CN110846015B - Solid corrosion inhibition capsule and preparation method and application method thereof - Google Patents
Solid corrosion inhibition capsule and preparation method and application method thereof Download PDFInfo
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- CN110846015B CN110846015B CN201911046429.3A CN201911046429A CN110846015B CN 110846015 B CN110846015 B CN 110846015B CN 201911046429 A CN201911046429 A CN 201911046429A CN 110846015 B CN110846015 B CN 110846015B
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- 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
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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
- C09K8/54—Compositions for in situ inhibition of corrosion in boreholes or wells
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- 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
The invention provides a solid corrosion inhibition capsule and a preparation method and an application method thereof, wherein the solid corrosion inhibition capsule comprises an inner core and an outer coating film wrapping the inner core; the inner core is composed of an inorganic nano framework, a weighting agent and a corrosion inhibitor according to a proportion; the outer covering film is a naturally degradable high molecular polymer film, can realize slow release of the slow release agent, can finally realize thorough degradation in oil well produced liquid, and has a dissolution speed meeting the requirement that corrosion inhibition particles are slowly released in the bottom of a well for 3 months. The preparation method comprises the steps of adopting a double-screw extrusion and injection machine to process the mixture into spherical particles with the diameter of 1-3 mm through a granulator, controlling the water content of the particles to be 3-8% so as to be beneficial to keeping the strength of the particles, and performing indoor evaluation to ensure that the particles can be stably released in water under the condition of 10 MPa.
Description
Technical Field
The invention belongs to the technical field of petrochemical engineering auxiliaries, and particularly relates to a solid corrosion inhibition capsule as well as a preparation method and an application method thereof.
Background
Most onshore oil fields in China are developed in middle and late stages, the water content of produced liquid is quite high, and CO with different degrees is dissolved in the produced liquid due to geological reasons2、H2S、O2Substances having corrosive effects on metals, such as bacteria and dissolved salts, are extremely easy to cause serious corrosion on related equipment and pipelines. The loss of corrosion in the petroleum and petrochemical industry reported in the literature is on average about 6% of the production value. If proper protective measures are taken, 30-40% of the corrosion loss can be recovered. Therefore, the corrosion prevention of the oilfield equipment and the pipeline can not only reduce safety accidents, but also obviously improve the income of enterprises. The prior methods for preventing and inhibiting corrosion of oil fields mainly comprise the methods of using special corrosion-resistant steel, protecting metal surface coatings, electrochemically protecting, adding corrosion inhibitors into corrosion media and the like, wherein the corrosion inhibitors have the advantages of good corrosion prevention effect, simple corrosion prevention process, lower corrosion prevention cost and the like, so the method for adding the corrosion inhibitors into the corrosion media is one of the most common methods.
Typically, the oilfield wellbore corrosion inhibitors used are mostly in liquid form and are typically injected continuously through the well annulus or periodically shut-down through the wellhead at high pressure. On one hand, production can be influenced by well closing through the well mouth for periodic injection, and on the other hand, the flowing distance of the corrosion inhibitor in the process of injecting from the well mouth is too long, so that the use efficiency of the corrosion inhibitor is low. And the corrosion inhibitor is easy to freeze in winter, which brings inconvenience to the addition of the corrosion inhibitor. Solid block-shaped anti-corrosion blocks are also adopted, but the anti-corrosion blocks have large shapes, the adding process is complicated, the well shut-down operation is required, and the anti-corrosion effect of the method is not ideal. Many corrosion-resistant blocks in the market are easy to be pulverized at high temperature and high pressure or the water-dissolving performance does not reach the standard, and the long-term anti-scaling and slow-release requirements cannot be met.
Currently, solid corrosion inhibitors used in the oilfield field are classified into the following categories:
(1) the preparation method of the micro-particles protected by the application number CN03813457.8 adopts a physical and chemical method to prepare the micro-particles which can be used for scale prevention and corrosion prevention of an oil field, and the natural settleability of the micro-particles prepared by the method in the using process needs to be further improved;
(2) the formula, the preparation method and the use method of the solid corrosion inhibitor protected by the application number CN200510090151.2 use epoxy resin as a bonding agent to prepare the annular solid corrosion inhibitor, and the corrosion inhibitor prepared by the method has more residues in the underground;
(3) the 'natural gas well instant solid corrosion inhibitor protected by Chinese patent CN201210580000.4 and the preparation method thereof' use Arabic gum as a binder to prepare a rod-shaped instant solid corrosion inhibitor for a natural gas well, and because the Arabic gum has good water solubility, the durability of the solid corrosion inhibitor at the bottom of the well needs to be further improved;
(4) the application number CN201510696426.X protects the solid scale and corrosion inhibitor for the oil well and the preparation method thereof, polyethylene glycol is used as a curing medium to prepare the solid scale and corrosion inhibitor for the oil well, and the polyethylene glycol also has the problem of poor stability in underground water-oil mixed liquor.
Disclosure of Invention
The embodiment of the invention provides a solid corrosion inhibition capsule, a preparation method and an application method thereof, aiming at solving the problems of poor natural settleability, more underground residues, poor durability and poor stability of the existing solid corrosion inhibitor; the second purpose is to solve the problem that the slow release rate of the corrosion inhibitor is not controllable.
In order to solve the technical problem, the invention provides a solid corrosion inhibition capsule, which comprises an inner core and an outer coating film wrapping the inner core;
the inner core is composed of an inorganic nano framework, a weighting agent and a corrosion inhibitor according to a proportion;
the outer covering film is a naturally degradable high molecular polymer film.
Further, the inorganic nano-framework is formed by mixing inorganic nano-particles and surface treatment liquid according to the mass ratio of 1 (10-30).
Preferably, the inorganic nanoparticles are any one of nano iron oxide and nano zinc oxide, or a combination of the two; the surface treatment liquid comprises, by mass, 1-10 parts of organosilane, 0.01-3 parts of hydrogen peroxide, 0.5-2 parts of a pH regulator and 0-3 parts of water.
Further, the inorganic nano-framework is prepared according to the following steps:
step 1, preparing a surface treatment liquid, namely mixing 1-10 parts of organosilane, 0.01-3 parts of hydrogen peroxide, 0.5-2 parts of a pH regulator and 0-3 parts of water, and uniformly stirring to prepare the surface treatment liquid;
and 2, mixing the inorganic nano particles with the surface treatment liquid according to the mass ratio of (10) - (30) in the step 1, stirring for 1-2 hours at 65-85 ℃ by using a magnetic ion stirrer to obtain treated inorganic nano particles, and sequentially filtering, cleaning and drying at constant temperature and negative pressure for 24-48 hours to obtain the inorganic nano framework.
Preferably, the weighting agent consists of 1-4 of sodium silicate, sodium nitrate, sodium sulfate, sodium carbonate, zinc sulfate, silicon dioxide and talcum powder; the corrosion inhibitor is any one of heterocyclic corrosion inhibitors, phosphonate corrosion inhibitors and organic amine corrosion inhibitors.
Further, the high-molecular polymer film comprises, by mass, 1-2 parts of vinyl acetate, 4-8.6 parts of methanol, 0.04-0.06 part of azobisisobutyronitrile, 0.6-1.5 part of hydroquinone, 0.5-1 part of sodium hexadecylsulfonate, 0.5-1 part of sorbitan monostearate, and 0-5 parts of lauryl alcohol ether phosphate.
Further, the high molecular polymer film is prepared according to the following steps:
step a, adding vinyl acetate, methanol and azodiisobutyronitrile into a reaction kettle according to the mixture ratio, reacting for 100min at the temperature of 60 ℃, adding hydroquinone, stopping heating, stirring for 5min, and cooling to room temperature to obtain a reactant PVAC-1;
b, adding vinyl acetate, methanol and azodiisobutyronitrile into a reaction kettle according to the mixture ratio, reacting for 130min at the temperature of 60 ℃, adding hydroquinone, stopping heating, stirring for 5min, and cooling to room temperature to obtain a reactant PVAC-2;
step c, adding vinyl acetate, methanol and azodiisobutyronitrile into a reaction kettle according to the mixture ratio, reacting for 180min at the temperature of 60 ℃, adding hydroquinone, stopping heating, stirring for 5min, and cooling to room temperature to obtain a reactant PVAC-3;
and d, uniformly mixing PVAC-1, PVAC-2 and PVAC-3 according to the mass ratio of 1 (1-3) to 0.5-2.5 to obtain a mixture PVAC-4, and heating at the temperature of 70 ℃ until the content of methanol in the mixture PVAC-4 is less than 10% to obtain the high polymer film.
The invention also provides a preparation method of the solid corrosion inhibition capsule, which comprises the following steps:
step S1, mixing the inorganic nano-framework and the corrosion inhibitor according to the mass ratio of 1 (50-80), and stirring for 4-8 hours by using a high-speed stirrer to form uniform and stable viscous liquid;
step S2, adding the weighting agent into the viscous liquid obtained in the step S1 according to the mass ratio of 1 (0.2-0.8) of the corrosion inhibitor to the weighting agent, stirring for 1-12 hours until the weighting agent is uniformly dispersed in the viscous liquid to form uniform liquid;
step S3, adding the uniform liquid obtained in the step S2, PVAC-4, sodium hexadecyl sulfonate, sorbitan monostearate and lauryl alcohol ether phosphate into a stirring kettle according to the proportion, and uniformly mixing to obtain PVAC-5;
and step S4, extruding PVAC-5 into strips by using a double-screw extruder, and then preparing spherical particles with the diameter of 1-3 mm and the water content of 3-8% and micropores by using a granulator to prepare the solid corrosion inhibition capsule.
The invention also provides an application method of the solid corrosion inhibition capsule, the prepared solid corrosion inhibition capsule is put into an oil casing, an oil well pump, a ground pipeline, ground equipment and the bottom of an oil well, when the solid corrosion inhibition capsule freely settles to a water layer in a pocket at the bottom of the well, the micropores of the solid corrosion inhibition capsule slowly release the corrosion inhibitor at a constant speed within 3 months, the released corrosion inhibitor is diffused into crude oil in a shaft, and an outer coating film of the solid corrosion inhibition capsule is degraded in produced liquid of the oil well, so that the corrosion prevention of the solid corrosion inhibition capsule on the oil field equipment is completed.
The invention has the following beneficial effects:
(1) the invention adopts the outer polymer composite membrane to wrap the inner inorganic framework to jointly form a stable structure, and the micropores on the solid microcapsule are utilized to slowly release the corrosion inhibitor, and the released corrosion inhibitor can gradually diffuse into the crude oil in the shaft, thereby achieving the purpose of one-time injection and long-term corrosion prevention.
(2) The invention adopts the normal temperature to fully mix the polymer composite membrane and the inorganic framework, adopts the twin-screw extrusion and the granulation machine to process the mixture into spherical particles with the diameter of 1mm to 3mm, the water content of the particles is controlled between 3 percent and 8 percent, which is beneficial to keeping the strength of the particles, and the indoor evaluation shows that the particles can be stably released in water under the condition of 10 MPa.
(3) The internal inorganic framework of the invention can meet the strength required by the product and can also achieve the purpose of dispersing inorganic materials; the external film can realize the slow release of the slow release agent, and finally can realize the complete degradation in the produced liquid of the oil well, and the dissolution speed meets the requirement that the corrosion inhibition particles are slowly released in the well bottom for 3 months.
(4) The density of the solid corrosion inhibition capsule prepared by the invention is 1.4g/cm3～1.5g/cm3Can freely settle to a water layer of a well bottom pocket, and is prevented from being brought out by produced fluid of an oil well.
Detailed Description
The following description of the embodiments of the present invention is provided for illustrative purposes, and other advantages and effects of the present invention will become apparent to those skilled in the art from the present disclosure.
Unless otherwise defined, terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Further, it will be understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and will not be interpreted in an idealized or overly formal sense.
The invention provides a solid corrosion inhibition capsule, which comprises an inner core and an outer coating film wrapping the inner core;
the inner core is composed of an inorganic nano framework, a weighting agent and a corrosion inhibitor according to a proportion;
the outer covering film is a naturally degradable high molecular polymer film.
The invention also provides a preparation method of the solid corrosion inhibition capsule, which comprises the following steps:
step S1, mixing the inorganic nano-framework and the corrosion inhibitor according to the mass ratio of 1 (50-80), and stirring for 4-8 hours by using a high-speed stirrer to form uniform and stable viscous liquid;
step S2, adding the weighting agent into the viscous liquid obtained in the step S1 according to the mass ratio of the corrosion inhibitor to the weighting agent of 1 (0.2-0.8), and stirring for 1-12 hours until the weighting agent is uniformly dispersed in the viscous liquid to form uniform liquid;
step S3, adding the uniform liquid obtained in the step S2, PVAC-4, sodium hexadecylsulfonate, sorbitan monostearate and lauryl alcohol ether phosphate into a stirring kettle according to the proportion, and uniformly mixing to obtain PVAC-5;
and step S4, extruding PVAC-5 into strips by using a double-screw extruder, and then preparing spherical particles with the diameter of 1-3 mm and the water content of 3-8% and micropores by using a granulator to prepare the solid corrosion inhibition capsule.
The invention also provides an application method of the solid corrosion inhibition capsule, the prepared solid corrosion inhibition capsule is put into an oil casing, an oil well pump, a ground pipeline, ground equipment and the bottom of an oil well, when the solid corrosion inhibition capsule freely settles to a water layer in a pocket at the bottom of the well, the micropores of the solid corrosion inhibition capsule slowly release the corrosion inhibitor at a constant speed within 3 months, the released corrosion inhibitor is diffused into crude oil in a shaft, and an outer coating film of the solid corrosion inhibition capsule is degraded in produced liquid of the oil well, so that the corrosion prevention of the solid corrosion inhibition capsule on the oil field equipment is completed.
Further, the inorganic nano-framework is formed by mixing inorganic nano-particles and surface treatment liquid according to the mass ratio of 1 (10-30); the inorganic nano particles are any one of nano iron oxide and nano zinc oxide or the combination of the two; the surface treatment liquid comprises, by mass, 1-10 parts of organosilane, 0.01-3 parts of hydrogen peroxide, 0.5-2 parts of a pH regulator and 0-3 parts of water.
Further, the inorganic nano-framework is prepared according to the following steps:
step 1, preparing a surface treatment liquid, namely mixing 1-10 parts of organosilane, 0.01-3 parts of hydrogen peroxide, 0.5-2 parts of a pH regulator and 0-3 parts of water, and uniformly stirring to prepare the surface treatment liquid;
and 3, mixing the inorganic nano particles with the surface treatment liquid according to the mass ratio of 1 (10-30), stirring for 1-2 hours at 65-85 ℃ by using a magnetic ion stirrer to obtain treated inorganic nano particles, and sequentially filtering, cleaning and drying at constant temperature and negative pressure for 24-48 hours to obtain the inorganic nano framework.
Preferably, the weighting agent is composed of 1-4 of sodium silicate, sodium nitrate, sodium sulfate, sodium carbonate, zinc sulfate, silicon dioxide and talcum powder; the corrosion inhibitor is any one of heterocyclic corrosion inhibitors, phosphonate corrosion inhibitors, aldehyde ketone corrosion inhibitors and organic amine corrosion inhibitors.
Further, the high-molecular polymer film comprises, by mass, 1-2 parts of vinyl acetate, 4-8.6 parts of methanol, 0.04-0.06 part of azobisisobutyronitrile, 0.6-1.5 part of hydroquinone, 0.5-1 part of sodium hexadecylsulfonate, 0.5-1 part of sorbitan monostearate, and 0-5 parts of lauryl alcohol ether phosphate.
Further, the high molecular polymer film is prepared according to the following steps:
step a, adding vinyl acetate, methanol and azodiisobutyronitrile into a reaction kettle according to the mixture ratio, reacting for 100min at the temperature of 60 ℃, adding hydroquinone, stopping heating, stirring for 5min, and cooling to room temperature to obtain a reactant PVAC-1;
b, adding vinyl acetate, methanol and azodiisobutyronitrile into a reaction kettle according to the mixture ratio, reacting for 130min at the temperature of 60 ℃, adding hydroquinone, stopping heating, stirring for 5min, and cooling to room temperature to obtain a reactant PVAC-2;
step c, adding vinyl acetate, methanol and azodiisobutyronitrile into a reaction kettle according to the mixture ratio, reacting for 180min at the temperature of 60 ℃, adding hydroquinone, stopping heating, stirring for 5min, and cooling to room temperature to obtain a reactant PVAC-3;
and d, uniformly mixing PVAC-1, PVAC-2 and PVAC-3 according to the mass ratio of 1 (1-3) to 0.5-2.5 to obtain a mixture PVAC-4, and heating at the temperature of 70 ℃ until the content of methanol in the mixture PVAC-4 is less than 10% to obtain the high polymer film.
First embodiment
This embodiment protects a solid corrosion inhibiting capsule comprising an inner core and an outer coating surrounding the inner core. The inner core is composed of inorganic nanometer skeleton, weighting agent and corrosion inhibitor according to a certain proportion.
Wherein the inorganic nano-skeleton is formed by mixing inorganic nano-particles and surface treatment liquid according to the mass ratio of 1: 10; the inorganic nano particles are nano ferric oxide; the surface treatment liquid comprises, by mass, 1 part of organosilane, 0.01 part of hydrogen peroxide, 0.5 part of pH regulator and 1 part of water.
The inorganic nano-framework is prepared by the following steps:
step 1, preparing a surface treatment solution, namely mixing 1 part of organosilane, 0.01 part of hydrogen peroxide, 0.5 part of pH regulator and 1 part of water according to a ratio and uniformly stirring to prepare the surface treatment solution;
and 2, mixing the inorganic nano particles with the surface treatment liquid according to the mass ratio of 1:10, stirring for 1-2 hours at 65-85 ℃ by using a magnetic ion stirrer to obtain treated inorganic nano particles, and sequentially filtering, cleaning and drying at constant temperature and negative pressure for 24-48 hours to obtain the inorganic nano framework.
The weighting agent is a mixture of sodium nitrate, zinc sulfate and silicon dioxide with the mesh number of 500.
The corrosion inhibitor comprises the following components in parts by mass: 60 parts of imidazoline and 40 parts of benzyl quinoline chloride.
The outer covering film is a naturally degradable high molecular polymer film, and the preparation steps are as follows:
step a, adding vinyl acetate, methanol and azobisisobutyronitrile into a reaction kettle, wherein 1 part of vinyl acetate, 4 parts of methanol and 0.05 part of azobisisobutyronitrile are added, the reaction temperature is controlled at 65 ℃, after the reaction is carried out for 100 minutes, adding 0.6 part of hydroquinone into the reaction system, stopping heating, continuing stirring for 5 minutes, and cooling to room temperature to obtain a reactant PVAC-1;
step b, the mixture ratio and the reaction conditions of reactants are the same as those in the step a, after the reaction is carried out for 130 minutes, 0.6 part of hydroquinone is added into the reaction system, the heating is stopped, the stirring is continued for 5 minutes, the temperature is reduced to the room temperature, and the obtained reactant is PVAC-2;
c, the mixture ratio and the reaction conditions of the reactants are the same as those in the step a, after the reaction is carried out for 180 minutes, the heating is stopped, the stirring is continued for 5 minutes, the temperature is reduced to the room temperature, and the obtained reactant is PVAC-3;
step d, uniformly mixing reactants PVAC-1, PVAC-2 and PVAC-3 according to the mass ratio of 1:2:1 to form a mixture PVAC-4; heating the mixture PVAC-4 to 65 ℃, and slowly evaporating the methanol and the incompletely reacted monomers in the mixed system to finally ensure that the content of the methanol in the mixed system is less than 10 percent to prepare the high molecular polymer film.
The steps for preparing the solid corrosion inhibition capsule in the embodiment are as follows:
step S1, corrosion inhibitor loading
Mixing the inorganic nanoparticles subjected to surface treatment with the corrosion inhibitor according to the mass ratio of 1:80, and stirring for 8 hours by using a high-speed stirrer to form uniform and stable viscous liquid;
step S2, adding weighting agent
Adding weighting agents (sodium nitrate, zinc sulfate and silicon dioxide) with the mesh number of 500 into the viscous liquid according to the mass ratio of 1:0.6 of the corrosion inhibitor to the weighting agents, and stirring for 60min to 12h until the weighting agents are uniformly dispersed in the liquid to form new uniform liquid;
step S3, preparation of capsules
Uniformly mixing the uniform liquid with a polymer film material PVAC-4, sodium hexadecyl sulfonate, span60 (sorbitan monostearate) and lauryl alcohol ether phosphate in a stirring kettle to obtain PVAC-5, wherein the addition amounts of the PVAC-5, the span60 and the lauryl alcohol ether phosphate are respectively 0.5 part of sodium hexadecyl sulfonate, 0.5 part of span60 and 3 parts of lauryl alcohol ether phosphate; extruding the mixture PVAC-5 into strips by using a double-screw extruder, and preparing the strips into strips with the diameter of 1mm and the density of 1.46g/cm by using a granulator3The solid capsule corrosion inhibition particles are obtained, and the coating rate of the organic corrosion inhibitor in the solid capsule corrosion inhibition particles is 66%.
Second embodiment
This embodiment protects a solid corrosion inhibiting capsule comprising an inner core and an outer coating surrounding the inner core. The inner core is composed of inorganic nanometer skeleton, weighting agent and corrosion inhibitor according to a certain proportion.
Wherein the inorganic nano-skeleton is formed by mixing inorganic nano-particles and surface treatment liquid according to the mass ratio of 1: 15; the inorganic nano particles are nano iron oxide; the surface treatment liquid comprises, by mass, 4 parts of organosilane, 1.5 parts of hydrogen peroxide, 1 part of pH regulator and 0 part of water.
The inorganic nano-framework is prepared by the following steps:
step 1, preparing a surface treatment liquid, namely mixing 4 parts of organosilane, 1.5 parts of hydrogen peroxide, 1 part of pH regulator and 0 part of water according to a ratio, and uniformly stirring to prepare the surface treatment liquid;
and 2, mixing the inorganic nano particles with the surface treatment liquid according to the mass ratio of 1:20, stirring for 1-2 hours at 65-85 ℃ by using a magnetic ion stirrer to obtain treated inorganic nano particles, and sequentially filtering, cleaning and drying at constant temperature and negative pressure for 24-48 hours to obtain the inorganic nano skeleton.
The weighting agent is a mixture of sodium carbonate, zinc sulfate, silicon dioxide and talcum powder with the mesh number of 500.
The corrosion inhibitor comprises the following components in parts by mass: 50 parts of phosphono carboxylic acid copolymer, 30 parts of ATMP (amino trimethylene phosphonic acid) and 20 parts of DTPMP (diethylenetriamine pentamethylene phosphonic acid).
The outer covering film is a naturally degradable high molecular polymer film, and the preparation steps are as follows:
step a, adding vinyl acetate, methanol and azobisisobutyronitrile into a reaction kettle, wherein the vinyl acetate is 1.5 parts, the methanol is 6 parts, the azobisisobutyronitrile is 0.04 part, the reaction temperature is controlled at 65 ℃, after the reaction is carried out for 100 minutes, adding 0.6 part of hydroquinone into the reaction system, stopping heating, continuously stirring for 5 minutes, and cooling to room temperature to obtain a reactant PVAC-1;
step b, the mixture ratio and the reaction conditions of the reactants are the same as those in the step a, after the reaction is carried out for 130 minutes, 1 part of hydroquinone is added into the reaction system, the heating is stopped, the stirring is continued for 5 minutes, the temperature is reduced to the room temperature, and the obtained reactant is PVAC-2;
c, the mixture ratio and the reaction conditions of the reactants are the same as those in the step a, after the reaction is carried out for 180 minutes, the heating is stopped, the stirring is continued for 5 minutes, the temperature is reduced to the room temperature, and the obtained reactant is PVAC-3;
step d, uniformly mixing reactants PVAC-1, PVAC-2 and PVAC-3 according to the mass ratio of 1:2.5:2 to form a mixture PVAC-4; heating the mixture PVAC-4 to 65 ℃, and slowly evaporating the methanol and the incompletely reacted monomers in the mixed system to finally ensure that the content of the methanol in the mixed system is less than 10 percent to prepare the high molecular polymer film.
The steps for preparing the solid corrosion inhibition capsule in the embodiment are as follows:
step S1, corrosion inhibitor loading
Mixing the inorganic nanoparticles subjected to surface treatment with a corrosion inhibitor according to a mass ratio of 1:60, and stirring for 8 hours by using a high-speed stirrer to form uniform and stable viscous liquid;
step S2, adding weighting agent
Adding weighting agents (sodium nitrate, zinc sulfate and silicon dioxide) with the mesh number of 500 into the viscous liquid according to the mass ratio of 1:0.2 of the corrosion inhibitor to the weighting agents, and stirring for 60min to 12h until the weighting agents are uniformly dispersed in the liquid to form new uniform liquid;
step S3, preparation of capsules
Uniformly mixing the uniform liquid with a polymer film material PVAC-4, sodium hexadecyl sulfonate, span60 (sorbitan monostearate) and lauryl alcohol ether phosphate in a stirring kettle to obtain PVAC-5, wherein the addition amounts of the PVAC-5 are 0.7 part of sodium hexadecyl sulfonate, 0.8 part of span60 and 1 part of lauryl alcohol ether phosphate respectively; extruding the mixture PVAC-5 into strips by using a double-screw extruder, and preparing the strips into strips with the diameter of 2mm and the density of 1.50g/cm by using a granulator3The solid capsule corrosion inhibition particles are obtained, and the coating rate of the organic corrosion inhibitor in the solid capsule corrosion inhibition particles is 59 percent.
Third embodiment
The embodiment protects a solid corrosion inhibiting capsule which comprises an inner core and an outer coating film wrapping the inner core. The inner core is composed of inorganic nanometer skeleton, weighting agent and corrosion inhibitor according to a certain proportion.
Wherein the inorganic nano-skeleton is formed by mixing inorganic nano-particles and surface treatment liquid according to the mass ratio of 1: 15; the inorganic nano particles are nano ferric oxide; the surface treatment liquid comprises, by mass, 8 parts of organosilane, 3 parts of hydrogen peroxide, 2 parts of a pH regulator and 3 parts of water.
The inorganic nano-framework is prepared by the following steps:
step 1, preparing a surface treatment solution, namely mixing 8 parts of organosilane, 3 parts of hydrogen peroxide, 2 parts of a pH regulator and 3 parts of water according to a ratio and uniformly stirring to prepare the surface treatment solution;
and 2, mixing the inorganic nano particles with the surface treatment liquid according to the mass ratio of 1:30, stirring for 1-2 hours at 65-85 ℃ by using a magnetic ion stirrer to obtain treated inorganic nano particles, and sequentially filtering, cleaning and drying at constant temperature and negative pressure for 24-48 hours to obtain the inorganic nano framework.
The weighting agent is a mixture of sodium silicate, sodium nitrate, sodium sulfate and sodium carbonate with the mesh number of 500.
The corrosion inhibitor comprises the following components in parts by mass: 60 parts of benzotriazole, 20 parts of EDTMPS (ethylene diamine tetra methylene phosphonic acid sodium) and 20 parts of HPAA (2-hydroxyphosphonoacetic acid).
The outer covering film is a naturally degradable high molecular polymer film, and the preparation steps are as follows:
step a, adding vinyl acetate, methanol and azobisisobutyronitrile into a reaction kettle, wherein the vinyl acetate is 2 parts, the methanol is 8.6 parts, the azobisisobutyronitrile is 0.06 part, the reaction temperature is controlled at 65 ℃, after the reaction is carried out for 100 minutes, adding 1.5 parts of hydroquinone into the reaction system, stopping heating, continuing stirring for 5 minutes, and cooling to room temperature to obtain a reactant PVAC-1;
step b, the mixture ratio and the reaction conditions of reactants are the same as those in the step a, after the reaction is carried out for 130 minutes, 1 part of hydroquinone is added into the reaction system, the heating is stopped, the stirring is continued for 5 minutes, the temperature is reduced to the room temperature, and the obtained reactant is PVAC-2;
c, the mixture ratio and the reaction conditions of the reactants are the same as those in the step a, after the reaction is carried out for 180 minutes, the heating is stopped, the stirring is continued for 5 minutes, the temperature is reduced to the room temperature, and the obtained reactant is PVAC-3;
step d, uniformly mixing reactants PVAC-1, PVAC-2 and PVAC-3 according to the mass ratio of 1:3:2 to form a mixture PVAC-4; heating the mixture PVAC-4 to 65 ℃, and slowly evaporating the methanol and the incompletely reacted monomers in the mixed system to finally ensure that the content of the methanol in the mixed system is less than 10 percent to prepare the high molecular polymer film.
The steps for preparing the solid corrosion inhibition capsule in the embodiment are as follows:
step S1, corrosion inhibitor loading
Mixing the inorganic nanoparticles subjected to surface treatment with a corrosion inhibitor according to a mass ratio of 1:60, and stirring for 8 hours by using a high-speed stirrer to form uniform and stable viscous liquid;
step S2, adding weighting agent
Adding weighting agents (sodium silicate, sodium nitrate, sodium sulfate and sodium carbonate) with the mesh number of 500 into the viscous liquid according to the mass ratio of 1:0.8 of the corrosion inhibitor to the weighting agents, and stirring for 60min to 12h until the weighting agents are uniformly dispersed in the liquid to form new uniform liquid;
step S3, preparation of capsules
Uniformly mixing the uniform liquid with a polymer film material PVAC-4, sodium hexadecyl sulfonate, span60 (sorbitan monostearate) and lauryl alcohol ether phosphate in a stirring kettle to obtain PVAC-5, wherein the addition amounts of the PVAC-5 are respectively 1 part of sodium hexadecyl sulfonate, 1 part of span60 and 5 parts of lauryl alcohol ether phosphate; extruding the mixture PVAC-5 into strips by using a double-screw extruder, and preparing the strips into strips with the diameter of 1.5mm and the density of 1.50g/cm by using a granulator3The solid capsule corrosion inhibition particles are obtained, and the coating rate of the organic corrosion inhibitor in the solid capsule corrosion inhibition particles is 66%.
Fourth embodiment
The invention adopts the normal temperature to fully mix the high molecular polymer film and the inorganic nanometer skeleton, adopts the twin-screw extrusion and injection to process into spherical particles with the diameter of 1 mm-3 mm by a granulator, the water content of the particles is controlled between 3 percent and 8 percent so as to be beneficial to keeping the strength of the particles, the particles can be stably released in water under the condition of 10MPa, and the indoor evaluation result shows that the release speed of the corrosion inhibitor is 8-10 mg/L.d.g.
The field test of 5 wells shows that the effective content test of the corrosion inhibitor in the produced liquid of the well head shows that:
starting from the third day after the corrosion inhibitor is put into the well, the effective content of the corrosion inhibitor in the produced liquid reaches 70-100 ppm, the content of the corrosion inhibitor in the produced liquid is stable after continuous tracking analysis for 5 months, the concentration of the corrosion inhibitor begins to decrease about 105 days, the concentration of the corrosion inhibitor in the produced liquid is reduced by 50ppm at 120 days, and the capsule corrosion inhibitor needs to be added.
The traditional solid corrosion inhibitor needs to be suspended at the bottom of an oil pumping pipe for filling through a special tool because of the problems of density, easy swelling, upward floating and the like in the release process, and a well is stopped and a pipe column is lifted when the traditional solid corrosion inhibitor is added.
The capsule corrosion inhibitor prepared by the invention is the biggest difference from the conventional solid corrosion inhibitor in that the traditional solid corrosion inhibitor is processed into particles by changing the formula and the processing technology, the adding technology is simple, and the release performance in a shaft is not reduced compared with the conventional solid corrosion inhibitor.
In conclusion, the invention adopts the outer polymer composite film to wrap the inner inorganic framework, and jointly forms a stable structure, the micro-pores on the solid microcapsule are utilized to slowly release the corrosion inhibitor, and the released corrosion inhibitor can gradually diffuse into the crude oil in the shaft, thereby achieving the purpose of one-time injection and long-term corrosion prevention; fully mixing the polymer composite film and the inorganic framework at normal temperature, extruding and injecting by adopting a double screw rod, processing into spherical particles with the diameter of 1-3 mm by using a granulator, controlling the water content of the particles to be 3-8% so as to be beneficial to keeping the strength of the particles, and performing indoor evaluation to ensure that the particles can be stably released in water under the condition of 10 MPa; the internal inorganic framework can meet the strength required by the product and can also play a role in dispersing inorganic materials; the slow release agent can be slowly released by the external film, and finally the complete degradation can be realized in the produced liquid of the oil well, and the dissolution speed meets the requirement that the corrosion inhibition particles are slowly released in the well bottom for 3 months; the prepared solid corrosion inhibition capsule has the density of 1.4g/cm3～1.5g/cm3Can freely settle to a water layer of a well bottom pocket, and is prevented from being brought out by produced fluid of an oil well.
It will be understood by those of ordinary skill in the art that the foregoing embodiments are specific examples for carrying out the invention, and that various changes in form and details may be made therein without departing from the spirit and scope of the invention in practice.
Claims (4)
1. A solid corrosion inhibition capsule is characterized by comprising an inner core and an outer coating film wrapping the inner core;
the inner core is composed of an inorganic nano-framework, a weighting agent and a corrosion inhibitor in proportion, and the inorganic nano-framework is prepared according to the following steps:
step 1, preparing a surface treatment liquid, namely taking 1-10 parts of organosilane, 0.01-3 parts of hydrogen peroxide, 0.5-2 parts of pH value regulator and 0-3 parts of water, mixing and uniformly stirring the components to prepare the surface treatment liquid;
step 2, mixing the inorganic nano particles and the surface treatment liquid according to the mass ratio of 1 (10-30), stirring for 1-2 hours at 65-85 ℃ by using a magnetic ion stirrer to obtain treated inorganic nano particles, and sequentially filtering, cleaning and drying at constant temperature and negative pressure for 24-48 hours to obtain an inorganic nano framework;
wherein the inorganic nano-particles are any one of nano-iron oxide and nano-zinc oxide or the combination of the two;
the outer covering film is a naturally degradable high molecular polymer film and comprises the following components, by mass, 1-2 parts of vinyl acetate, 4-8.6 parts of methanol, 0.04-0.06 part of azodiisobutyronitrile, 0.6-1.5 parts of hydroquinone, 0.5-1 part of sodium hexadecylsulfonate, 0.5-1 part of sorbitan monostearate and 0-5 parts of lauryl alcohol ether phosphate;
the preparation method of the solid corrosion inhibition capsule comprises the following steps:
step S1, mixing the inorganic nano-framework and the corrosion inhibitor according to the mass ratio of 1 (50-80), and stirring for 4-8 hours by using a high-speed stirrer to form uniform and stable viscous liquid;
step S2, adding the weighting agent into the viscous liquid obtained in the step S1 according to the mass ratio of the corrosion inhibitor to the weighting agent of 1 (0.2-0.8), and stirring for 1-12 hours until the weighting agent is uniformly dispersed in the viscous liquid to form uniform liquid;
step S3, adding the uniform liquid obtained in the step S2, a polymer membrane material PVAC-4, sodium hexadecyl sulfonate, sorbitan monostearate and lauryl alcohol ether phosphate into a stirring kettle according to a ratio, and uniformly mixing to obtain PVAC-5;
step S4, extruding PVAC-5 into strips by using a double-screw extruder, and then preparing spherical particles with 1-3 mm diameter and 3-8% water content and micropores by using a granulator to prepare solid corrosion inhibition capsules;
the polymer membrane material PVAC-4 is prepared by the following steps:
step a, adding vinyl acetate, methanol and azodiisobutyronitrile into a reaction kettle according to the mixture ratio, reacting for 100min at the temperature of 60 ℃, adding hydroquinone, stopping heating, stirring for 5min, and cooling to room temperature to obtain a reactant PVAC-1;
b, adding vinyl acetate, methanol and azodiisobutyronitrile into a reaction kettle according to the mixture ratio, reacting for 130min at the temperature of 60 ℃, adding hydroquinone, stopping heating, stirring for 5min, and cooling to room temperature to obtain a reactant PVAC-2;
step c, adding vinyl acetate, methanol and azodiisobutyronitrile into a reaction kettle according to the mixture ratio, reacting for 180min at the temperature of 60 ℃, adding hydroquinone, stopping heating, stirring for 5min, and cooling to room temperature to obtain a reactant PVAC-3;
and d, uniformly mixing the PVAC-1, the PVAC-2 and the PVAC-3 according to the mass ratio of 1 (1-3) to 0.5-2.5 to obtain a mixture PVAC-4, and heating at the temperature of 70 ℃ until the content of methanol in the mixture PVAC-4 is less than 10% to obtain the polymer membrane material PVAC-4.
2. The solid corrosion inhibiting capsule of claim 1, wherein the weighting agent is comprised of 1 to 4 of sodium silicate, sodium nitrate, sodium sulfate, sodium carbonate, zinc sulfate, silica, talc; the corrosion inhibitor is any one of heterocyclic corrosion inhibitors, phosphonate corrosion inhibitors and organic amine corrosion inhibitors.
3. A process for the preparation of a solid corrosion inhibiting capsule according to claim 1 or 2, wherein the process comprises the steps of:
step S1, mixing the inorganic nano-framework and the corrosion inhibitor according to the mass ratio of 1 (50-80), and stirring for 4-8 hours by using a high-speed stirrer to form uniform and stable viscous liquid;
step S2, adding the weighting agent into the viscous liquid obtained in the step S1 according to the mass ratio of the corrosion inhibitor to the weighting agent of 1 (0.2-0.8), and stirring for 1-12 hours until the weighting agent is uniformly dispersed in the viscous liquid to form uniform liquid;
step S3, adding the uniform liquid obtained in the step S2, a polymer membrane material PVAC-4, sodium hexadecyl sulfonate, sorbitan monostearate and lauryl alcohol ether phosphate into a stirring kettle according to a ratio, and uniformly mixing to obtain PVAC-5;
and step S4, extruding PVAC-5 into strips by using a double-screw extruder, and then preparing spherical particles with the diameter of 1-3 mm and the water content of 3-8% and micropores by using a granulator to prepare the solid corrosion inhibition capsule.
4. An application method of the solid corrosion inhibition capsule is characterized in that the solid corrosion inhibition capsule prepared by the preparation method of claim 3 is put into an oil casing, an oil well pump, a ground pipeline, ground equipment and the bottom of an oil well, when the solid corrosion inhibition capsule freely settles to a water layer in a pocket at the bottom of the well, micro pores of the solid corrosion inhibition capsule slowly release corrosion inhibitors at a constant speed within 3 months, the released corrosion inhibitors diffuse into crude oil in a shaft, and an outer coating film of the solid corrosion inhibition capsule is degraded in produced liquid of the oil well, so that the corrosion prevention of the solid corrosion inhibition capsule on the oil field equipment is completed.
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| CN111827931A (en) * | 2020-08-06 | 2020-10-27 | 中国石油天然气股份有限公司 | Method for filling capsule anti-scale particles for oil well |
| CN112063376A (en) * | 2020-08-20 | 2020-12-11 | 汉中聚智达远环能科技有限公司 | Solid corrosion inhibition capsule for oil extraction and preparation method and application method thereof |
| CN116023920A (en) * | 2022-11-11 | 2023-04-28 | 天津大港油田滨港集团博弘石油化工有限公司 | Environment-friendly tetracyclic imidazoline solid corrosion inhibitor and preparation method thereof |
| CN116396739A (en) * | 2023-04-13 | 2023-07-07 | 河北浩威旭光新材料科技有限公司 | Solid slow-release anti-corrosion particles for oil well and preparation method thereof |
| CN117488307B (en) * | 2023-11-03 | 2024-04-16 | 东莞市德硕化工有限公司 | Metal surface treating agent and preparation method thereof |
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