CN112063376A - Solid corrosion inhibition capsule for oil extraction and preparation method and application method thereof - Google Patents
Solid corrosion inhibition capsule for oil extraction and preparation method and application method thereof Download PDFInfo
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- 230000007797 corrosion Effects 0.000 title claims abstract description 146
- 238000005260 corrosion Methods 0.000 title claims abstract description 146
- 239000002775 capsule Substances 0.000 title claims abstract description 90
- 230000005764 inhibitory process Effects 0.000 title claims abstract description 82
- 239000007787 solid Substances 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000000605 extraction Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000003112 inhibitor Substances 0.000 claims abstract description 61
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 34
- 239000002262 Schiff base Substances 0.000 claims abstract description 20
- 150000004753 Schiff bases Chemical group 0.000 claims abstract description 20
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011257 shell material Substances 0.000 claims abstract description 18
- 150000003934 aromatic aldehydes Chemical class 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 239000003921 oil Substances 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 239000012530 fluid Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 239000003094 microcapsule Substances 0.000 claims description 10
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 9
- 238000005536 corrosion prevention Methods 0.000 claims description 9
- 235000010413 sodium alginate Nutrition 0.000 claims description 9
- 239000000661 sodium alginate Substances 0.000 claims description 9
- 229940005550 sodium alginate Drugs 0.000 claims description 9
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 229920001661 Chitosan Polymers 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910001200 Ferrotitanium Inorganic materials 0.000 claims description 5
- 239000001110 calcium chloride Substances 0.000 claims description 5
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000010779 crude oil Substances 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 230000008961 swelling Effects 0.000 claims description 4
- 235000010410 calcium alginate Nutrition 0.000 claims description 3
- 239000000648 calcium alginate Substances 0.000 claims description 3
- 229960002681 calcium alginate Drugs 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical compound [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- 229940045110 chitosan Drugs 0.000 claims description 2
- 229940117916 cinnamic aldehyde Drugs 0.000 claims description 2
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910003460 diamond Inorganic materials 0.000 claims description 2
- 239000010432 diamond Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 2
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 2
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 2
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 229960002901 sodium glycerophosphate Drugs 0.000 claims description 2
- 235000019830 sodium polyphosphate Nutrition 0.000 claims description 2
- REULQIKBNNDNDX-UHFFFAOYSA-M sodium;2,3-dihydroxypropyl hydrogen phosphate Chemical compound [Na+].OCC(O)COP(O)([O-])=O REULQIKBNNDNDX-UHFFFAOYSA-M 0.000 claims description 2
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 claims description 2
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 claims description 2
- 235000012141 vanillin Nutrition 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims 5
- 239000011162 core material Substances 0.000 abstract description 17
- 229910052751 metal Inorganic materials 0.000 abstract description 9
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- 238000005553 drilling Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
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- 238000004364 calculation method Methods 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
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- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
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- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
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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
- C09K8/54—Compositions for in situ inhibition of corrosion in boreholes or wells
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
Abstract
A solid corrosion inhibition capsule for oil extraction comprises the following components in parts by weight: 10-60 parts of shell material; 20-70 parts of a weighting agent; 1-10 parts of a curing agent; 15-50 parts of a modified corrosion inhibitor; the modified corrosion inhibitor is a Schiff base type corrosion inhibitor and is prepared by reacting aniline and aromatic aldehyde VB; the solid corrosion inhibition capsule is wrapped by a shell made of degradable high polymer materials by an orifice-coagulation bath method, and the core material is a novel Schiff base type corrosion inhibitor prepared by aniline and aromatic aldehyde through chemical reaction; the degradable material shell can be naturally degraded in a high-temperature environment underground, the purpose of controllable release is achieved, and a good protection effect is achieved on equipment. The self-made corrosion inhibitor has good adsorptivity and protective property to metal, and the preparation process is simple and environment-friendly. The solid corrosion inhibition capsule added with the weighting agent has better mechanical property and good sedimentation and release performance, and can play a good role in protection in high-temperature, high-pressure and high-salt environments.
Description
Technical Field
The invention relates to a solid corrosion inhibition capsule, in particular to a solid corrosion inhibition capsule for oil extraction and a preparation method thereof, wherein the solid corrosion inhibition capsule can delay corrosion of steel facilities in the processes of crude oil extraction and transportation.
Background
In the development and transportation process of oil and gas resources, a large amount of H2S, CO2, inorganic salt and other substances are often dissolved in oilfield produced water, so that accidents such as casing perforation, drilling equipment failure and the like are often caused, and serious economic loss and potential safety hazards are generated. Statistically, 70% of petroleum equipment failures are associated with corrosion. Therefore, the protection of oil field drilling and production and transportation equipment is more and more emphasized.
The reasonable use and the addition of the corrosion inhibitor can effectively prevent the metal corrosion, and the method is more and more widely applied in recent years due to the characteristics of convenience, high efficiency, low price and the like. The liquid corrosion inhibitor is convenient to use, but the action time of the liquid corrosion inhibitor cannot be controlled, so that the solid capsule type corrosion inhibitor which can regulate the release rate of the corrosion inhibitor in the shell through the optimization of shell layer materials becomes a hot point of research. Patent CN 103937477A prepares a controlled release solid corrosion inhibitor, which takes calcium alginate as a carrier and a shell layer, and a weighting agent and an oil field conventional corrosion inhibitor are wrapped in the shell layer. The prepared solid corrosion inhibitor capsule has good sedimentation performance, and the corrosion inhibitor is gradually released in the swelling and crushing process of the capsule, thereby playing an effective protection role on oilfield equipment.
Disclosure of Invention
The invention aims to solve the problems that in the process of development and transportation of oil and gas resources in the prior art, a large amount of H2S, CO2, inorganic salt and other substances are often dissolved in oilfield produced water, so that accidents such as casing perforation, drilling equipment failure and the like are often caused, and serious economic loss and potential safety hazards are generated.
The technical scheme adopted by the invention is as follows: the invention provides a preparation method of a solid corrosion inhibition capsule for oil extraction, the solid corrosion inhibition capsule is wrapped by a shell made of degradable high polymer materials by an orifice-coagulation bath method, and a core material is a novel Schiff base type corrosion inhibitor prepared by aniline and aromatic aldehyde through chemical reaction. The degradable material shell can be naturally degraded in a high-temperature environment underground, the purpose of controllable release is achieved, and a good protection effect is achieved on equipment. The self-made corrosion inhibitor has good adsorptivity and protective property to metal, and the preparation process is simple and environment-friendly. The solid corrosion inhibition capsule added with the weighting agent has better mechanical property and good sedimentation and release performance, and can play a good role in protection in high-temperature, high-pressure and high-salt environments.
The technical scheme of the invention is as follows:
a solid corrosion inhibition capsule for oil extraction is characterized in that: the solid corrosion inhibition capsule comprises the following components in parts by weight:
10-60 parts of shell material;
20-70 parts of a weighting agent;
1-10 parts of a curing agent;
15-50 parts of a modified corrosion inhibitor;
the modified corrosion inhibitor is a Schiff base type corrosion inhibitor, is prepared by reacting aniline and aromatic aldehyde VB, and has the following chemical structure:
wherein R is1The group is an alkoxy functional group having 1 to 3 carbon atoms or a hydrogen atom, R2The radicals being hydroxyl or hydrogen atoms, R3The group is an alkoxy functional group containing 1-3 carbon atoms or a hydrogen atom, and the value of n is in the range of 0-1.
Further, the preparation method of the solid corrosion inhibition capsule for oil extraction is characterized by comprising the following steps: the method specifically comprises the following steps:
(1) dissolving 15-50 parts by weight of modified corrosion inhibitor into 100 parts of water at 25 ℃, and stirring at 200rpm for 30min to obtain a uniform solution;
(2) adding 20-70 parts by weight of weighting agent into the solution obtained in the step (1), and uniformly stirring under the same conditions in the step one;
(3)3, adding 10-60 parts by weight of shell material into the solution obtained in the step (2), and uniformly stirring under the same conditions obtained in the step one to obtain a core solution;
(4) dissolving 1-10 parts by weight of curing agent in 100 parts of water, and uniformly stirring;
(5) dripping all the core solution obtained in the step (3) into the curing agent solution obtained in the step (4) by using an orifice device, and standing for 20-60min to form a spherical microcapsule encapsulating the corrosion inhibitor and the weighting agent; taking out the spherical microcapsule, and drying at 25 ℃ for 12-36h to obtain the solid corrosion inhibition capsule.
Further, the preparation method of the Schiff base type corrosion inhibitor comprises the following steps: adding 0.02mol of aniline and 40mol of absolute ethyl alcohol into a three-neck flask provided with a common magnetic stirring device, a reflux condenser and a thermometer, heating to 70-90 ℃, and stirring until the aniline is completely dissolved; and then 0.02mol of p-hydroxybenzaldehyde, vanillin or cinnamaldehyde is added into the three-necked bottle, and the Schiff base type corrosion inhibitor is obtained after reaction for 3 to 6 hours.
Preferably, the shell material is one or more of sodium alginate, calcium alginate, chitosan or hydroxypropyl methyl cellulose.
Preferably, the weighting agent is one or more of silicon dioxide, ferrotitanium powder, diamond iron powder, calcium carbonate and barium sulfate.
Preferably, the curing agent is one or more of calcium chloride, acetic acid, sodium hydroxide, sodium polyphosphate or sodium glycerophosphate.
An application method of a solid corrosion inhibition capsule for oil extraction comprises the following steps: mixing one or more of a solid corrosion inhibition capsule and fracturing fluid, plugging regulating fluid, plugging agent or carrying fluid (the carrying fluid can be any common liquid for an oil field, and only needs to meet corresponding neutral pH value and use temperature range when in use), and then injecting the mixture into a well, wherein the solid corrosion inhibition capsule gradually releases a corrosion inhibitor in the swelling and crushing process, and the released corrosion inhibitor is diffused into crude oil in a shaft, so that the corrosion prevention of the solid corrosion inhibition capsule on oil field equipment is completed.
The invention has the beneficial effects that:
1. the solid corrosion inhibition capsule provided by the invention has strong affinity with metal, is easy to adsorb on the surface of the metal, and can play good corrosion prevention and corrosion inhibition roles.
2. The weighting agent used by the solid corrosion inhibition capsule provided by the invention improves the sedimentation and mechanical properties of the capsule, so that the solid corrosion inhibition capsule can smoothly sink underground without being damaged in midway.
3. The solid corrosion inhibition capsule shell material provided by the invention is a degradable high polymer material with certain mechanical property, and the corrosion inhibitor of the core can be slowly released through the original pore canal generated by degradation, so that the long-acting corrosion inhibition effect is achieved.
4. The preparation method of the solid corrosion inhibition capsule adopts an orifice-coagulation bath method, is simple, convenient, safe and environment-friendly, has good effect and higher application value.
Drawings
FIG. 1 is a thermogravimetric plot of a Schiff base type corrosion inhibitor prepared;
Detailed Description
The invention is described in further detail below with reference to the following detailed description and accompanying drawings:
the following examples are presented to enable those skilled in the art to more fully understand the present invention and are not intended to limit the invention in any way.
Example 1
The solid corrosion inhibition capsule for oil extraction comprises the following components in parts by weight:
30 parts of sodium alginate;
55 parts of barium sulfate;
2 parts of calcium chloride;
13 parts of Schiff base type corrosion inhibitor;
the preparation method of the solid corrosion inhibition capsule for oil extraction comprises the following preparation processes:
(1) dissolving the Schiff base type corrosion inhibitor in water, and uniformly stirring;
(2) adding barium sulfate, and stirring uniformly;
(3) adding sodium alginate, and stirring to obtain core solution;
(4) dripping the core solution into the calcium chloride solution by using an orifice device, and standing for 30min to form the spherical microcapsule encapsulating the corrosion inhibitor and the weighting agent. Taking out, drying at normal temperature for 24h to obtain the solid corrosion inhibition capsule.
The density measuring method comprises the following steps: and (3) measuring the density of the solid corrosion inhibition capsule by adopting a drainage method. The capsule with mass m is put into a measuring cylinder, and water is added to the measuring cylinder until the volume is 100mL, wherein the total mass of the materials in the measuring cylinder is m 1. 100mL of water was further weighed to obtain m2 as a mass. The density of the capsule is 0.01 Xm 2/(m + m2-m 1).
Method for determining Release Performance: 1g of solid corrosion inhibition capsule (accurate to 0.0001g) is accurately weighed into a 20mL sample bottle, 10mL deionized water is added, and then the sample bottle is placed into an oscillating water bath at 70 ℃ (accurate to 0.2 ℃) and oscillated at the frequency of 150 times per minute with the oscillation amplitude of about 1 cm. And filtering the water body by using a sample separating sieve after a certain time, drying the solid material at the constant temperature of 70 ℃ for 8-10 h, taking out the solid material, putting the solid material into a dryer, cooling the solid material to the room temperature, and weighing the solid material. If the weight is not constant, the drying is repeated until the weight is constant.
The release rate calculation formula is as follows:
the release rate is (m0-m1)/m0 × 100%
In the formula: m0 — initial mass of sample, g;
m 1-mass of sample after a certain time in water bath, g.
And (3) corrosion inhibition performance testing: a20 cm by 20cm piece of P110 carbon steel was put into 1.0L of a 3.5% NaCl solution at pH 4, and 5g of a solid corrosion-inhibiting capsule was added, and the solution was changed every day while maintaining an environment of 70 ℃. And observing the time when the carbon steel test piece generates rust marks for the first time.
The practical application method comprises the following steps: mixing one or more of a solid corrosion inhibition capsule and fracturing fluid, plugging regulating fluid, plugging agent or carrying fluid (the carrying fluid can be any common liquid for an oil field, and only needs to meet corresponding neutral pH value and use temperature range when in use), and then injecting the mixture into a well, wherein the solid corrosion inhibition capsule gradually releases a corrosion inhibitor in the swelling and crushing process, and the released corrosion inhibitor is diffused into crude oil in a shaft, so that the corrosion prevention of the solid corrosion inhibition capsule on oil field equipment is completed.
Example 2
The solid corrosion inhibition capsule for oil extraction comprises the following components in parts by weight:
18 parts of sodium alginate;
50 parts of barium sulfate;
2 parts of calcium chloride;
30 parts of Schiff base type corrosion inhibitor;
the preparation method of the solid corrosion inhibition capsule for oil extraction comprises the following preparation processes:
(1) dissolving the Schiff base type corrosion inhibitor in water, and uniformly stirring;
(2) adding barium sulfate, and stirring uniformly;
(3) adding sodium alginate, and stirring to obtain core solution;
(4) dripping the core solution into the calcium chloride solution by using an orifice device, and standing for 30min to form the spherical microcapsule encapsulating the corrosion inhibitor and the weighting agent. Taking out, drying at normal temperature for 24h to obtain the solid corrosion inhibition capsule.
The test procedures for density, release and etch properties were the same as in example 1.
Example 3
The solid corrosion inhibition capsule for oil extraction comprises the following components in parts by weight:
the preparation method of the solid corrosion inhibition capsule for oil extraction comprises the following preparation processes:
(1) dissolving the Schiff base type corrosion inhibitor in water, and uniformly stirring;
(2) adding ferrotitanium powder and stirring uniformly;
(3) adding chitosan and acetic acid, and stirring uniformly to obtain a core solution;
(4) dripping the core solution into the sodium hydroxide solution by using an orifice device, and standing for 30min to form the spherical microcapsule encapsulating the corrosion inhibitor and the weighting agent. Taking out, drying at normal temperature for 24h to obtain the solid corrosion inhibition capsule.
The test procedures for density, release and etch properties were the same as in example 1.
Example 4
The embodiment 4 of the solid corrosion inhibition capsule for oil extraction comprises the following components in parts by weight:
the preparation method of the solid corrosion inhibition capsule for oil extraction comprises the following preparation processes:
(1) dissolving the Schiff base type corrosion inhibitor in water, and uniformly stirring;
(2) adding calcium carbonate, and stirring uniformly;
(3) adding chitosan and acetic acid, and stirring uniformly to obtain a core solution;
(4) dripping the core solution into the sodium hydroxide solution by using an orifice device, and standing for 30min to form the spherical microcapsule encapsulating the corrosion inhibitor and the weighting agent. Taking out, drying at normal temperature for 24h to obtain the solid corrosion inhibition capsule.
The test procedures for density, release and etch properties were the same as in example 1.
Comparative example 1
The comparative example 1 of the solid corrosion inhibition capsule for oil extraction without adding the Schiff base corrosion inhibitor comprises the following components in parts by weight:
20 parts of sodium alginate;
34 parts of barium sulfate;
4 parts by weight of calcium chloride;
the preparation method of the solid corrosion inhibition capsule for oil extraction comprises the following preparation processes:
(1) dissolving sodium alginate in water, and stirring;
(2) adding barium sulfate, and stirring uniformly to obtain a core solution;
(3) dripping the core solution into the calcium chloride solution by using an orifice device, and standing for 30min to form the spherical microcapsule encapsulating the corrosion inhibitor and the weighting agent. Taking out, drying at normal temperature for 24h to obtain the solid corrosion inhibition capsule.
The test procedures for density, release and etch properties were the same as in example 1.
Comparative example 2
The comparative example 2 of the solid corrosion inhibition capsule for oil extraction without adding the Schiff base corrosion inhibitor comprises the following components in parts by weight:
40 parts of chitosan;
20 parts of ferrotitanium powder;
4 parts by weight of acetic acid;
4 parts by weight of sodium hydroxide;
the preparation method of the solid corrosion inhibition capsule for oil extraction comprises the following preparation processes:
(1) dissolving ethanol in water, and stirring uniformly;
(2) adding chitosan, and stirring uniformly;
(2) adding ferrotitanium powder, and uniformly stirring to prepare a core solution;
(3) dripping the core solution into the sodium hydroxide solution by using an orifice device, and standing for 30min to form the spherical microcapsule encapsulating the corrosion inhibitor and the weighting agent. Taking out, drying at normal temperature for 24h to obtain the solid corrosion inhibition capsule.
The test procedures for density, release and etch properties were the same as in example 1.
Table 1 shows the density data for the samples of examples 1-4 and comparative examples 1 and 2. As shown in Table 1, the density of all the samples of the examples and the comparative examples added with the weighting agent is between 1.40 and 1.60g/mL, and the addition of the corrosion inhibitor has little influence on the density of the solid corrosion inhibition capsule. The density of the solid corrosion inhibition capsules is higher than that of water, so that the solid corrosion inhibition capsules can freely settle into a bottom water layer in the corrosion prevention and corrosion inhibition occasions and cannot be entrained by produced fluid of an oil well to be discharged.
TABLE 1 test results of Density of examples and comparative examples
As shown in Table 1, the density of the solid sustained release capsules varied depending mainly on the amount of the weighting agent added. In different application occasions, the density of the underground water layer and the depth of an oil well are different, and the addition amount of the weighting agent can be changed, so that the density of the capsule is changed between 1.40 and 1.60g/mL, and the capsule is suitable for different well conditions.
Table 2 shows the results of the test of the release properties of the samples of examples 1 to 4 and comparative examples 1 and 2.
Table 2 test results of release properties of examples and comparative examples
As can be seen from the table 2, the release performance of the solid corrosion inhibition capsules of the examples and the comparative examples is approximately equivalent, after 2 hours, the capsules are fully swelled, and the loss of substances such as shell materials and the like exceeds 50%; after 8h, the capsules had broken and their main structure had disappeared. Therefore, after the solid corrosion inhibition capsule is coated with the shell made of the degradable high polymer material, the solid corrosion inhibition capsule has better delayed release performance, and in the actual use process, the capsule can avoid the loss along the sedimentation path and directly reaches the corresponding position to start acting.
Table 3 shows the results of the corrosion inhibition performance of the samples of examples 1 to 4 and comparative examples 1 and 2 on a P110 carbon steel coupon.
TABLE 3 test results of corrosion inhibition Performance of the examples and comparative examples
As can be seen from the data in Table 3, the solid corrosion inhibition capsule added with the Schiff base type corrosion inhibitor has obvious corrosion prevention and inhibition effects on the carbon steel test piece. After 13% of corrosion inhibitor is added, the time for the carbon steel test piece to keep the original property is prolonged from 5 days to 9 days. The main reason is that the effect of the corrosion inhibitor is that the lone pair of electrons of the heteroatom in the Schiff base type corrosion inhibitor is easy to form a coordination covalent bond with the metal, so that the corrosion inhibitor is adsorbed on the metal surface; meanwhile, the corrosion inhibitor contains pi bonds such as-C-N-and the like, is easy to interact with the metal surface, can be adsorbed on the metal surface to form a compact molecular film, and has strong corrosion prevention and corrosion inhibition effects. Meanwhile, when the addition amount of the corrosion inhibitor is increased from 13% to 40%, the corrosion inhibition performance is prolonged from 9 days to 19 days, which shows that if long-acting corrosion prevention is needed, the long-acting corrosion prevention can be realized by increasing the consumption amount of the corrosion inhibitor.
FIG. 1 is a Thermogravimetric (TGA) analysis curve of a solid extended release capsule, the temperature range of the thermogravimetric analysis being between 0-400 ℃. As shown in FIG. 1, the mass residual rate at 100 ℃ was 97.6%, and the mass reduction at this time was mainly due to the volatilization of the small molecules and the residual moisture in the capsules; the mass residual rate of the capsule at 150 ℃ is 95.6 percent, which shows that the structure of the main component of the solid corrosion inhibition capsule is not decomposed due to overhigh temperature in the using temperature range, the mass reduction is still only caused by the removal of the bound water by the sodium alginate, and the overall performance is not damaged. At 283 ℃, the degradation rate reaches the fastest speed, which indicates that the effective substances of the capsule begin to degrade at the moment, and the corrosion inhibition performance of the capsule gradually loses efficacy near the temperature.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only for the purpose of illustrating the structural relationship and principles of the present invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (7)
1. A solid corrosion inhibition capsule for oil extraction is characterized in that: the solid corrosion inhibition capsule comprises the following components in parts by weight:
10-60 parts of shell material;
20-70 parts of a weighting agent;
1-10 parts of a curing agent;
15-50 parts of a modified corrosion inhibitor;
the modified corrosion inhibitor is a Schiff base type corrosion inhibitor, is prepared by reacting aniline and aromatic aldehyde VB, and has the following chemical structure:
wherein R is1The group is an alkoxy functional group having 1 to 3 carbon atoms or a hydrogen atom, R2The radicals being hydroxyl or hydrogen atoms, R3The group is an alkoxy functional group containing 1-3 carbon atoms or a hydrogen atom, and the value of n is in the range of 0-1.
2. The method for preparing the solid corrosion inhibition capsule for oil recovery according to claim 1, wherein the solid corrosion inhibition capsule comprises: the method specifically comprises the following steps:
(1) dissolving 15-50 parts by weight of modified corrosion inhibitor into 100 parts of water at 25 ℃, and stirring at 200rpm for 30min to obtain a uniform solution;
(2) adding 20-70 parts by weight of weighting agent into the solution obtained in the step (1), and uniformly stirring under the same conditions in the step one;
(3)3, adding 10-60 parts by weight of shell material into the solution obtained in the step (2), and uniformly stirring under the same conditions obtained in the step one to obtain a core solution;
(4) dissolving 1-10 parts by weight of curing agent in 100 parts of water, and uniformly stirring;
(5) dripping all the core solution obtained in the step (3) into the curing agent solution obtained in the step (4) by using an orifice device, and standing for 20-60min to form a spherical microcapsule encapsulating the corrosion inhibitor and the weighting agent; taking out the spherical microcapsule, and drying at 25 ℃ for 12-36h to obtain the solid corrosion inhibition capsule.
3. The method for preparing the solid corrosion inhibition capsule for oil recovery according to claim 1, wherein the solid corrosion inhibition capsule comprises: the preparation method of the Schiff base type corrosion inhibitor comprises the following steps: adding 0.02mol of aniline and 40mol of absolute ethyl alcohol into a three-neck flask provided with a common magnetic stirring device, a reflux condenser and a thermometer, heating to 70-90 ℃, and stirring until the aniline is completely dissolved; and then 0.02mol of p-hydroxybenzaldehyde, vanillin or cinnamaldehyde is added into the three-necked bottle, and the Schiff base type corrosion inhibitor is obtained after reaction for 3 to 6 hours.
4. The method for preparing the solid corrosion inhibition capsule for oil recovery according to claim 1, wherein the solid corrosion inhibition capsule comprises: the shell material is one or more of sodium alginate, calcium alginate, chitosan or hydroxypropyl methyl cellulose.
5. The method for preparing the solid corrosion inhibition capsule for oil recovery according to claim 1, wherein the solid corrosion inhibition capsule comprises: the weighting agent is one or more of silicon dioxide, ferrotitanium powder, diamond iron powder, calcium carbonate and barium sulfate.
6. The method for preparing the solid corrosion inhibition capsule for oil recovery according to claim 1, wherein the solid corrosion inhibition capsule comprises: the curing agent is one or more of calcium chloride, acetic acid, sodium hydroxide, sodium polyphosphate or sodium glycerophosphate.
7. An application method of a solid corrosion inhibition capsule for oil extraction is characterized in that: mixing the solid corrosion inhibition capsule with one or more of fracturing fluid, plugging adjusting fluid, plugging agent or carrier fluid, and then injecting the mixture into a well, wherein the solid corrosion inhibition capsule gradually releases the corrosion inhibitor in the swelling and crushing process, and the released corrosion inhibitor is diffused into crude oil in a shaft, so that the corrosion prevention of the solid corrosion inhibition capsule on oilfield equipment is completed.
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| CN117488307A (en) * | 2023-11-03 | 2024-02-02 | 东莞市德硕化工有限公司 | Metal surface treating agent and preparation method thereof |
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