. a kind of visco-elastic surfactant acid liquid system of the quaternary ammonium alkyl of base containing erucic acid salt surfactant according to claim 3,
Characterized in that, adjusting the pH in reactor, and pH using sodium hydroxide in step b>7.
5. a kind of visco-elastic surfactant acid liquid system of the quaternary ammonium alkyl of base containing erucic acid salt surfactant according to claim 3,
Characterized in that, catalyst described in step a is phosphorous acid.
6. the visco-elastic surfactant acid liquid system of the quaternary ammonium alkyl salt surfactant of base containing erucic acid as described in right 3, it is characterised in that
The mol ratio of N, N- dimethyl -1,3- propane diamine and erucic acid is 1:1；Erucyl amide and dimethyl suflfate mol ratio are 1:1.
7. the visco-elastic surfactant acid liquid system of the quaternary ammonium alkyl salt surfactant of base containing erucic acid according to right 1, its feature exists
In acid solution includes any one or a few in hydrochloric acid, mud acid, MH acid, hydrofluoric acid, fluoboric acid, nitric acid and acetic acid.
8. the visco-elastic surfactant acid liquid system of the quaternary ammonium alkyl salt surfactant of base containing erucic acid according to right 1, its feature exists
In erucic acid base quaternary ammonium alkyl salt surfactant accounts for 0.2-8% in visco-elastic surfactant acid liquid system according to quality.
9. the visco-elastic surfactant acid liquid system of the quaternary ammonium alkyl salt surfactant of base containing erucic acid according to right 1, its feature exists
In ferrous stability accounts for 1-3% in visco-elastic surfactant acid liquid system according to quality.
10. the visco-elastic surfactant acid liquid system of the quaternary ammonium alkyl salt surfactant of base containing erucic acid as described in right 1, its feature exists
In corrosion inhibiter accounts for 1-6% in visco-elastic surfactant acid liquid system according to quality.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108102633A (en) * | 2017-11-17 | 2018-06-01 | 中国石油天然气股份有限公司 | A kind of viscoplasticity acid-base fracturing fluid and preparation method thereof |
| CN108191694A (en) * | 2018-01-08 | 2018-06-22 | 西南石油大学 | A kind of Shuangzi zwitterionic surfactant and preparation method thereof and the steering acid prepared using surfactant |
| CN108837772A (en) * | 2018-06-25 | 2018-11-20 | 江南大学 | Dimeric surfactant worm-like micelle systems with pH response |
| CN110439527A (en) * | 2019-07-18 | 2019-11-12 | 西南石油大学 | A kind of carbonate reservoir presses method from drop acid filtering |
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| CN102395348A (en) * | 2009-02-27 | 2012-03-28 | 拜尔斯道夫股份有限公司 | Use of charged surfactants to reduce fabric staining by antiperspirants |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108102633A (en) * | 2017-11-17 | 2018-06-01 | 中国石油天然气股份有限公司 | A kind of viscoplasticity acid-base fracturing fluid and preparation method thereof |
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| CN108191694A (en) * | 2018-01-08 | 2018-06-22 | 西南石油大学 | A kind of Shuangzi zwitterionic surfactant and preparation method thereof and the steering acid prepared using surfactant |
| CN108837772A (en) * | 2018-06-25 | 2018-11-20 | 江南大学 | Dimeric surfactant worm-like micelle systems with pH response |
| CN110439527A (en) * | 2019-07-18 | 2019-11-12 | 西南石油大学 | A kind of carbonate reservoir presses method from drop acid filtering |
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Effective date of registration: 20210125 Address after: 100010 16 ande Road, Dongcheng District, Beijing Patentee after: PetroChina Co.,Ltd. Patentee after: Chengdu Mingya Technology Co.,Ltd. Patentee after: Zhang Shaonan Patentee after: Lu Yuan Patentee after: Hu Ming Address before: 610000 Jiepai village, Qingliu Town, Xindu District, Chengdu City, Sichuan Province Patentee before: Chengdu Mingya Technology Co.,Ltd. Patentee before: LANGFANG BRANCH INSTITUTE OF RESEARCH INSTITUTE OF PETROLEUM EXPLORATION & DEVELOPMENT OF PETROCHINA Co.,Ltd. Patentee before: Zhang Shaonan Patentee before: Lu Yuan Patentee before: Hu Ming |