CN106281273B - It is a kind of for being acidified the acid fluid system of carbonate reservoir - Google Patents
It is a kind of for being acidified the acid fluid system of carbonate reservoir Download PDFInfo
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- CN106281273B CN106281273B CN201510250296.7A CN201510250296A CN106281273B CN 106281273 B CN106281273 B CN 106281273B CN 201510250296 A CN201510250296 A CN 201510250296A CN 106281273 B CN106281273 B CN 106281273B
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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
- C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
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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
- C09K2208/32—Anticorrosion additives
Abstract
The invention discloses a kind of for being acidified the acid fluid system of carbonate reservoir, belongs to petrochemical industry.The acid fluid system includes the component of following mass percentage: the sulfamic acid of 10%-50%, 10%-50% urea nitrate, the organic monoacid of 3%-15%, the cosolvent of 0.1%-5%, 0.1%-2% corrosion inhibiter, surplus is water.Acid fluid system provided by the invention has the advantages that corrosion rate is high, the increasing degree of corrosion rate is big, corrosion rate is low etc..In addition, acid fluid system formula provided in an embodiment of the present invention is simple, the contained each component source of goods is wide, and convenient transportation is low in cost, more conducively scale site operation application.
Description
Technical field
It is the present invention relates to petrochemical industry, in particular to a kind of for being acidified the acid fluid system of carbonate reservoir.
Background technique
Acidification is the Main Yield-increasing measure of carbonate reservoir, and method is exactly by injecting acid solution, dissolution storage to stratum
The substance that reservoir is blocked during layer rock mineral composition and drilling well, complete well, well workover, oil producing operation, improves reservoir
Permeance property, to improve Oil & Gas Productivity.It generallys use hydrochloric acid and (Wang Desheng, modern oil is acidified to carbonate reservoir
Hide fracture acidizing mining novel technology application manual, Beijing petroleum industry publishing house, 2006), in acidization, hydrochloric acid and carbonic acid
Rock salt is swift in response, and effectively corrosion carbonate rock mineral and can generate great amount of carbon dioxide gas in the short time, and acid solution is anti-when arranging
Generate sufficiently large back pressure.However, oil-gas Layer temperature gradually rises, carbonate reservoir as oil-gas mining is seted out to deep-well
Hydrochloric acid acidification be faced with following problems: (1) reservoir temperature is high, and reservoir temperature is usually between 80 DEG C -90 DEG C.This is easy to make salt
Acid plus carbonate rock is swift in response, so that a large amount of acid solutions are depleted in nearly well location, corrosion rate increasing degree reduces, acid solution
It is difficult to penetrate reservoir deeper part injury area.Therefore, under the high temperature conditions, hydrochloric acid acidification is difficult to realize the depth of carbonate reservoir
Degree acidification.(2) bottom hole temperature (BHT) is high, so that acid solution be caused to aggravate the corrosion of down-hole string and equipment, down-hole string and equipment make
With reduced lifetime, maintenance replacement cost is increased considerably.
In order to solve the above-mentioned technical problem, CN102399550A discloses a kind of for high temperature carbonate rock deep acidizing
Liquid formulations, Applicable temperature is 60 DEG C -150 DEG C, by mass percentage, by the organic ester of 10%-50%, the halogen of 0-50%
Sour series, or mixtures thereof the formaldehyde of the ammonium halide of 0-45%, 0-50%, 0.1%-5% surfactant form.The liquid is matched
[H can be discharged by adjusting+]=2.2mol/L-4mol/L is lauched solution in 60 DEG C of -150 DEG C of temperature conditions and generates H+, with control
Acid solution rate of release solves the rate of the reaction of high temperature carbonate rock reservoir between 0.5h-6h, realizes deep acidizing.
The inventor finds that the existing technology has at least the following problems:
The acid system higher cost that the prior art provides, it is difficult to scale site operation application.
Summary of the invention
The technical problem to be solved by the embodiment of the invention is that provide a kind of low cost for being acidified carbonate rock
The acid fluid system of reservoir.Specific technical solution is as follows:
It is a kind of for being acidified the acid fluid system of carbonate reservoir, the component including following mass percentage: 10%-
50% sulfamic acid, 10%-50% urea nitrate, the organic monoacid of 3%-15%, the cosolvent of 0.1%-5%, 0.1%-2%
Corrosion inhibiter, surplus is water.
Preferably, the acid fluid system includes the component of following mass percentage: the sulfamic acid of 15%-30%,
15%-30% urea nitrate, the organic monoacid of 5%-12%, the cosolvent of 0.5%-5%, 0.4%-1.5% corrosion inhibiter, surplus
For water.
Specifically, the organic monoacid is formic acid and/or acetic acid.
Specifically, the cosolvent is made of the first cosolvent and the second cosolvent；
First cosolvent is sodium chloride and/or potassium chloride；
Second cosolvent is selected from least one of ethyl alcohol, crude oil, diesel oil, condensate.
Specifically, the corrosion inhibiter is thiocarbamide corrosion inhibiter and/or imidazoline inhibitor.
Technical solution provided in an embodiment of the present invention has the benefit that
The acid fluid system provided in an embodiment of the present invention for being used to be acidified carbonate reservoir, passes through each component of said ratio
Between collaboration complex role, preparation-obtained acid fluid system has that corrosion rate is high, corrosion rate increasing degree is big, corrosion speed
The low advantage of rate.In particular, acid fluid system formula provided in an embodiment of the present invention is simple, and the contained each component source of goods is wide, transport
It is convenient, low in cost, more conducively scale site operation application.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, embodiment of the present invention will be made into one below
Step ground detailed description.
The embodiment of the invention provides a kind of for being acidified the acid fluid system of carbonate reservoir, including following quality percentage
The component of content: the sulfamic acid of 10%-50%, 10%-50% urea nitrate, the organic monoacid of 3%-15%, 0.1%-5%
The corrosion inhibiter of cosolvent, 0.1%-2%, surplus are water.
The acid fluid system provided in an embodiment of the present invention for being used to be acidified carbonate reservoir, passes through each component of said ratio
Between collaboration complex role, preparation-obtained acid fluid system has that corrosion rate is high, corrosion rate increasing degree is big, corrosion speed
The low advantage of rate, so that the corruption to down-hole string and equipment can be effectively reduced in acid fluid system while realizing deep acidizing again
Erosion.In particular, acid fluid system formula provided in an embodiment of the present invention is simple, and the contained each component source of goods is wide, convenient transportation, cost
It is cheap, more conducively scale site operation application.
Specifically, acid fluid system provided in an embodiment of the present invention, under hot conditions (such as 70 DEG C -120 DEG C), to amino
It, will greatly due to common-ion effect when the lesser organic monoacid of dissociation constant being added in the mixed solution of sulfonic acid and urea nitrate
The degree of ionization for reducing organic monoacid promotes the mixed solution of sulfamic acid and urea nitrate mainly to play corrosion work near the borehole wall
With, and organic monoacid can remotely play corrosion on stratum.And in the process, acid solution can be effectively reduced in optional corrosion inhibiter
Corrosion rate of the system to down-hole string and equipment.Therefore, compared with hydrochloric acid, the acid fluid system is effectively improving corrosion rate
While increasing degree, the corrosion to down-hole string and equipment is also effectively reduced.
Inventor the study found that (1) with mass concentration be 15% hydrochloric acid compared with, acid solution body provided in an embodiment of the present invention
System can be improved 76% or more to the corrosion rate of In Carbonate Rock.(2) acid fluid system provided in an embodiment of the present invention can effectively improve
Corrosion rate increasing degree slows down acid-rock reaction rate, increases effective sour rock operating distance, to realize deep acidizing.In phase
With under acid-rock reaction time conditions, the corrosion rate increasing degree of acid fluid system provided in an embodiment of the present invention is that mass concentration is
5.9 times or more of 15% hydrochloric acid.(3) corrosion mitigating effect of acid fluid system provided in an embodiment of the present invention is obvious, in identical corrosion
Under time conditions, compared with mass concentration is 15% hydrochloric acid, the corrosion rate of acid fluid system provided in an embodiment of the present invention is only
Be 0.14% or so of hcl corrosion rate, corrosion mitigating effect be above " acidification corrosion inhibiter method for testing performance and evaluation refer to
Mark " (SY/T 5405-1996) first class index.(4) hydrochloric acid good to practical rock core correctional effect, being 15% with mass concentration
It compares, the acid fluid system that 1-4 of the embodiment of the present invention is provided is to the hydrochloric acid that the correctional effect of practical rock core is that mass concentration is 15%
2 times or more (5) acid fluid system provided in an embodiment of the present invention of correctional effect is low in cost, and the source of goods is wide, convenient transportation, to reservoir
Injure it is small, convenient for extensive live acidizing treatment application.
Preferably, the acid fluid system includes the component of following mass percentage: the sulfamic acid of 15%-30%,
15%-30% urea nitrate, the organic monoacid of 5%-12%, the cosolvent of 0.5%-5%, 0.4%-1.5% corrosion inhibiter, surplus
For water.
Under the premise of guaranteeing that the acid fluid system has excellent properties as above, in order to which its cost is effectively reduced, in order to it
Scale site operation application, preferably, the organic monoacid is formic acid and/or acetic acid；The cosolvent by the first cosolvent and
Second cosolvent composition；Wherein, the first cosolvent is sodium chloride and/or potassium chloride；Second cosolvent is selected from ethyl alcohol, crude oil, bavin
At least one of oil, condensate；The corrosion inhibiter is thiocarbamide corrosion inhibiter and/or imidazoline inhibitor.
Specifically, the preparation method of the acid fluid system is as follows: with the mass percentage of each component in acid fluid system
Meter sequentially adds the hydrotropy of the sulfamic acid of 10%-50%, 10%-50% urea nitrate, 0.1%-5% in a kettle first
After stirring 5min-30min at room temperature, organic monoacid, the 0.1%- of 3%-15% is successively added in agent into the reaction kettle
2% corrosion inhibiter and the water of surplus, after mixing evenly up to the acid fluid system.As it can be seen that acid provided in an embodiment of the present invention
The preparation method of liquid system is simple, easy to control, is conducive to large-scale industrial application.
In the embodiment of the present invention, room temperature can be understood as the arbitrary temp value between 10 DEG C -25 DEG C.
Hereinafter the present invention will be further described through by specific embodiment.
In following specific embodiments, condition person is not specified in related operation, according to normal conditions or manufacturer
It is recommended that condition carry out.It is raw materials used production firm is not specified and specification person be can be with conventional products that are commercially available.
Embodiment 1
It present embodiments provides a kind of for being acidified the acid fluid system of carbonate reservoir comprising following quality percentage contains
The component of amount: 19.8% sulfamic acid, 15.0% urea nitrate, 7.0% formic acid, 0.5% potassium chloride, 2.0% second
Alcohol, 0.5% imidazoline inhibitor and the water of surplus.
The preparation method of the acid fluid system is as follows:
According to the mass percentage of each component in acid fluid system, at room temperature first by sulfamic acid, urea nitrate, chlorination
Potassium, ethyl alcohol, which are placed in reaction kettle, stirs 10min, and formic acid, imidazoline inhibitor and water, stirring is then added into reaction kettle again
The acid fluid system of the present embodiment is obtained after uniformly.
Embodiment 2
It present embodiments provides a kind of for being acidified the acid fluid system of carbonate reservoir comprising following quality percentage contains
The component of amount: 21.0% sulfamic acid, 20.0% urea nitrate, 8.0% acetic acid, 1.5% sodium chloride, 2.0% original
Oil, 0.6% thiocarbamide corrosion inhibiter and the water of surplus.
The preparation method of the acid fluid system is as follows:
According to the mass percentage of each component in acid fluid system, at room temperature first by sulfamic acid, urea nitrate, chlorination
Sodium, crude oil, which are placed in reaction kettle, stirs 10min, and acetic acid, thiocarbamide corrosion inhibiter and water is then added into reaction kettle again, and stirring is equal
The acid fluid system of the present embodiment is obtained after even.
Embodiment 3
It present embodiments provides a kind of for being acidified the acid fluid system of carbonate reservoir comprising following quality percentage contains
The component of amount: 22.5% sulfamic acid, 16.0% urea nitrate, 5.5% acetic acid, 1.0% sodium chloride, 3.0% bavin
Oil, 0.8% imidazoline inhibitor and the water of surplus.
The preparation method of the acid fluid system is as follows:
According to the mass percentage of each component in acid fluid system, at room temperature first by sulfamic acid, urea nitrate, chlorination
Sodium, diesel oil, which are placed in reaction kettle, stirs 10min, and acetic acid, imidazoline inhibitor and water, stirring is then added into reaction kettle again
The acid fluid system of the present embodiment is obtained after uniformly.
Embodiment 4
It present embodiments provides a kind of for being acidified the acid fluid system of carbonate reservoir comprising following quality percentage contains
The component of amount: 30% sulfamic acid, 25.0% urea nitrate, 5.0% formic acid, 2.0% potassium chloride, 2.5% condensation
Oil, 1.0% thiocarbamide corrosion inhibiter and the water of surplus.
The preparation method of the acid fluid system is as follows:
According to the mass percentage of each component in acid fluid system, at room temperature first by sulfamic acid, urea nitrate, chlorination
Potassium, condensate, which are placed in reaction kettle, stirs 15min, and formic acid, thiocarbamide corrosion inhibiter and water, stirring is then added into reaction kettle again
The acid fluid system of the present embodiment is obtained after uniformly.
Embodiment 5
Under the conditions of 90 DEG C, under identical operating conditions, the present embodiment is utilized respectively the acid fluid system of embodiment 1-4 offer
And the hydrochloric acid solution that mass concentration is 15% carries out corrosion experiment, experiment to the rock core clast (landwaste) of the carbonate rock of acquisition
The results are shown in Table 1:
The acid fluid system that 1 hydrochloric acid of table and embodiment 1-4 are provided is under the different acid-rock reaction times to the corrosion rate of landwaste
| The acid-rock reaction time (min) | 10 | 30 | 60 | 90 | 120 | 180 | 240 |
| Corrosion rate (%) of the hydrochloric acid to landwaste | 63.95 | 64.03 | 64.27 | 64.51 | 64.67 | 64.86 | 65.32 |
| Corrosion rate (%) of 1 acid fluid system of embodiment to landwaste | 41.78 | 43.28 | 45.95 | 47.84 | 49.11 | 49.24 | 49.89 |
| Corrosion rate (%) of 2 acid fluid system of embodiment to landwaste | 42.46 | 45.86 | 47.52 | 48.95 | 49.68 | 50.34 | 50.73 |
| Corrosion rate (%) of 3 acid fluid system of embodiment to landwaste | 43.87 | 47.34 | 49.07 | 49.89 | 51.64 | 52.32 | 52.62 |
| Corrosion rate (%) of 4 acid fluid system of embodiment to landwaste | 45.34 | 48.56 | 50.22 | 50.96 | 52.41 | 53.88 | 54.19 |
As shown in Table 1, it under the conditions of at a temperature of 90 °C, is provided with the extension of acid-rock reaction time, embodiment 1-4
The hydrochloric acid that acid fluid system and mass concentration are 15% increases the corrosion rate of landwaste.And the acid-rock reaction time is in 10min-
When 240min, the hydrochloric acid that mass concentration is 15% is smaller to the corrosion rate increasing degree of landwaste, and corrosion rate only increases by 1.37%；And
Embodiment 1-4 provide acid fluid system to the corrosion rate increasing degree of landwaste more than 8.11%, the increasing degree of corrosion rate
It is 5.9 times or more of the hydrochloric acid that mass concentration is 15%.As it can be seen that 1-4 of the embodiment of the present invention provide acid fluid system show it is bright
Aobvious slow effect, in same acids rock reaction time range, the acid fluid system that embodiment 1-4 is provided can effectively improve this explanation
Corrosion rate increasing degree slows down acid-rock reaction rate, increases sour rock EFFECTIVE RANGE, to realize deep acidizing.Meanwhile this
When the acid-rock reaction time for the acid fluid system that inventive embodiments 1-4 is provided is 240min, corrosion rate can reach mass concentration
It is 76% or more of the corrosion rate of 15% hydrochloric acid solution, live acidizing treatment demand can be met.
Embodiment 6
Under conditions of temperature is 90 DEG C, etching time is 240min, under identical operating conditions, the present embodiment is sharp respectively
The average corrosion rate of N80 steel disc is carried out with the hydrochloric acid that the embodiment 1-4 acid fluid system provided and mass concentration are 15%
Test, test result are as shown in table 2:
Average corrosion rate of the acid fluid system that 2 hydrochloric acid of table and embodiment 1-4 are provided to N80 steel disc
As shown in Table 2, the acid fluid system that embodiment 1-4 is provided is respectively less than 2g/ to the average corrosion rate of N80 steel disc
(m2H), average corrosion rate is only 0.14% or so of the hydrochloric acid solution average corrosion rate that mass concentration is 15%, far
Far below the average corrosion rate of the hydrochloric acid solution.As it can be seen that the corrosion mitigating effect for the acid fluid system that 1-4 of the embodiment of the present invention is provided is bright
It is aobvious, and its corrosion mitigating effect is above " oil field acidification corrosion inhibitor test method and evaluation index " (Q/SY XJ0041-2001)
(its corrosion rate is 3g/ (m to first class index2·h)-4g/(m2H)), this illustrates the acid solution body that 1-4 of the embodiment of the present invention is provided
The corrosion rate of down-hole string and equipment can be effectively reduced in system, extend the service life of down-hole string and equipment, reduce maintenance more
Change this into.
Embodiment 7
Under the same operating conditions, the present embodiment be utilized respectively embodiment 1-4 offer acid fluid system and quality it is dense
Degree has carried out acidification transformation, acidification transformation to the rock core of same type of several actual carbonate reservoirs for 15% hydrochloric acid
The permeability variation of front and back, rock core is as shown in table 3.
The acid fluid system that 3 hydrochloric acid of table and embodiment 1-4 are provided carries out acidification transformation front and back, the permeability of rock core to rock core
As shown in Table 3, although the hydrochloric acid that acid fluid system and mass concentration that 1-4 of the embodiment of the present invention is provided are 15% is to reality
Border core permeability has preferable correctional effect, but the acid fluid system that 1-4 of the embodiment of the present invention is provided changes practical rock core
Make the 2 times or more that effect is the hydrochloric acid that mass concentration is 15%.This illustrates the acid fluid system of 1-4 of embodiment of the present invention offer to reality
The correctional effect of border core permeability is substantially better than the hydrochloric acid that mass concentration is 15%, and also the embodiment of the present invention will be further explained for this
The deep acidizing of carbonate reservoir may be implemented in the acid fluid system that 1-4 is provided.
In addition, find during the experiment, after the acid fluid system that 1-4 of the embodiment of the present invention is provided is mixed with water flooding, nothing
Precipitating generates, this illustrates that acid fluid system and water flooding compatibility provided in an embodiment of the present invention are good, small to reservoir damage, is conducive to
Large-scale industrial application.
The foregoing is merely presently preferred embodiments of the present invention, the protection scope being not intended to limit the invention, all in this hair
Within bright spirit and principle, any modification, equivalent replacement, improvement and so on should be included in protection scope of the present invention
Within.
Claims (2)
1. it is a kind of for being acidified the acid fluid system of carbonate reservoir, it is grouped as by the group of following mass percentage: 15%-
50% sulfamic acid, the urea nitrate of 10%-50%, the organic monoacid of 5%-12%, 0.1%-5% cosolvent, 0.1%-
2% corrosion inhibiter, surplus are water,
The cosolvent is made of the first cosolvent and the second cosolvent；
First cosolvent is sodium chloride and/or potassium chloride；
Second cosolvent is selected from least one of ethyl alcohol, crude oil, diesel oil, condensate；
The corrosion inhibiter is thiocarbamide corrosion inhibiter and/or imidazoline inhibitor；
The organic monoacid is formic acid and/or acetic acid.
2. acid fluid system according to claim 1, which is characterized in that the acid fluid system includes following mass percentage
Component: the sulfamic acid of 15%-30%, 15%-30% urea nitrate, the organic monoacid of 5%-12%, 0.5%-5% hydrotropy
Agent, 0.4%-1.5% corrosion inhibiter, surplus is water.
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| CN109021950B (en) * | 2018-09-27 | 2021-06-01 | 陕西友邦石油工程技术有限公司 | Solid chelating acid for increasing injection of water injection well and preparation method thereof |
| CN116877042B (en) * | 2023-07-12 | 2023-12-19 | 大庆井升伟业油田技术服务有限公司 | Clean acidification process suitable for improving oil well yield |
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| CN1583716A (en) * | 2004-06-14 | 2005-02-23 | 陕西福奥特实业有限公司 | Preparing method for inactive nitric acid powder |
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