CN113881413B - Acidizing fluid for preventing generation of hydrogen sulfide - Google Patents

Acidizing fluid for preventing generation of hydrogen sulfide Download PDF

Info

Publication number
CN113881413B
CN113881413B CN202111173475.7A CN202111173475A CN113881413B CN 113881413 B CN113881413 B CN 113881413B CN 202111173475 A CN202111173475 A CN 202111173475A CN 113881413 B CN113881413 B CN 113881413B
Authority
CN
China
Prior art keywords
inhibitor
parts
acidizing fluid
stirring
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202111173475.7A
Other languages
Chinese (zh)
Other versions
CN113881413A (en
Inventor
李明
石国新
宫兆波
罗强
唐可
白雷
李织宏
王凤清
曹强
刘佳幸
李凯
林莉莉
张旭阳
田辉
贺代兰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Petrochina Co Ltd
Original Assignee
Petrochina Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Petrochina Co Ltd filed Critical Petrochina Co Ltd
Priority to CN202111173475.7A priority Critical patent/CN113881413B/en
Publication of CN113881413A publication Critical patent/CN113881413A/en
Application granted granted Critical
Publication of CN113881413B publication Critical patent/CN113881413B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
    • C09K8/528—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning inorganic depositions, e.g. sulfates or carbonates
    • C09K8/532—Sulfur
    • 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
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH DRILLING; MINING
    • E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/25—Methods for stimulating production
    • E21B43/26—Methods for stimulating production by forming crevices or fractures
    • E21B43/27—Methods for stimulating production by forming crevices or fractures by use of eroding chemicals, e.g. acids
    • 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
    • C09K2208/12—Swell inhibition, i.e. using additives to drilling or well treatment fluids for inhibiting clay or shale swelling or disintegrating
    • 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
    • C09K2208/20—Hydrogen sulfide elimination
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

The invention belongs to the field of oilfield chemistry, and particularly relates to an acidizing fluid for preventing hydrogen sulfide generation, which specifically comprises the following components in parts by weight: 10-20 parts of hydrochloric acid, 1-5 parts of corrosion inhibitor, 3-10 parts of antiscale agent, 0.5-5 parts of clay stabilizer and 0.1-1 part of inhibitor. The preparation method comprises the steps of adding hydrochloric acid into water, stirring, heating to 85-95 ℃, adding the corrosion inhibitor, and mixing; then regulating the temperature to 50-60 ℃, and sequentially adding the scale inhibitor and the clay stabilizer for mixing; and finally adding an inhibitor, stirring and dispersing uniformly to obtain the product. The acidizing fluid for preventing the generation of the hydrogen sulfide provided by the invention has good compatibility with the oil field well entering fluid, and the acidizing effect is ensured; meanwhile, the hydrogen sulfide gas can be controlled from the source, and the safety of site construction is guaranteed.

Description

Acidizing fluid for preventing generation of hydrogen sulfide
Technical Field
The invention belongs to the field of oilfield chemistry, and particularly relates to an acidizing fluid for preventing hydrogen sulfide generation.
Background
The hydrogen sulfide associated with a certain concentration in the production process of the oil-gas field is colorless and extremely toxic gas with odor of eggs, and can form weak acid which has strong corrosion and destruction effects on metal materials after being dissolved in water, thereby easily causing damages such as breaking of a pipe column in an oil well, corrosion of a wellhead metal device and a ground pipeline and the like. In recent years, the oil and gas industry is vigorously developed, the workload of exploration wells and production wells is continuously increased, and meanwhile, a large amount of hydrogen sulfide is likely to be generated in the processes of conveying, processing, using and the like of oil and gas, so that the danger of oil and gas production is undoubtedly increased. Moreover, people often inhale a small amount of high-concentration hydrogen sulfide, so that the danger of death is caused in a short time; under the condition of low concentration, the medicine also has certain influence on eyes, respiratory system and central nerve of human body.
The Sinkiang oil field Marhu tight oil reservoir has the characteristics of extremely low permeability of a reservoir layer, poor permeability, no natural productivity of a single well or low natural productivity lower than the lower limit of industrial oil flow, quick energy attenuation and the like, so that the key for realizing benefit exploitation is to implement high-efficiency acidizing fracturing reformation by adopting a horizontal well volume fracturing technology, but hydrogen sulfide with the concentration of 20-1000ppm is generated at a well mouth accounting for about 63% of the fracturing operation, and the damage is very strong.
At present, the formation mechanism of hydrogen sulfide is generally considered by scholars at home and abroad to be mainly divided into 4 types of acid rock reaction cause, biological cause, thermal chemical cause and magma cause. The thermal chemical cause and the magma cause both need high temperature of more than 120 ℃, the biological cause needs less than 50 ℃, and the temperature of most strata in a Xinjiang Marhu tight oil reservoir test area is 90 DEG CLeft and right. Research shows that a large amount of sulfides exist in stratum sediments of a Xinjiang Ma lake tight oil reservoir, and part of the sulfides exist in the form of AVS (acid volatile sulfur), such as amorphous FeS, sulfides of divalent metals (Ni, Pb, Zn and the like) and pyrite (Fe) 3 S 4 ) And markenoite and the like. So that the acidizing fluid entering the well reacts with AVS in the stratum sediment to generate hydrogen sulfide in the process of implementing efficient acidizing fracturing reformation in the test area. Therefore, the elimination of hydrogen sulfide generated during acid fracturing is particularly important.
The Chinese patent application CN201610524427.0 discloses a composite desulfurizer and a preparation method thereof, wherein a complex iron salt desulfurizer in purified natural gas hydrogen sulfide is adopted to desulfurize inorganic sulfur and organic sulfur produced in an oil field, so that a strong effect is achieved; the Chinese invention patent application CN201410115684.X discloses a filling mining method for preventing spontaneous combustion of coal seams containing coal mines and removing hydrogen sulfide, which is to spray liquid foam with functions of removing hydrogen sulfide and flame retardance on the coal seams, wherein the liquid foam consists of a hydrogen sulfide alkaline absorbent, an inorganic salt inhibitor, a composite foaming agent, an auxiliary agent and water, so that the harmful gas hydrogen sulfide in the coal mines can be removed, and the spontaneous combustion of coal can be prevented. However, the above two inventions can exert the effect only under the alkaline condition; the Chinese patent application CN201310256989.8 discloses a desulfurizer and a preparation method thereof, wherein the desulfurizer has high sulfur capacity, can remove hydrogen sulfide and other sulfides produced on the oil field with high precision, but has poor compatibility with acidizing fluid entering the oil field and stratum, and can not inhibit the generation of the hydrogen sulfide from the root.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the acidizing fluid for preventing the generation of the hydrogen sulfide, which has good compatibility with the well fluid of the oil field and ensures the acidizing effect; meanwhile, the hydrogen sulfide gas can be controlled from the source, and the safety of site construction is guaranteed.
The purpose of the invention is realized by the following technical scheme:
an acidizing fluid for preventing hydrogen sulfide generation comprises the following components in parts by weight: 10-20 parts of hydrochloric acid, 1-5 parts of corrosion inhibitor, 3-10 parts of antiscale agent, 0.5-5 parts of clay stabilizer and 0.1-1 part of inhibitor.
Preferably, the inhibitor is a mixture of potassium persulfate, sodium persulfate, ammonium persulfate and graphene;
preferably, the anti-scaling agent is a mixture of fatty alcohol ether sulfosuccinic acid, polyepoxysuccinic acid, hydroxypropyl acrylate copolymer and polymethacrylic acid.
Preferably, the acidizing fluid comprises the following components in parts by weight: 13-18 parts of hydrochloric acid, 1-5 parts of corrosion inhibitor, 5-8 parts of antiscale agent, 0.5-2 parts of clay stabilizer and 0.2-1 part of inhibitor.
Preferably, the composition further comprises water.
Preferably, the inhibitor is a mixture of potassium persulfate, sodium persulfate, ammonium persulfate and graphene in a mass ratio of 0.5-1:1:2-4: 0.1-0.5.
Preferably, the corrosion inhibitor consists of SDSH quaternary ammonium salt corrosion inhibitor and urotropin in the mass ratio of 1-3: 0.5-1.
Preferably, the antiscalant is a mixture of fatty alcohol ether sulfosuccinic acid, polyepoxysuccinic acid, hydroxypropyl acrylate copolymer and polymethacrylic acid in a mass ratio of 1:2-5:0.1-0.5: 0.1-0.5.
Preferably, the clay stabilizer is a potassium salt.
The invention also aims to provide a preparation method of the acidizing fluid, which comprises the following steps:
(1) adding hydrochloric acid into water, stirring, heating to 85-95 ℃, and adding a corrosion inhibitor for mixing;
(2) then regulating the temperature to 50-60 ℃, and adding the scale inhibitor and the clay stabilizer in sequence for mixing;
(3) and finally adding an inhibitor and stirring to obtain the product.
Preferably, the stirring time in the step (1) is 3-10 min; the mixing is carried out for 10-15min under the rotating speed of 100-300 r/min;
preferably, the mixing time in step (2) is 5-20 min;
preferably, the stirring is at 70-80 ℃ for 5-20 min.
The invention also aims to provide the application of the acidizing fluid in preventing the generation of hydrogen sulfide gas during the production of oil and gas fields.
Compared with the prior art, the invention has the beneficial effects that:
(1) the acidizing fluid has good compatibility with oil field in-situ well fluid and formation water, and simultaneously utilizes the catalytic oxidation principle to control hydrogen sulfide gas generated by the reaction of the acidizing fluid and acid volatile sulfur in reservoir sediments in the reservoir modification process from the source, thereby ensuring the safety of in-situ construction.
(2) According to the invention, a specific scale inhibitor and an inhibitor are adopted, the acidification effect of the acidizing fluid can be cooperatively exerted, the mixture of potassium persulfate, sodium persulfate, ammonium persulfate and graphene in a certain proportion is adopted, the efficiency of preventing the overflow of hydrogen sulfide gas is higher and more complete, and the solution has good stability and good compatibility with the oil field well entering fluid by compatibility with other components.
(3) The acidizing fluid composition has high hydrogen sulfide gas removal rate, is simple and convenient to operate and has strong practicability.
Drawings
FIG. 1 is a standard curve diagram of "a method for detecting sulfur ions by ultraviolet spectrophotometry and measurement of a standard curve", in which the abscissa axis represents the content of sulfur ions in mg and the ordinate axis represents the absorbance (A).
Detailed Description
The present invention will be further described with reference to the following examples.
The raw materials used in the following embodiments are all commercially available conventional materials. Wherein the hydroxypropyl acrylate copolymer is purchased from Hubei Braschoko chemical industry Co., Ltd, the polymethacrylic acid is purchased from Wuhan Hongdeuoxin medicine science and technology Co., Ltd, the polyepoxysuccinic acid is purchased from Shandongtai and water treatment science and technology Co., Ltd, and the SDSH quaternary ammonium salt corrosion inhibitor is purchased from Xinjiang Claritytada New technology Co., Ltd.
Ultraviolet spectrophotometry sulfur ion detection method and determination of standard curve
According to the method for measuring water quality sulfide (GB/T16489-1996), nine 100mL cuvettes with stoppers are taken, 20mL of zinc acetate-sodium acetate solution is added into each cuvette (50 g of zinc acetate and 12.5g of sodium acetate are weighed and dissolved in 1000mL of distilled water, shaking is carried out), 0.00, 0.50, 1.00, 2.00, 3.00, 4.00, 5.00, 6.00 and 7.00mL of sodium sulfide solution are taken respectively (0.75 g of sodium sulfide is weighed and dissolved in a small amount of water, transferring into a 100mL volumetric flask, diluting with distilled water to a marked line and shaking is carried out), transferring into the cuvette, adding water to about 60mL, slowly adding 10mLN, N-dimethyl-p-phenylenediamine solution along the wall of the cuvette (2 g of N, N-dimethyl-p-phenylenediamine is weighed and dissolved in 200mL of distilled water, slowly adding 200mL of concentrated sulfuric acid, cooling, diluting with distilled water to 1000mL, shaking is carried out), immediately plugging and slowly inverting once, adding 1mL of ferric ammonium sulfate solution (25 g of ferric ammonium sulfate dissolved in 5mL of concentrated sulfuric acid, diluted to 250mL with distilled water and shaken up), the stopper is immediately stoppered and shaken up well. Standing for 10min, diluting with water to marked line, and shaking. The absorbance was measured at a wavelength of 665nm using a 1cm cuvette with distilled water as a reference, and a blank test was conducted. The measured absorbance of the blank test subtracted from different concentrations is used as the ordinate, the content (mg) of sulfur ions in corresponding different solutions is used as the abscissa to draw a standard curve, and the result is shown in figure 1.
Second, measuring the sulfur ion content of' Mega 133 well reservoir core debris 500g
500g of core debris of a Ma 133 well reservoir stratum is taken, the core debris is ground into powder by a diamond grinding pestle, uniform core debris powder is filtered by a 40-mesh filtering screen, 20g of the uniform powder is taken to react with 170ml of 15% hydrochloric acid in a closed container, gas generated by the reaction is detected by the ultraviolet spectrophotometry sulfur ion detection method, and is substituted into the standard curve, and the content of volatile sulfur in the mineral of the reaction reservoir stratum is calculated to be 26.50 mg.
Example 1
The composition of the acidizing fluid for preventing the generation of the hydrogen sulfide in the embodiment is as follows: 15 parts of hydrochloric acid, 2 parts of corrosion inhibitor, 5 parts of antiscale, 1 part of clay stabilizer potassium chloride, 0.1 part of inhibitor and 76.9 parts of distilled water.
Wherein the antiscaling agent is a mixture of fatty alcohol ether sulfosuccinic acid, polyepoxysuccinic acid, hydroxypropyl acrylate copolymer and polymethacrylic acid in a mass ratio of 1:3:0.5: 0.5;
the inhibitor is a mixture of potassium persulfate, sodium persulfate, ammonium persulfate and graphene in a mass ratio of 0.7:1:3: 0.2.
Wherein the corrosion inhibitor consists of SDSH quaternary ammonium salt corrosion inhibitor and urotropine in the mass ratio of 1: 0.5.
The preparation method comprises the following steps:
(1) slowly adding hydrochloric acid into distilled water at a speed of 200r/min, stirring for 5min, heating to 90 ℃, adding the corrosion inhibitor, and stirring at a speed of 200r/min for 15 min;
(2) then regulating the temperature to 50 ℃, sequentially adding the scale inhibitor and the clay stabilizer, and stirring for 15min at 200 r/min;
(3) and finally adding an inhibitor at 70 ℃ and stirring for 15min to obtain an acidizing fluid, and sealing and storing the acidizing fluid by using an acid-resistant reagent bottle for later use.
Taking 500g of core debris of a reservoir of a Ma 133 well, grinding the core debris into powder by using a diamond grinding pestle, filtering out uniform core debris powder by using a 40-mesh filtering screen, taking 20g of the uniform core debris powder to react with 170ml of acidizing fluid in a closed container, detecting gas generated by the reaction by using the ultraviolet spectrophotometry sulfur ion detection method, substituting the gas into the standard curve, and calculating to obtain the volatile sulfur content of 4.50mg and the removal efficiency of 83.64% (the removal efficiency is 1-the volatile sulfur content after the acidizing fluid is added/the volatile sulfur content in the mineral of the reservoir to be reacted).
Example 2
The composition of the acidizing fluid for preventing the generation of hydrogen sulfide in the embodiment is as follows: 15 parts of hydrochloric acid, 2 parts of corrosion inhibitor, 5 parts of antiscale, 1 part of clay stabilizer potassium chloroacetate, 0.2 part of inhibitor and 76.8 parts of water.
Wherein the antiscaling agent is a mixture of fatty alcohol ether sulfosuccinic acid, polyepoxysuccinic acid, hydroxypropyl acrylate copolymer and polymethacrylic acid in a mass ratio of 1:3:0.5: 0.5;
the inhibitor is a mixture of potassium persulfate, sodium persulfate, ammonium persulfate and graphene in a mass ratio of 0.7:1:3: 0.2.
Wherein the corrosion inhibitor consists of SDSH quaternary ammonium salt corrosion inhibitor and urotropine in a mass ratio of 3: 1.
The preparation method comprises the following steps:
(1) adding hydrochloric acid into distilled water at a speed of 200r/min, stirring for 5min, heating to 90 ℃, adding the corrosion inhibitor, and stirring at a speed of 200r/min for 15 min;
(2) then regulating the temperature to 50 ℃, sequentially adding the scale inhibitor and the clay stabilizer, and stirring for 15min at 200 r/min;
(3) and finally adding an inhibitor at 70 ℃ and stirring for 15min to obtain an acidizing fluid, and sealing and storing the acidizing fluid by using an acid-resistant reagent bottle for later use.
Taking 500g of core debris of a reservoir of a Ma 133 well, grinding the core debris into powder by using a diamond grinding pestle, filtering out uniform core debris powder by using a 40-mesh filter screen, taking 20g of the uniform core debris powder to react with 170ml of acidizing fluid in a closed container, detecting gas generated by the reaction by using the ultraviolet spectrophotometry sulfur ion detection method, substituting the gas into the standard curve, and calculating to obtain the volatile sulfur content of 1.50mg and the removal efficiency of 94.55% (the removal efficiency is 1-the volatile sulfur content after the acidizing fluid is added/the volatile sulfur content in the mineral of the reservoir is reacted).
Example 3
The composition of the acidizing fluid for preventing the generation of hydrogen sulfide in the embodiment is as follows: 15 parts of hydrochloric acid, 2 parts of corrosion inhibitor, 5 parts of antiscale, 1 part of clay stabilizer potassium chloride, 0.3 part of inhibitor and 76.7 parts of water.
Wherein the antiscaling agent is a mixture of fatty alcohol ether sulfosuccinic acid, polyepoxysuccinic acid, hydroxypropyl acrylate copolymer and polymethacrylic acid in a mass ratio of 1:3:0.5: 0.5;
the inhibitor is a mixture of potassium persulfate, sodium persulfate, ammonium persulfate and graphene in a mass ratio of 0.7:1:3: 0.2.
Wherein the corrosion inhibitor consists of SDSH quaternary ammonium salt corrosion inhibitor and urotropine in the mass ratio of 1: 0.5.
The preparation method comprises the following steps:
(1) adding hydrochloric acid into distilled water at a speed of 200r/min, stirring for 5min, heating to 90 ℃, adding the corrosion inhibitor, and stirring at a speed of 200r/min for 15 min;
(2) then regulating the temperature to 50 ℃, sequentially adding the scale inhibitor and the clay stabilizer, and stirring for 15min at 200 r/min;
(3) and finally adding an inhibitor at 70 ℃ and stirring for 15min to obtain an acidizing fluid, and sealing and storing the acidizing fluid by using an acid-resistant reagent bottle for later use.
Taking 500g of core debris of a reservoir of a Ma 133 well, grinding the core debris into powder by using a diamond grinding pestle, filtering out uniform core debris powder by using a 40-mesh filter screen, taking 20g of the uniform core debris powder to react with 170ml of acidizing fluid in a closed container, detecting gas generated by the reaction by using the ultraviolet spectrophotometry sulfur ion detection method, substituting the gas into the standard curve, and calculating to obtain the volatile sulfur content of 0.00mg and the removal efficiency of 100.00% (the removal efficiency is 1-the volatile sulfur content after the acidizing fluid is added/the volatile sulfur content in the mineral of the reservoir.
Example 4
The composition of the acidizing fluid for preventing the generation of the hydrogen sulfide in the embodiment is as follows: 10 parts of hydrochloric acid, 1 part of corrosion inhibitor, 10 parts of antiscaling agent, 5 parts of clay stabilizer potassium chloride, 0.1 part of inhibitor and 73.9 parts of water.
Wherein the antiscaling agent is a mixture of fatty alcohol ether sulfosuccinic acid, polyepoxysuccinic acid, hydroxypropyl acrylate copolymer and polymethacrylic acid in a mass ratio of 1:5:0.1: 0.1;
the inhibitor is a mixture of potassium persulfate, sodium persulfate, ammonium persulfate and graphene in a mass ratio of 1:1:2: 0.5.
Wherein the corrosion inhibitor consists of SDSH quaternary ammonium salt corrosion inhibitor and urotropine in a mass ratio of 2: 1.
The preparation method comprises the following steps:
(1) adding hydrochloric acid into distilled water at a speed of 100r/min, stirring for 10min, heating to 85 ℃, adding the corrosion inhibitor, and stirring for 15min at a speed of 100 r/min;
(2) then regulating the temperature to 60 ℃, sequentially adding the scale inhibitor and the clay stabilizer, and stirring for 20min at 100 r/min;
(3) and finally adding an inhibitor at 70 ℃ and stirring for 5min to obtain an acidizing fluid, and sealing and storing the acidizing fluid by using an acid-resistant reagent bottle for later use.
Taking 500g of Ma 133 well reservoir core debris, grinding the core debris into powder by using a diamond grinding pestle, filtering out uniform core debris powder by using a 40-mesh filtering screen, taking 20g of the uniform core debris powder, reacting the uniform core debris powder with 170ml of acidizing fluid in a closed container, detecting gas generated by the reaction by using the ultraviolet spectrophotometry sulfur ion detection method, substituting the gas into the standard curve, and calculating to obtain the volatile sulfur content of 0.00mg with the removal efficiency of 100.00% (the removal efficiency is 1-the volatile sulfur content after the acidizing fluid is added/the volatile sulfur content in the reservoir minerals is reacted).
Example 5
The acidizing fluid of the present embodiment comprises the following components: 20 parts of hydrochloric acid, 5 parts of corrosion inhibitor, 3 parts of antiscaling agent, 0.5 part of clay stabilizer potassium chloride, 1 part of inhibitor and 70.5 parts of water.
Wherein the antiscaling agent is a mixture of fatty alcohol ether sulfosuccinic acid, polyepoxysuccinic acid, hydroxypropyl acrylate copolymer and polymethacrylic acid in a mass ratio of 1:2:0.3: 0.3;
the inhibitor is a mixture of potassium persulfate, sodium persulfate, ammonium persulfate and graphene in a mass ratio of 0.5:1:4: 0.1.
The corrosion inhibitor consists of SDSH quaternary ammonium salt corrosion inhibitor and urotropine in the mass ratio of 1: 0.5.
The preparation method comprises the following steps:
(1) adding hydrochloric acid into distilled water at a speed of 300r/min, stirring for 3min, heating to 95 ℃, adding the corrosion inhibitor, and stirring for 10min at a speed of 300 r/min;
(2) then regulating the temperature to 50 ℃, sequentially adding the scale inhibitor and the clay stabilizer, and stirring for 5min at 300 r/min;
(3) and finally adding an inhibitor at 80 ℃ and stirring for 20min to obtain an acidizing fluid, and sealing and storing the acidizing fluid by using an acid-resistant reagent bottle for later use.
Taking 500g of core debris of a reservoir of a Ma 133 well, grinding the core debris into powder by using a diamond grinding pestle, filtering out uniform core debris powder by using a 40-mesh filter screen, taking 20g of the uniform core debris powder to react with 170ml of acidizing fluid in a closed container, detecting gas generated by the reaction by using the ultraviolet spectrophotometry sulfur ion detection method, substituting the gas into the standard curve, and calculating to obtain the volatile sulfur content of 0.00mg and the removal efficiency of 100.00% (the removal efficiency is 1-the volatile sulfur content after the acidizing fluid is added/the volatile sulfur content in the mineral of the reservoir.
Comparative example 1
The difference between the comparative example and the example 3 is that the components of the acidizing fluid have different proportions, specifically: 15 parts of hydrochloric acid, 6 parts of corrosion inhibitor, 1 part of antiscaling agent, 1.5 parts of clay stabilizer potassium chloride and 0.08 part of inhibitor, and the balance of water, wherein the total amount is 100 parts. The rest corresponds to example 3. And detecting gas generated by the reaction by using the ultraviolet spectrophotometry sulfur ion detection method, substituting the gas into the standard curve, and calculating to obtain the gas with the volatile sulfur content of 10.34mg and the removal efficiency of 60.98% (the removal efficiency is 1-the volatile sulfur content after the acidizing fluid is added/the volatile sulfur content in the mineral of the reaction reservoir).
Comparative example 2
The difference between the comparative example and the example 3 is that the component proportion of the inhibitor is different, and the total part of the inhibitor is not changed. The method specifically comprises the following steps:
the inhibitor is a mixture of potassium persulfate, sodium persulfate, ammonium persulfate and graphene in a mass ratio of 0.2:1:1: 0.05.
The rest corresponds to example 3. And detecting gas generated by the reaction by using the ultraviolet spectrophotometry sulfur ion detection method, substituting the gas into the standard curve, and calculating to obtain the gas with the volatile sulfur content of 8.75mg and the removal efficiency of 66.98% (the removal efficiency is 1-the volatile sulfur content after the acidizing fluid is added/the volatile sulfur content in the mineral of the reaction reservoir).
Comparative example 3
The difference between the comparative example and the example 3 is that the inhibitor is adjusted to be equal parts of hydrogen peroxide, and the rest is kept consistent with the example 3. Gas generated by reaction is detected by the ultraviolet spectrophotometry sulfur ion detection method, and is substituted into the standard curve, the volatile sulfur content is calculated and produced to be 12.39mg, the removal efficiency is 53.24% (the removal efficiency is 1-the volatile sulfur content after the acidizing fluid is added/the volatile sulfur content in the reaction reservoir minerals), the oil field fluid entering the well is a low polymer fracturing fluid, hydrogen peroxide has strong oxidizability, has certain destructive effect on polymers in the fracturing fluid, causes the physicochemical properties such as viscosity of the polymers to be changed, and obviously deteriorates the compatibility of the acidizing fluid and the oil field fluid entering the well.
Comparative example 4
The difference between the comparative example and the example 3 is that the preparation method is different, and specifically:
(1) slowly adding hydrochloric acid into distilled water at a speed of 200r/min, stirring for 5min, sequentially adding the corrosion inhibitor, the scale inhibitor and the clay stabilizer at room temperature, and stirring for 30min at a speed of 200 r/min;
(3) and finally adding an inhibitor and stirring for 15min to obtain an acidizing fluid. The rest remained the same as in example 3.
And (3) detecting the gas generated by the reaction by using the ultraviolet spectrophotometry sulfur ion detection method, substituting the detected gas into the standard curve, and calculating to obtain the gas with the volatile sulfur content of 6.52mg and the removal efficiency of 75.39% (the removal efficiency is 1-the volatile sulfur content after the acidizing fluid is added/the volatile sulfur content in the mineral in the reaction reservoir). The acidizing fluid prepared by the method is not uniformly dispersed, has poor compatibility with the fluid entering a well oil field and has poor compatibility.
The above detailed description is specific to one possible embodiment of the present invention, and the embodiment is not intended to limit the scope of the present invention, and all equivalent implementations or modifications without departing from the scope of the present invention should be included in the technical scope of the present invention.

Claims (11)

1. The acidizing fluid for preventing the generation of hydrogen sulfide is characterized by comprising the following components in parts by weight: 10-20 parts of hydrochloric acid, 1-5 parts of corrosion inhibitor, 3-10 parts of antiscale agent, 0.5-5 parts of clay stabilizer and 0.1-1 part of inhibitor, wherein the inhibitor is a mixture of potassium persulfate, sodium persulfate, ammonium persulfate and graphene; the antiscaling agent is a mixture of fatty alcohol ether sulfosuccinic acid, polyepoxy succinic acid, hydroxypropyl acrylate copolymer and polymethacrylic acid;
the inhibitor is a mixture of potassium persulfate, sodium persulfate, ammonium persulfate and graphene in a mass ratio of 0.5-1:1:2-4: 0.1-0.5;
the preparation method of the acidizing fluid comprises the following steps:
(1) adding hydrochloric acid into water, stirring, heating to 85-95 ℃, adding a corrosion inhibitor, and mixing;
(2) then regulating the temperature to 50-60 ℃, and sequentially adding the scale inhibitor and the clay stabilizer for mixing;
(3) and finally adding an inhibitor, stirring and dispersing uniformly to obtain the product.
2. The acidizing fluid of claim 1 which comprises the following components, by weight: 13-18 parts of hydrochloric acid, 1-5 parts of corrosion inhibitor, 5-8 parts of antiscale agent, 0.5-2 parts of clay stabilizer and 0.2-1 part of inhibitor.
3. The acidizing fluid of claim 1, where the components further comprise water.
4. The acidizing fluid of claim 1, wherein the corrosion inhibitor is composed of SDSH quaternary ammonium salt corrosion inhibitor and urotropin in a mass ratio of 1-3: 0.5-1.
5. The acidizing fluid of claim 1, wherein said anti-scaling agent is a mixture of fatty alcohol ether sulfosuccinic acid, polyepoxysuccinic acid, hydroxypropyl acrylate copolymer and polymethacrylic acid in a mass ratio of 1:2-5:0.1-0.5: 0.1-0.5.
6. The acidizing fluid of claim 1 wherein said clay stabilizing agent is a potassium salt.
7. A method for preparing the acidizing fluid of any one of claims 1 to 6 which comprises the steps of:
(1) adding hydrochloric acid into water, stirring, heating to 85-95 ℃, adding a corrosion inhibitor, and mixing;
(2) then regulating the temperature to 50-60 ℃, and sequentially adding the scale inhibitor and the clay stabilizer for mixing;
(3) and finally adding an inhibitor, stirring and dispersing uniformly to obtain the product.
8. The method according to claim 7, wherein the stirring time in the step (1) is 3 to 10 min; the mixing is carried out for 10-15min under the rotating speed of 100-300 r/min.
9. The method of claim 7, wherein the mixing in step (2) is performed for a period of 5 to 20 min.
10. The method according to claim 7, wherein the stirring in the step (3) is performed at 70 to 80 ℃ for 5 to 20 min.
11. Use of an acidizing fluid according to any one of the claims 1 to 6 in the production of oil and gas fields.
CN202111173475.7A 2021-10-08 2021-10-08 Acidizing fluid for preventing generation of hydrogen sulfide Active CN113881413B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111173475.7A CN113881413B (en) 2021-10-08 2021-10-08 Acidizing fluid for preventing generation of hydrogen sulfide

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111173475.7A CN113881413B (en) 2021-10-08 2021-10-08 Acidizing fluid for preventing generation of hydrogen sulfide

Publications (2)

Publication Number Publication Date
CN113881413A CN113881413A (en) 2022-01-04
CN113881413B true CN113881413B (en) 2022-09-06

Family

ID=79005573

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111173475.7A Active CN113881413B (en) 2021-10-08 2021-10-08 Acidizing fluid for preventing generation of hydrogen sulfide

Country Status (1)

Country Link
CN (1) CN113881413B (en)

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9213628D0 (en) * 1992-06-26 1992-08-12 Blythe William Ltd Scavenging
CN103408880B (en) * 2013-06-27 2015-10-14 安徽百特新材料科技有限公司 A kind of preparation method of polyacrylonitrile/grcomposite composite material
CN112457833B (en) * 2020-11-24 2022-06-03 中国石油天然气股份有限公司 Hydrogen sulfide inhibitor for oil-water well acidification, preparation method and application thereof

Also Published As

Publication number Publication date
CN113881413A (en) 2022-01-04

Similar Documents

Publication Publication Date Title
CN102976509B (en) A kind of high sulfur-bearing gas production method for treating waste liquid
US8591767B2 (en) Functional fluid and a process for the preparation of the functional fluid
US5073270A (en) Use of reducing agents to control scale deposition from high temperature brine
US20150307375A1 (en) Preventing mobilization of trace metals in subsurface aquifers due to the introduction of oxygenated water
CN103880202B (en) Sulfuric acid gas field gas production waste water reinjection treatment process
MX2013011702A (en) Method and compositions for enhanced oil recovery.
CN103459306A (en) Chlorine dioxide precursor and methods of using same
CN101612516A (en) The removal method of hydrogen sulfide in ferrous hydrogen sulfide remover and the gas
CN105419772A (en) Polyacrylamide polymer viscosity reducer
CN106281281A (en) A kind of oil well H2S SCAVENGER and using method thereof
CN103097495A (en) Process, method, and system for removing heavy metals from fluids
CN113881413B (en) Acidizing fluid for preventing generation of hydrogen sulfide
CN111732603A (en) Temperature-resistant and salt-resistant fracturing fluid imbibition agent and preparation method and application thereof
CN101319608A (en) Method for down-hole removing hydrogen sulphide in natural gas
Chen et al. Rate-based model for predicting and evaluating H2S absorption in the haloalkaliphilic biological desulfurization process
CN110104891B (en) Method for reducing and removing heavy metal ions in photovoltaic cell wastewater
Yuliang et al. Study on Release Mechanism and Control Technology of Hydrogen Sulfide Gas in Coal Mine.
US8574441B2 (en) Process for removing oxidants from water injected into a subsurface aquifer to prevent mobilization of trace metals
CN106497540A (en) A kind of chemical formulation of the souring soln for improving coal seam permeability
CN102797446B (en) Steam flooding Injection Well suppresses oil reservoir to generate the method and apparatus of hydrogen sulfide
CN102775978B (en) Treating agent for inhibiting generation of hydrothion in oil reservoir in steam flooding injection well and application thereof
CN114715992B (en) Desulfurizing deodorant and preparation method and application thereof
Bonyo Scaling and Corrosion Mitigation in Olkaria Using Brine and Condensate Mixing Method
Sun et al. Experimental Study on the Influence of Hydraulic Fracturing on Hydrogen Sulfide Generation in Longxi Block of Daqing Oilfield
CN204027978U (en) A kind of novel frozen glue sulfur resistance evaluating apparatus

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant