CN109294551A - A kind of cleaning low damage agent of molecular cluster and its application - Google Patents
A kind of cleaning low damage agent of molecular cluster and its application Download PDFInfo
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- CN109294551A CN109294551A CN201811216469.3A CN201811216469A CN109294551A CN 109294551 A CN109294551 A CN 109294551A CN 201811216469 A CN201811216469 A CN 201811216469A CN 109294551 A CN109294551 A CN 109294551A
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- 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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Abstract
The invention discloses a kind of cleaning low damage agent of molecular cluster and its applications in oil well acidation, additionally provide a kind of novel molecular cluster cleaning self-diverting acid.To solve the problems, such as that low damage agent in the prior art only rises to 4 or more in pH value, could form highly viscous gel under the increased collective effect of calcium ion concentration；The rear no scrap problems of broken glue are solved simultaneously.Molecular cluster provided by the present invention cleans low damage agent, and composition is simple, can turn in real time to stratum；It is not limited by acid solution type, is not also limited by acid strength；Molecular cluster can be achieved in different acid fluid systems and clean low damage.
Description
Technical field
The application belongs to technical field of petrochemical industry, cleans low damage agent in particular to a kind of molecular cluster and its answers
With.
Background technique
During the synthetic jobs such as oil drilling and complete well process and long-term production, there are different degrees of oil reservoir damages
Evil, mainly has the filtrates such as 1, mud, cement slurry and particle to formation leakage, causes the damage of reservoir；2, since formation rock can
There can be " five is quick ", i.e., it is acid-sensitive, salt is quick, alkali is quick, water-sensitive, speed are quick etc..3, since formation water salinity is high, heavy constituent glue in crude oil
Matter asphalt content is high, causes the heavy constituent near wellbore zone fouling and crude oil to deposit, seriously affects oil well output and water injection well
Injection rate.For this purpose, to the reservoir reconstruction and to reservoir solution depollution of being hurt, to improve crude output, acidification be important means it
One.
With the development of oil field development technology, the long well sections oil well such as directional well, horizontal well is more and more.It is non-due to reservoir
Homogenieity and intrinsic fracture exist, and the flow direction for injecting formation fluid can advance by leaps and bounds in high permeability zone and crack.And middle less permeable layer
Acidizing effect is not had, makes to be acidified efficiency reduction.Particularly with horizontal well, acidification is through separating the different layers on stratum frequently with tool
Section, greatly increases operating cost, removes tool and also brings risk to operation (such as tool salvages difficulty).For this purpose, to long well section
Acidification uses steering technique, and by the way that diversion agent is added, according to the minimum principle of pressure in injection process, diversion agent preferentially enters stratum
These layer of position is temporarily blocked up in high permeability zone and crack, is made less permeable layer in subsequent acid solution entrance, is reached the mesh of uniform acid distribution
's.This method can solve the problems, such as long well section grease well acidizing.
Initial acidified diverting agent is solid particle, can be divided into oil-soluble particle and water-soluble granular, using particle in height
Permeable interval forms filter cake by the blocking of macropore bridge formation or pore throat surface, makes acid solution not and can enter these intervals, to turn
To.But such bad control of diversion agent dosage, and will not be completely dissolved, new pollution, formation damage can be generated to stratum
Greatly.
To overcome such disadvantage, viscous acid is developed, i.e., acidproof high-molecular compound is added into acid solution, improves acid solution
Viscosity.Using the toughness of acid solution, achieve the purpose that acid solution turns to.Thickening agent in viscous acid is water soluble polymer, is existed
Two big disadvantages cause the row of returning difficult, the row's of returning low efficiency first is that viscous fluid is trapped in stratum and crack.Influence the infiltration on stratum
Saturating rate.Second is that polymer forms filter cake in the earth formation, the interstitial space on stratum and crack is blocked, reduces in-place permeability and crack
Flow conductivity.
Cross-linked acid is acidproof high-molecular compound to be added in acid solution, while crosslinking agent is added, and hands over high-molecular compound
Connection forms space network, forms frozen glue.The viscosity of the frozen glue is far longer than viscous acid.Acid solution is carried out using its viscosity to turn
To.It completes after turning to, the frozen glue of formation needs brokenly glue.But often break glue and be not thorough, injury is generated to stratum.
Visco-elastic surfactant acid developed in recent years is a kind of novel acid fluid system of non-polymer class, it is by viscoelastic surface
Activating agent is added in acid solution, spherical (or rodlike) micella is originally formed, when acid strength gradually decreases, in acid solution corrosion stratum
Carbonate (dirt), generates a large amount of Ca2+Ion, in Ca2+Under ionization, spherical (or rodlike) micella is changed into vermiform glue
Beam is mutually wound, and generates viscoelastic colloidal, and viscosity increases significantly, and row temporarily blocks up when can be to high permeability zone, realizes that the steering of acid solution is temporary
Stifled effect.Completed with acid-rock reaction, pH value rises to 4 or more, under the increased collective effect of calcium ion concentration, vermiculate glues to
Globular micelle converts and breaks glue automatically.The hydrocarbons (such as crude oil, natural gas) in stratum are such as encountered, broken glue will be accelerated.
When above cleaning self-diverting acid can be seen that the cleaning low damage dosage form of addition into memory fluid, need several
A condition: 1, it after forming micella, needs in calcium chloride (CaCl2) interact therewith, can just have sufficiently high viscosity (it is general >=
400mPa.s)；It 2, is the highest turning point of viscosity when the acid strength in acid fluid system reaches pH value range.And it is being acidified
In, when acid solution hydrogen ion concentration reaches pH grades, concentration is at a fairly low, is not easy to realize in acidization.3, diversion agent glue is generated
Group needs brokenly glue, and broken glue is not thorough.Also new damage can be generated to stratum.
Summary of the invention
The main purpose of the application be to provide a kind of novel molecular cluster cleaning low damage agent and its in oil well acidation
Application, additionally provide a kind of novel molecular cluster cleaning self-diverting acid.To solve low damage agent in the prior art only in pH value
The problem of rising to 4 or more, highly viscous gel could be formed under the increased collective effect of calcium ion concentration；Broken glue is solved simultaneously
Rear no scrap problems.
To achieve the goals above, this application provides a kind of molecular clusters to clean low damage agent.
The component and content of the molecular cluster cleaning low damage agent are as follows:
Specifically, the surfactant is Shuangzi hexadecyltrimethylammonium chloride, Shuangzi dodecyl dimethyl
Benzyl ammonium chloride, empgen BB, dodecyldimethyl ammonium oxide, dodecyl trimethyl ammonium bromide octadecyl two
One or more of ethoxy amine oxide, cocoanut fatty acid diethanolamide.
Specifically, the cosurfactant are as follows: one or more of glycerine, ethylene glycol, n-butanol.
Specifically, the network interpenetrating agent are as follows: to be chelated made from polyethylene polyamine and transition metal element ferrous iron
Object.Further, it selects along safe energy science and technology Development Co., Ltd product HA-2, SH-3, WT-1.
Present invention also provides a kind of application methods of molecular cluster cleaning low damage agent, and above-mentioned molecular cluster is cleaned rotation
It is acidified to agent, forms acid fluid system, be added in the oil reservoir for needing to turn to.PH value remains less than 4 in application process.
Specifically, insulating liquid need to be added in acidization, the insulating liquid includes sodium-chloride water solution, potassium chloride
The one or more combination of aqueous solution, ammonia chloride water solution.The concentration of the insulating liquid is 2~5% (mass concentrations).
The additional amount of diversion agent is added according to the formation temperature of required steering and the strong and weak of heterogeneity, usual every rice bran oil
Layer is added molecular cluster and cleans 10~50kg of self-diverting acid diversion agent.
Present invention also provides a kind of molecular clusters to clean self-diverting acid, and the molecular cluster cleaning self-diverting acid is mainly by upper
What the molecular cluster cleaning low damage agent stated and acid solution formed, the acid solution includes: main body acid solution, acidification corrosion inhibitor, additive.
Specifically, the main body acid solution is hydrochloric acid, mud acid, sulfamic acid, MH acid, small molecular organic acid etc..
Specifically, the additive is ferrous stability, clay swell agent, cleanup additive.
The utility model has the advantages that molecular cluster provided by the present invention cleans low damage agent, composition is simple；Stratum can be turned in real time
To.
Molecular cluster cleaning low damage agent of the invention is not limited by acid solution type, is not also limited by acid strength.?
Different acid fluid systems can be achieved molecular cluster and clean low damage.
Molecular cluster cleaning self-diverting acid of the invention is not limited by the calcium ion concentration in water flooding, and molecular cluster cleaning is certainly
Diversion agent and acid solution meet and can form gel, realize that acid solution turns to；Calcium is needed when turning to different from current cleaning self-diverting acid
Ion participates in forming micelle, could turn to.
Molecular cluster in the present invention cleans self-diverting acid, can carry out acid solution steering in arbitrary period.Gel is formed when steering
Intensity controlled (amount that diversion agent is added is bigger, and it is bigger to form gel strength).
Molecular cluster of the invention cleans self-diverting acid, after steering forms gel, the molecule of the surfactant molecule of formation
Cluster.It is soluble in water, the aqueous solution containing surfactant, no residue are equivalent to after dissolution.To stratum fanout free region.Due to molten
It is aqueous surfactant solution after solution, reduces the surface tension and interfacial tension of water, increases the water conservancy diversion of formation fluid in the earth formation
Ability, " Jamin effect " of the generation for overcoming fluid to flow in formation pore.
Specific embodiment
In order to make those skilled in the art more fully understand application scheme, below in conjunction with the specific implementation of the application
Example, the technical scheme in the embodiment of the application is clearly and completely described, it is clear that described embodiment is only this
Apply for the embodiment of a part, instead of all the embodiments.
Embodiment 1
Molecular cluster cleans low damage agent, formula are as follows: 60 parts of Shuangzi hexadecyltrimethylammonium chlorides, 15 parts of glycerine, 1 part
Network interpenetrating agent, 24 parts of water.The network interpenetrating agent is to chelate made from polyethylene polyamine and transition metal element ferrous iron
Object (specific to select along safe energy science and technology Development Co., Ltd product HA-2).
Acid solution 500ml sour based on hydrochloric acid is prepared, wherein concentration of hydrochloric acid is 10%, and hydrochloric acid density of corrosion inhibitor 1% glues
Native expansion-resisting agent 2%, ferrous stability 1%.
50ml molecular cluster is added into acid solution and cleans low damage agent.Gel is generated in acid solution immediately.Its viscosity is greater than
1000mPa.s.It is taken out from acid solution and generates micelle, weighing, quality 102g.It will be impregnated in micelle add-back acid solution.In static shape
Under state, be completely dissolved within 3 hours, acid solution without it is muddy, without precipitating.Illustrate that there is good broken colloidality.Acid solution is measured using hanging ring method
Surface tension and interfacial tension: the surface tension of acid solution be 31mN.m-1；Interfacial tension is 1.1mN.m-1.Illustrate that molecular cluster is clear
Clean low damage agent is not limited when turning to by acid strength, and high surface activity.
Embodiment 2
Molecular cluster cleans low damage agent, formula are as follows: 50 parts of dodecyldimethyl ammonium oxide and empgen BB
Mixture, 15 parts of ethylene glycol, 1 part of network interpenetrating agent, 34 parts of water.The network interpenetrating agent is with polyethylene polyamine and transition metal
Chelate made from element ferrous iron (specific to select along safe energy science and technology Development Co., Ltd product SH-3).
Acid solution 500ml sour based on sulfamic acid is prepared, wherein sulfamic acid concentration is 10%, density of corrosion inhibitor
1%, anti-clayswelling agent 1%, ferrous stability 0.5%.
50ml molecular cluster is added into acid solution and cleans low damage agent.Gel is generated in acid solution immediately.Its viscosity is greater than
1000mPa.s.It is taken out from acid solution and generates micelle, weighing, quality 112g.It will be impregnated in micelle add-back acid solution.In static shape
Under state, be completely dissolved within 3 hours, acid solution without it is muddy, without precipitating.Illustrate that there is good broken colloidality.Acid solution is measured using hanging ring method
Surface tension and interfacial tension: the surface tension of acid solution be 30mN.m-1；Interfacial tension is 1.4mN.m-1.Illustrate that molecular cluster is clear
Clean low damage agent is suitable for different acid solutions, is not limited by acid strength.And high surface activity.
Embodiment 3~7
The formula of 3~embodiment of embodiment 7, it is substantially the same manner as Example 1, the difference is that, the surface-active
Agent replace with respectively Shuangzi dodecyl benzyl dimethyl ammonium chloride, empgen BB, dodecyldimethyl ammonium oxide,
Dodecyl trimethyl ammonium bromide octadecyl dihydroxy ethyl amine oxide, cocoanut fatty acid diethanolamide.
Embodiment 8~11
The formula of 8~embodiment of embodiment 11, it is substantially the same manner as Example 1, the difference is that, described helps surface living
Property agent replaces with the mixture of the mixture of ethylene glycol, n-butanol, ethylene glycol and glycerine, glycerine and n-butanol.
Embodiment 12~14
The formula of 12~embodiment of embodiment 14, it is substantially the same manner as Example 2, the difference is that, the surface is living
Property agent replaces with the mixture of empgen BB and dodecyldimethyl ammonium oxide, trimethyl bromination respectively
The mixture of ammonium octadecyl dihydroxy ethyl amine oxide and cocoanut fatty acid diethanolamide, Shuangzi dodecyl dimethyl benzyl
The mixture of ammonium chloride and Shuangzi hexadecyltrimethylammonium chloride.
Embodiment 15~18
The formula of 15~embodiment of embodiment 18, it is substantially the same manner as Example 2, the difference is that, described helps surface
Activating agent replaces with the mixture of the mixture of glycerine, n-butanol, ethylene glycol and glycerine, glycerine and n-butanol.
Concrete application of the invention:
According to formation temperature, core intersection, formation rock property and stratum liquid property design acid fluid system, dosage.And
The dosage of design cleaning low damage agent.
Acidification technique process are as follows: acidification prepad fluid is acidified working solution.When working solution is added according to the heterogeneous of stratum
Property, cleaning low damage agent is added in the length of well section.The cleaning of 50-200kg molecular cluster generally is added certainly to the every rice bran oil layer of high permeability zone
Diversion agent.After completion working solution has been infused, displacement fluid is finally injected.Acid filling finishes.Closing well.
Diversion agent adding manner.When first segment turns to are as follows: when calculating acidification working solution has been filled with pit shaft, that is, inject first
Section diversion agent.It injects before molecular cluster cleaning low damage agent.Inject 2m3-3m3The aqueous solution one of sodium chloride, potassium chloride or ammonium chloride
Kind.Acid solution and molecular cluster cleaning low damage agent is isolated.Injection first segment molecular cluster cleans low damage agent later.After having infused, then
Inject insulating liquid 2m3-3m3The aqueous solution of sodium chloride, potassium chloride or ammonium chloride is a kind of.
Continue injection acidification working solution, observe the variation of injection pressure, if injection pressure rises, then continues to inject acid solution.
It is long to be such as acidified well section, molecular cluster cleaning low damage agent injecting program is reinjected according to design and is same as above.
After completing acidification, according to formation temperature and injection length, the closed-in time is determined.To prevent acid solution from generating secondary damage
Evil.Shorten the closed-in time as far as possible.
After the completion of closing well, drive a well work of resuming production.
Embodiment 19
Mode is acidified using oil pipe to 6 mouthfuls of wells (stratum Mishrif), acidization application molecular cluster cleans low damage agent.
Complete whole self-spray, goes into operation successfully after acidification；Entirely reach or be more than expected production capacity, 2 mouthfuls of well skin factors of test be 3.91 and-
1.554.Wherein, it goes into operation after the complete well of certain well M258, yield is 874bbl/d before being acidified, and is 4185bbl/d, volume increase after acidification
3311bbl/d, effect are the most obvious.
Acidification corrosion inhibitor, ferrous stability, anti-clayswelling agent, cleanup additive is added in the acid solution based on hydrochloric acid.With obtained
The acid solution arrived, concentration 15%.
Work progress: injecting pit shaft for acid solution, when having been filled with pit shaft, records injection pressure.Inject 2~3m310%
Sodium-chloride water solution is then injected into the cleaning low damage agent of first segment molecular cluster, at this point, the acid in acid solution removes and occurs with response of stratum
Outside corrosion, acid strength of the acid in liquid is far longer than pH range.After molecular cluster cleaning low damage agent has been infused, 2~3m is reinjected3
10% sodium-chloride water solution, continue inject acid solution, observe the variation of injection pressure, injection pressure obviously rises, and explanation plays
Steering-effecting.Continue to inject acid solution.When pressure injection decline in injection process, segment molecule cluster cleaning low damage is reinjected
Agent；One section of sodium chloride insulating liquid is squeezed into injection front and back.After reinject acid solution.After infusing acid solution, working solution is replaced with for setting liquid
Enter stratum closing well 4 hours, that is, drives a well and reproduce.
Certain oil field self-diverting acid Acidizing Technology well example is cleaned using molecular cluster
Complete whole self-spray, goes into operation successfully after acidification；It entirely reaches or more than expected production capacity, 2 mouthfuls of well skin factors of test
It is 3.91 and -1.554.Wherein, it goes into operation after the complete well of certain well M258, yield is 874bbl/d before being acidified, and is after acidification
4185bbl/d, increases production 3311bbl/d, and effect is the most obvious.
Embodiment 20
Basic step is identical as embodiment 19, and difference is, main body acid solution small molecular organic acid (formic acid, acetic acid, propionic acid
Mixture) obtained acid solution is prepared, anti-sensitizer is added simultaneously in concentration 10%: ferrous stability 0.5%, anti-clayswelling agent
1%.
In certain oil field oil recovery factory horizontal well construction, 270 meters of extended horizontal depth, it is acidified using coiled tubing.In order to make acid
Liquid more evenly enters stratum, takes three sections of injection modes.I.e. oil pipe elder generation tripping in horizontal segment end inject 1/3 blockages relieving fluid, then on
It mentions and injects 1/3 blockages relieving fluid in the middle part of tubing string to horizontal segment, finally last 1/3 blockages relieving fluid is injected in upper lifting pipe post to horizontal segment root again.
Main body acid solution dosage 220m3。
When every section of injection, two segment molecule clusters are added and clean low damage agent.Every section is added 50 kilograms；Front and back is added to squeeze into respectively
2% potassium chloride insulating liquid, 3 side.Every time after injection molecular cluster cleaning low damage agent, injection pressure averagely rises 3-4MPa.Full well is total
It injects molecular cluster and cleans 300 kilograms of low damage agent.Full well acidizing shares 18 hours.
Initial stage increases day by day liquid 13.5t, the oily 12.6t that increases day by day (73 days)；Validity period increases day by day liquid 3.7t, and increase day by day oily 3t, adds up to increase oil
1010t。
For the above embodiment of the present invention, alkaline matter is not added in the whole process, pH value is respectively less than 4.
Claims (10)
1. a kind of molecular cluster cleans low damage agent, which is characterized in that the component and content of the molecular cluster cleaning low damage agent
Are as follows:
2. molecular cluster according to claim 1 cleans low damage agent, which is characterized in that the surfactant is Shuangzi
Hexadecyltrimethylammonium chloride, Shuangzi dodecyl benzyl dimethyl ammonium chloride, empgen BB, dimethyl
Base amine-oxides, dodecyl trimethyl ammonium bromide octadecyl dihydroxy ethyl amine oxide, in cocoanut fatty acid diethanolamide
One or more.
3. molecular cluster according to claim 1 cleans low damage agent, which is characterized in that the cosurfactant are as follows:
One or more of glycerine, ethylene glycol, n-butanol.
4. molecular cluster according to claim 1 cleans low damage agent, which is characterized in that the network interpenetrating agent are as follows: with
Chelate made from polyethylene polyamine and transition metal element ferrous iron.
5. a kind of application method of molecular cluster cleaning low damage agent, which is characterized in that clean molecular cluster described in claim 1
Low damage agent acidification, forms acid fluid system, is added in the oil reservoir for needing to turn to.
6. application method according to claim 5, which is characterized in that in acidization, insulating liquid need to be added, it is described
Insulating liquid include sodium-chloride water solution, potassium chloride solution, ammonia chloride water solution one or more combination.
7. application method according to claim 6, the concentration of the insulating liquid is 2~5%.
8. a kind of molecular cluster cleans self-diverting acid, which is characterized in that the molecular cluster cleaning self-diverting acid is mainly wanted by right
What diversion agent described in asking 1 and acid solution formed, the acid solution includes: main body acid solution, acidification corrosion inhibitor, additive.
9. molecular cluster according to claim 8 cleans self-diverting acid, which is characterized in that the main body acid solution be hydrochloric acid,
Mud acid, sulfamic acid, MH acid, small molecular organic acid.
10. molecular cluster according to claim 8 cleans self-diverting acid, which is characterized in that the additive is iron ion
Stabilizer, clay swell agent, cleanup additive.
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| CN110358514A (en) * | 2019-07-02 | 2019-10-22 | 中国石油天然气股份有限公司 | A kind of accumulation type water solubility diverting agent and preparation method thereof |
| CN110564398A (en) * | 2019-09-23 | 2019-12-13 | 西南石油大学 | Retarded acid system |
| CN111778009A (en) * | 2020-07-10 | 2020-10-16 | 陕西华天能源科技有限公司 | Composite steering micelle acid acidification de-plugging liquid and preparation method thereof |
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