CN109554714B - A kind of granular solids corrosion inhibiter and preparation method thereof - Google Patents
A kind of granular solids corrosion inhibiter and preparation method thereof Download PDFInfo
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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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Abstract
The present invention relates to a kind of granular solids corrosion inhibiter and preparation method thereof, belong to metal material technical field of anticorrosion.Granular solids corrosion inhibiter of the invention, the component including following parts by weight: 50~55 parts of inhibition host agent, 5~10 parts of synergist, 2.5~21 parts of film forming agent, 4~11 parts of adhesive, 3~5 parts of lubricant, 5~8 parts of nonionic surfactant and 20~25 parts of heavy weight additive；The inhibition host agent is imidazoline quaternary ammonium salt.Granular solids corrosion inhibiter of the invention, nontoxic, to oil reservoir fanout free region, dissolved medicament is dispersed in production fluid, is uniformly adsorbed on oil jacket inside pipe wall with liquid is produced, is played the role of inhibiting corrosion, extend the anti-corrosion period.
Description
Technical field
The present invention relates to a kind of granular solids corrosion inhibiter and preparation method thereof, belong to metal material technical field of anticorrosion.
Background technique
As the continuous exploitation of oil gas field produces, the composite water cut of oil/gas well is persistently increased, and contains in production fluid
A large amount of corrosive medium causes downhole production tube corrosion to aggravate.The common method for inhibiting corrosion is to add liquid inhibition at present
Column solid corrosion inhibitor is added when agent and operation.But there are dosing heavy workloads, field conduct management when liquid corrosion inhibitor fills
Drawback difficult, medicine machine input cost is high, and it is unable to control tubing and casing under card shut-in well packer or less and normal production well pump
The problem of corrosion；Solid corrosion inhibitor has many advantages, such as that dosage is small compared with liquid corrosion inhibitor, but column solid corrosion inhibitor dosing method is deposited
In limitation, it can only throw in oil gas well operations to shaft bottom, under normal production status, cannot supplement and add, control can not be extended
The rotten period.
In the prior art, the Chinese invention patent that application publication number is CN103014718A discloses a kind of natural gas well speed
Molten solid corrosion inhibitor, the solid corrosion inhibitor be by oleic acid, tetraethylenepentamine, galic essential oil, Arabic gum high―temperature nuclei host agent with
Sodium acetate or the organic salt of tetrabutylammonium bromide mix injection mold extrusion forming and are made, and solid corrosion inhibitor deenergized period is compared with liquid
Body corrosion inhibiter is long and environment friendly and pollution-free, but corrosion inhibiter is directly exposed in the solution of underground, shortens service life.Application publication number
Disclose a kind of solution oil well for the Chinese invention patent of CN103937477A and corrode controlled release solid corrosion inhibitor, be by
Calcium alginate and the heavy weight additive being present in calcium alginate duct and solid-state corrosion inhibiter are constituted, and heavy weight additive uses BaSO4, ferrotianium
Powder, sparring powder, CaCO3Or the metal powders such as zinc powder, iron powder, the solid corrosion inhibitor realize sedimentation and controlled release, but only according to
Corrosion inhibition is played by solid-state corrosion inhibiter, it is difficult to meet inhibition demand.Application publication number is that the Chinese invention of CN104480473A is special
Benefit discloses a kind of solid corrosion inhibitor, including coating wax and solid corrosion inhibitor particle ball, and the coating wax is uniformly wrapped in described
Solid corrosion inhibitor particle ball surface, the solid corrosion inhibitor particle ball contain water soluble rust inhibitor, solid binder, synergist and
Foam disintegrating agent；Water soluble rust inhibitor is glucose amide corrosion inhibiter or imidazoline corrosion inhibitor, and solid binder is water solubility
Starch, Self- raising flour, gummi arabicum pulveratum, sodium cellulose glycolate, synergist are sodium sulfite, acetoxime, thiocarbamide, and the solid is slow
Erosion agent can be realized the protection to long range last tube, but oil/gas well cannot add use during normal production, it is necessary to operation
When disposably add, cannot supplement on time, anti-corrosion timeliness is limited.
Summary of the invention
The object of the present invention is to provide a kind of dispensings flexibly, the anti-corrosion period is long, favorable anti-corrosion effect granular solids corrosion inhibiter.
The present invention also provides a kind of preparation methods of above-mentioned granular solids corrosion inhibiter.
In order to achieve the goal above, technical solution used by granular solids corrosion inhibiter of the invention is:
A kind of granular solids corrosion inhibiter, the component including following parts by weight: 50~55 parts of inhibition host agent, synergist 5~
10 parts, 2.5~21 parts of film forming agent, 4~11 parts of adhesive, 3~5 parts of lubricant, 5~8 parts of nonionic surfactant and exacerbation
20~25 parts of agent；The inhibition host agent is imidazoline quaternary ammonium salt.
Granular solids corrosion inhibiter of the invention, nontoxic, to oil reservoir fanout free region, dissolved medicament is dispersed in production fluid,
It is uniformly adsorbed on oil jacket inside pipe wall with liquid is produced, plays the role of inhibiting corrosion, extends the anti-corrosion period, have following excellent
Point: 1) it can in due course supplement: be added at any time in the case where oil-water well normally produces, without waiting for operation；2) on-site construction operations
Simplicity can be added at any time by oil jacket annulus or be added in oil jacket annulus by dedicated filing provision through sleeve valve, fall into well
Bottom, well head greatly reduce the investment of medicine machine without being equipped with device for continuously adding medicine；3) service life is long；Medicament is sink to well
Bottom extends action time, validity period at 90 days or more, reduces field management difficulty by being slowly dissolved release；4) live
Safety is added, is less prone to blocking phenomenon with water carrying when adding；5) rate of dissolution is controllable；It can be according to scene temperature, Liquid output
Etc. demands, medicament is adjusted, is effectively controlled the rate of dissolution of granular solids corrosion inhibiter, extends action time；6) prevent
Rotten effect is good, and absorption film-forming performance is good, has the control high CO of high temperature2/H2Corrosion under S partial pressure and high liquid measure to metal pipe material, is protected
Demonstrate,prove oil/gas well service life.
Preferably, solid corrosion inhibitor includes the component of following parts by weight: 50~55 parts of inhibition host agent, synergist 5~8
Part, 4~21 parts of film forming agent, 4~11 parts of adhesive, 3~5 parts of lubricant, 5~7 parts of nonionic surfactant and heavy weight additive 20
~25 parts；The inhibition host agent is imidazoline quaternary ammonium salt.
The granular solids corrosion inhibiter includes corrosion inhibiter particle and the coating material for being coated on corrosion inhibiter particle surface；It is described
Corrosion inhibiter particle is mainly composed of the following parts by weight: 50~55 parts of inhibition host agent, 5~10 parts of synergist, film forming agent
2.5~21 parts, 4~11 parts of adhesive, 3~5 parts of lubricant, 5~8 parts of nonionic surfactant and 20~25 parts of heavy weight additive；
The mass ratio of the coating material and corrosion inhibiter particle is 1:30~100.It is coated in corrosion inhibiter particle surface more enough into one
Step extends the service life of granular solids corrosion inhibiter.
Preferably, the solid corrosion inhibitor is mainly composed of the following parts by weight: 50~55 parts of inhibition host agent increases
Imitate 5~8 parts of agent, 4~21 parts of film forming agent, 4~11 parts of adhesive, 3~5 parts of lubricant, 5~7 parts of nonionic surfactant and
20~25 parts of heavy weight additive.
The partial size of the granular solids corrosion inhibiter is 5~10mm.
The imidazoline quaternary ammonium salt is benzoic acid imidazoline quaternary ammonium salt, imidazole salicylate hyamine, oleic imidazolinone season
At least one of ammonium salt.
The molecular structure of the imidazoline quaternary ammonium salt are as follows:
Wherein, R is phenyl, o-hydroxy-phenyl or CH3(CH2)7CH=CH (CH2)7-；R1For phenyl or-COONa.
The imidazoline quaternary ammonium salt is made using the method included the following steps: by imidazoline intermediate, quaternizing agent,
Ethylene glycol is added in the reactor equipped with condensation reflux unit simultaneously according to the ratio that molar ratio is 1:0.95:0.2,120
At DEG C react 4h to get；The quaternizing agent is benzyl chloride or sodium chloroacetate, is reacted as follows:
Wherein, R is phenyl, o-hydroxy-phenyl or CH3(CH2)7CH=CH (CH2)7-；R1CH2Cl is benzyl chloride or monoxone
Sodium.
Preferably, the nonionic surfactant be fatty alcohol polyoxyethylene ether, in alkyl phenol polyoxyethylene ether extremely
Few one kind.
It is further preferred that the fatty alcohol polyoxyethylene ether is AEO-20 or AEO-9 at least one.The alkyl phenol is poly-
Ethylene oxide ether is NP-30.
Preferably, the synergist is at least one of hexamethylenetetramine, sodium nitrite.It is further preferred that institute
Synergist is stated to be made of hexamethylenetetramine and sodium nitrite；The mass ratio of hexamethylenetetramine and sodium nitrite be 0.5~
1.5:1。
Preferably, described adhesive is at least one of Petropols, polyvinyl alcohol.It is further preferred that described viscous
Mixture is made of Petropols and polyvinyl alcohol；The mass ratio of Petropols and polyvinyl alcohol is 1~3:1.Still more preferably
, the mass ratio of Petropols and polyvinyl alcohol is 1.5~2:1.
Preferably, the lubricant is at least one of polyethylene glycol, talcum powder.Preferably, the polyethylene glycol
Molecular weight is 3000~5000.
Preferably, the film forming agent is at least one of pregelatinized starch, sodium carboxymethyl starch.
Preferably, in step 3), the film forming agent is that pregelatinized starch and sodium carboxymethyl starch form, pregelatinized starch and
The mass ratio of sodium carboxymethyl starch is 1:0.35~2.
Preferably, the heavy weight additive is sodium chloride.
Preferably, the coating material includes basis material；Described matrix material is acrylic resin, carboxylic hydroxypropyl methyl fibre
Tie up at least one of element.
It is further preferred that the coating material further includes wetting agent；The mass ratio of described matrix material and wetting agent is
2:4~6.
The wetting agent is at least one of Tween 80, polysorbate60.The acrylic resin is by II He of acrylic resin
Acrylic resin III forms, and the mass ratio of acrylic resin II and acrylic resin III is 2~4:1.
The application method of granular solids corrosion inhibiter of the invention:
Granular granular solids corrosion inhibiter is added by oil jacket annulus to well by sleeve valve, granular solids corrosion inhibiter
It is sink to shaft bottom, by being slowly dissolved release, validity period was up to 90 days or more；Dissolved medicament is dispersed in production fluid, adjoint
It produces liquid and is uniformly adsorbed on oil jacket inside pipe wall, play the role of inhibiting corrosion；And the granular solids corrosion inhibiter can add at any time,
Oil/gas well production is not influenced.
For the well of not casing pressure, oil jacket annulus can be added by sleeve valve by spiral propeller in granular solids corrosion inhibiter
It is interior, it can also be carried by water to oil jacket annulus；For there is the well of casing pressure, granular solids corrosion inhibiter can pass through special resistance to press fitting
It sets, one end connects cementing truck one end connecting sleeve valve, is added by oil jacket annulus.Since granular solids corrosion inhibiter density is 1.1
~1.5g/cm3, shaft bottom can be fallen to automatically.
Technical solution used by the preparation method of granular solids corrosion inhibiter of the invention are as follows:
A kind of preparation method of above-mentioned granular solids corrosion inhibiter, comprising the following steps:
1) at 80~100 DEG C, synergist is uniformly mixed with inhibition host agent, keeps the temperature, obtains intermediate M1；
2) by nonionic surfactant and intermediate M1It mixes, obtains intermediate M2；
3) by adhesive, film forming agent, lubricant, heavy weight additive and intermediate M2It mixes, obtains intermediate M3；
4) by intermediate M3Be made corrosion inhibiter particle to get.
Compared with the preparation method of the prior art, the preparation method of granular solids corrosion inhibiter of the invention, simple process, life
Produce it is high-efficient, it is easy to promote and utilize.
Preferably, in step 1), the synergist is at least one of hexamethylenetetramine, sodium nitrite.Further
Preferably, the synergist is made of hexamethylenetetramine and sodium nitrite；The mass ratio of hexamethylenetetramine and sodium nitrite
For 0.5~1.5:1.
Preferably, the time of the heat preservation is 20~40min.
Preferably, in step 2), the nonionic surfactant is fatty alcohol polyoxyethylene ether, alkylphenol-polyethenoxy
At least one of ether.
When nonionic surfactant is at normal temperature non-liquid, after needing to melt nonionic surfactant heating again
With intermediate M1It mixes.
It is further preferred that the fatty alcohol polyoxyethylene ether is AEO-20 or AEO-9 at least one, the alkyl phenol is poly-
Ethylene oxide ether is NP-30.
Preferably, in step 3), described adhesive is at least one of Petropols, polyvinyl alcohol.Further preferably
, described adhesive is made of Petropols and polyvinyl alcohol；The mass ratio of Petropols and polyvinyl alcohol is 1~3:1.More into
One step is preferred, and the mass ratio of Petropols and polyvinyl alcohol is 1.5~2:1.
Preferably, in step 3), by adhesive, film forming agent, lubricant, heavy weight additive and intermediate M2It mixes, is that will first add
Heavy prescription, adhesive and intermediate M2It mixes, intermediate M is made21, then by intermediate M21It is mixed with film forming agent, lubricant.
Preferably, in step 3), the film forming agent is at least one of pregelatinized starch, sodium carboxymethyl starch.
Preferably, in step 3), the film forming agent is that pregelatinized starch and sodium carboxymethyl starch form, pregelatinized starch and
The mass ratio of sodium carboxymethyl starch is 1:0.35~2.
Preferably, in step 3), the lubricant is at least one of polyethylene glycol, talcum powder.Preferably, described poly-
The molecular weight of ethylene glycol is 3000~5000.
Preferably, in step 3), the heavy weight additive is sodium chloride.
Preferably, in step 4), by intermediate M3Corrosion inhibiter particle is made using formed in mould method.The mould
By intermediate M when tool molding3Be heated to 100~130 DEG C, be then injected into mold, it is cooling, shake to get.Corrosion inhibiter particle
Size can be adjusted as needed.
The preparation method of above-mentioned solid corrosion inhibitor, further includes: 5) corrosion inhibiter particle obtained is coated.
Preferably, in step 5), the coating is to disperse coating material in a solvent, to be then sprayed at corrosion inhibiter particle
Surface, then be dried.The mass ratio of the coating material and corrosion inhibiter particle is 1:30~100.The solvent is ethyl alcohol, water
At least one of.
Preferably, the coating material includes basis material；Described matrix material is acrylic resin or carboxylic hydroxypropyl methyl
Cellulose.
It is further preferred that the coating material further includes wetting agent；The mass ratio of described matrix material and wetting agent is
2:4~6.
It is first to disperse basis material in a solvent, then to add wetting agent in a solvent by the dispersion of coating material solvent
It is uniformly dispersed.When preferably, using acrylic resin as basis material, using ethyl alcohol as solvent.With carboxylic propyl methocel
When as basis material, using water as solvent.
The wetting agent is at least one of Tween 80, polysorbate60.The acrylic resin is by II He of acrylic resin
Acrylic resin III forms, and the mass ratio of acrylic resin II and acrylic resin III is 2~4:1.
Detailed description of the invention
Fig. 1 is the shape appearance figure of the granular solids corrosion inhibiter of embodiment 1；
Fig. 2 is schematic diagram when evaluating in experimental example 1 granular solids corrosion inhibiter dissolubility using device；Wherein, 1- Φ
62mm lucite tube, 2- valve, 3- are pumped, 4- heated at constant temperature case, at 5- granular solids corrosion inhibiter dispensing, at 6- sampling.
Specific embodiment
Below in conjunction with specific embodiment, further description of the technical solution of the present invention.
Imidazoline quaternary ammonium salt employed in specific embodiment is prepared using method comprising the following steps:
Imidazoline intermediate, quaternizing agent, ethylene glycol are added simultaneously according to the ratio that molar ratio is 1:0.95:0.2
To equipped with condensation reflux unit reactor in, at 120 DEG C react 4h to get；It reacts as follows:
Wherein, R is phenyl, o-hydroxy-phenyl or suitable CH3-(CH2)7- CH=CH- (CH2)7-；R1CH2Cl be benzyl chloride or
Sodium chloroacetate.
The imidazoline quaternary ammonium salt being prepared when R is phenyl is benzoic acid imidazoline quaternary ammonium salt, when R is o-hydroxy-phenyl,
The imidazoline quaternary ammonium salt being prepared is imidazole salicylate hyamine, and R is along CH3-(CH2)7- CH=CH- (CH2)7When, system
Standby obtained imidazoline quaternary ammonium salt is oleic imidazolinone quaternary ammonium salt.
The quaternizing agent that imidazoline quaternary ammonium salt in Examples 1 to 3 uses in the preparation is benzyl chloride, in embodiment 4
The quaternizing agent that uses in the preparation of imidazoline quaternary ammonium salt for sodium chloroacetate.
Embodiment 1
The granular solids corrosion inhibiter of the present embodiment, is shown in Fig. 1, and partial size is 5~10mm, including corrosion inhibiter particle and is coated on slow
Lose the coating material of agent particle surface；Corrosion inhibiter particle is composed of the following parts by weight: 50 parts of inhibition host agent, synergist
5 parts, 4 parts of film forming agent, 11 parts of adhesive, 3 parts of lubricant, 5 parts of nonionic surfactant and 22 parts of heavy weight additive；It is used slow
Erosion host agent is oleic imidazolinone quaternary ammonium salt；Synergist is made of hexamethylenetetramine, sodium nitrite, hexamethylenetetramine, nitrous
The mass ratio of sour sodium is 1:1；Film forming agent is pre-paying starch；Adhesive is made of Petropols and polyvinyl alcohol, Petropols
Mass ratio with polyvinyl alcohol is 7:4；Lubricant is PEG4000；Nonionic surfactant is AEO-20；Heavy weight additive is chlorination
Sodium；The mass ratio of coating material and corrosion inhibiter particle is 1:50；Coating material by acrylic resin III, acrylic resin II and
TW80 composition；Acrylic resin III, acrylic resin II and TW80 mass ratio be 1:3:10.
The preparation method of the granular solids corrosion inhibiter of the present embodiment, comprising the following steps:
1) imidazoline quaternary ammonium salt is heated to 90 DEG C, synergist is then added and stirs evenly, constant temperature 30min obtains centre
Body M1；
2) nonionic surfactant is heated to 50 DEG C of fusings, intermediate M made from step 1) is then added1In, it stirs
It mixes uniformly, obtains intermediate M2；
3) heavy weight additive, adhesive are added to the resulting intermediate M of step 2)2In, it stirs evenly, obtains intermediate M21,
Again by intermediate M21It is mixed with film forming agent, lubricant, obtains intermediate M3；
4) mold forms: by intermediate M3110 DEG C are heated to, is added dropwise in mold, cooling, concussion is to get corrosion inhibiter
Grain；
5) to corrosion inhibiter granule coating: acrylic resin III and acrylic resin II is added in ethyl alcohol, is made into acrylic acid tree
The ethanol solution that rouge mass fraction is 2%, adds the TW80 of ethanol solution quality 5%, obtains coating solution；Again by corrosion inhibiter
Grain is put into coating pan, and coating solution is uniformly sprayed to corrosion inhibiter particle surface by atomizer, controls the amount of coating, is dried
It is dry to get.
Embodiment 2
The granular solids corrosion inhibiter of the present embodiment, partial size is 5~10mm, including corrosion inhibiter particle and is coated on corrosion inhibiter
The coating material on grain surface；Corrosion inhibiter particle is composed of the following parts by weight: 55 parts of inhibition host agent, 5 parts of synergist, at
2.5 parts of film, 7.5 parts of adhesive, 3 parts of lubricant, 7 parts of nonionic surfactant and 20 parts of heavy weight additive；Used inhibition
Host agent is benzoic acid imidazoline quaternary ammonium salt；Synergist is made of hexamethylenetetramine, sodium nitrite, hexamethylenetetramine, nitrous
The mass ratio of sour sodium is 1:1；Film forming agent is pregelatinized starch；Adhesive is made of Petropols and polyvinyl alcohol, Petropols
Mass ratio with polyvinyl alcohol is 2:1；Lubricant is PEG4000；Nonionic surfactant is AEO-9；Heavy weight additive is chlorination
Sodium；The mass ratio of coating material and corrosion inhibiter particle is 1:30；Coating material by acrylic resin III, acrylic resin II and
TW80 composition；Acrylic resin III, acrylic resin II and TW80 mass ratio be 1:3:10.
The preparation method of the granular solids corrosion inhibiter of the present embodiment, comprising the following steps:
1) imidazoline quaternary ammonium salt is heated to 90 DEG C, synergist is then added and stirs evenly, constant temperature 30min obtains centre
Body M1；
2) nonionic surfactant is heated to 50 DEG C of fusings, intermediate M made from step 1) is then added1In, it stirs
It mixes uniformly, obtains intermediate M2；
3) heavy weight additive, adhesive are added to the resulting intermediate M of step 2)2In, it stirs evenly, obtains intermediate M21,
Again by intermediate M21It is mixed with film forming agent, lubricant, obtains intermediate M3；
4) mold forms: by intermediate M3110 DEG C are heated to, is added dropwise in mold, cooling, concussion is to get corrosion inhibiter
Grain；
5) to corrosion inhibiter granule coating: acrylic resin III and acrylic resin II is added in ethyl alcohol, is made into acrylic acid tree
The ethanol solution that rouge mass fraction is 2%, adds the TW80 of ethanol solution quality 5%, obtains coating solution；Again by corrosion inhibiter
Grain is put into coating pan, and coating solution is uniformly sprayed to corrosion inhibiter particle surface by atomizer, controls the amount of coating, is dried
It is dry to get.
Embodiment 3
The granular solids corrosion inhibiter of the present embodiment, partial size is 5~10mm, including corrosion inhibiter particle and is coated on corrosion inhibiter
The coating material on grain surface；Corrosion inhibiter particle is composed of the following parts by weight: 50 parts of inhibition host agent, 8 parts of synergist, at
21 parts of film, 4 parts of adhesive, 4 parts of lubricant, 5 parts of nonionic surfactant and 25 parts of heavy weight additive；Used inhibition host agent
For imidazole salicylate hyamine；Synergist is made of hexamethylenetetramine, sodium nitrite, hexamethylenetetramine, sodium nitrite
Mass ratio be 0.5:1；Film forming agent is made of sodium carboxymethyl starch and pre-paying starch, carboxymethyl starch and pre-paying starch
Mass ratio is 5:2；Adhesive is polyvinyl alcohol；Lubricant is talcum powder；Nonionic surfactant is NP-30；Heavy weight additive is
Sodium chloride；The mass ratio of coating material and corrosion inhibiter particle is 1:75；Coating material is by hydroxypropyl methyl cellulose and TW80 group
At；Acrylic resin III, acrylic resin II and TW80 mass ratio be 1:4:10.
The preparation method of the granular solids corrosion inhibiter of the present embodiment, comprising the following steps:
1) imidazoline quaternary ammonium salt is heated to 100 DEG C, synergist is then added and stirs evenly, constant temperature 20min obtains centre
Body M1；
2) nonionic surfactant is heated to 50 DEG C of fusings, intermediate M made from step 1) is then added1In, it stirs
It mixes uniformly, obtains intermediate M2；
3) heavy weight additive, adhesive are added to the resulting intermediate M of step 2)2In, it stirs evenly, obtains intermediate M21,
Again by intermediate M21It is mixed with film forming agent, lubricant, obtains intermediate M3；
4) mold forms: by intermediate M3110 DEG C are heated to, is added dropwise in mold, cooling, concussion is to get corrosion inhibiter
Grain；
5) to corrosion inhibiter granule coating: acrylic resin III and acrylic resin II is added in ethyl alcohol, is made into acrylic acid tree
The ethanol solution that rouge mass fraction is 2.5%, adds the TW80 of ethanol solution quality 5%, obtains coating solution；Again by corrosion inhibiter
Particle is put into coating pan, and coating solution is uniformly sprayed to corrosion inhibiter particle surface by atomizer, controls the amount of coating, is dried
It is dry to get.
Embodiment 4
The granular solids corrosion inhibiter of the present embodiment, partial size is 5~10mm, including corrosion inhibiter particle and is coated on corrosion inhibiter
The coating material on grain surface；Corrosion inhibiter particle is composed of the following parts by weight: 50 parts of inhibition host agent, 5 parts of synergist, at
9.7 parts of film, 5.3 parts of adhesive, 3 parts of lubricant, 5 parts of nonionic surfactant and 22 parts of heavy weight additive；Used inhibition
Host agent is oleic imidazolinone quaternary ammonium salt；Synergist is made of hexamethylenetetramine, sodium nitrite, hexamethylenetetramine, nitrous acid
The mass ratio of sodium is 1.5:1；Film forming agent is made of sodium carboxymethyl starch and pregelatinized starch；Carboxymethyl starch and pre-paying starch
Mass ratio be 7:2.6；Adhesive is polyvinyl alcohol；Lubricant is talcum powder；Nonionic surfactant is NP-30；It aggravates
Agent is sodium chloride；The mass ratio of coating material and corrosion inhibiter particle is 1:100；Coating material by hydroxypropyl methyl cellulose and
TW60 composition；The mass ratio of hydroxypropyl methyl cellulose and TW60 are 1:2.
The preparation method of the granular solids corrosion inhibiter of the present embodiment, comprising the following steps:
1) imidazoline quaternary ammonium salt is heated to 80 DEG C, synergist is then added and stirs evenly, constant temperature 40min obtains centre
Body M1；
2) nonionic surfactant is heated to 50 DEG C of fusings, intermediate M made from step 1) is then added1In, it stirs
It mixes uniformly, obtains intermediate M2；
3) heavy weight additive, adhesive are added to the resulting intermediate M of step 2)2In, it stirs evenly, obtains intermediate M21,
Again by intermediate M21It is mixed with film forming agent, lubricant, obtains intermediate M3；
4) mold forms: by intermediate M3110 DEG C are heated to, is added dropwise in mold, cooling, concussion is to get corrosion inhibiter
Grain；
5) to corrosion inhibiter granule coating: hydroxypropyl methyl cellulose is added to the water, and is made into hydroxypropyl methyl cellulose quality
The aqueous solution that score is 1%, adds the TW60 of the aqueous solution quality 2%, obtains coating solution；Corrosion inhibiter particle is put into packet again
In clothing pot, coating solution is uniformly sprayed at by atomizer by corrosion inhibiter particle surface, controls the amount of coating, drying to get.
Embodiment 5
The granular solids corrosion inhibiter of the present embodiment, partial size is 5~10mm, including corrosion inhibiter particle and is coated on corrosion inhibiter
The coating material on grain surface；Corrosion inhibiter particle is composed of the following parts by weight: 50 parts of inhibition host agent, 5 parts of synergist, at
2.5 parts of film, 11 parts of adhesive, 5 parts of lubricant, 5 parts of nonionic surfactant and 21.5 parts of heavy weight additive；Used inhibition
Host agent is benzoic acid imidazoline quaternary ammonium salt；Synergist is sodium nitrite composition；Film forming agent is pregelatinized starch and carboxymethyl starch
The mass ratio of sodium composition, pregelatinized starch and sodium carboxymethyl starch is 1:2；Adhesive is made of Petropols and polyvinyl alcohol,
The mass ratio of Petropols and polyvinyl alcohol is 2:1；Lubricant is PEG4000；Nonionic surfactant is AEO-9；It aggravates
Agent is sodium chloride；The mass ratio of coating material and corrosion inhibiter particle is 1:50；Coating material is by acrylic resin III, acrylic acid
Resin II and TW80 composition；Acrylic resin III, acrylic resin II and TW80 mass ratio be 1:3:10.
The preparation method of the granular solids corrosion inhibiter of the present embodiment, comprising the following steps:
1) imidazoline quaternary ammonium salt is heated to 90 DEG C, synergist is then added and stirs evenly, constant temperature 30min obtains centre
Body M1；
2) nonionic surfactant is heated to 50 DEG C of fusings, intermediate M made from step 1) is then added1In, it stirs
It mixes uniformly, obtains intermediate M2；
3) heavy weight additive, adhesive are added to the resulting intermediate M of step 2)2In, it stirs evenly, obtains intermediate M21,
Again by intermediate M21It is mixed with film forming agent, lubricant, obtains intermediate M3；
4) mold forms: by intermediate M3110 DEG C are heated to, is added dropwise in mold, cooling, concussion is to get corrosion inhibiter
Grain；
5) to corrosion inhibiter granule coating: acrylic resin III and acrylic resin II is added in ethyl alcohol, is made into acrylic acid tree
The ethanol solution that rouge mass fraction is 2%, adds the TW80 of ethanol solution quality 6%, obtains coating solution；Again by corrosion inhibiter
Grain is put into coating pan, and coating solution is uniformly sprayed to corrosion inhibiter particle surface by atomizer, controls the amount of coating, is dried
It is dry to get.
Experimental example 1
Experimental example 1 is using laboratory simulation scene oil jacket device (as shown in Figure 2) to granular solids corrosion inhibiter solubility property
Evaluation:
Evaluation method: oil field output water is taken to carry out the evaluation of granular solids corrosion inhibiter dissolubility.
1) the granular solids corrosion inhibiter 100g (being accurate to 0.01g) of difference precise Examples 1 to 5, is thrown to simulation
5 at the granular solids corrosion inhibiter dispensing of 1 bottom of Φ 62mm lucite tube of device；
2) oil field output water is taken to be added in heated at constant temperature case 4, extremely by 4 temperature adjustment of heated at constant temperature case to 70 DEG C of experimental temperature heat preservations
The temperature of oil field output water is 70 DEG C, and 3 discharge capacities of pump are adjusted to 3L/h；Valve 2 is opened, 6 sampling monitoring corrosion inhibiter are dense at sampling
Degree, continuous monitoring 7 days；According to density of corrosion inhibitor monitoring quantity, corrosion inhibiter solution rate is calculated.
The rate of dissolution of the granular solids corrosion inhibiter for each embodiment that detection clearing obtain is shown in Table 1.
The rate of dissolution of the granular solids corrosion inhibiter of 1 Examples 1 to 5 of table
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Rate of dissolution (mg (dcm2)-1) | 2~3 | 3~4 | 4~5 | 2~3 | 3~4 |
Experimental example 2
Experimental example 2 is the granular solids corrosion inhibiter corrosion inhibition evaluation to Examples 1 to 5: oil field output water is taken, by standard
SY/T5273-2014 " oil field extracted water corrosion inhibiter method of evaluating performance " measures its corrosion inhibition rate and corrosion rate.
Specific experiment condition: corrosive medium is oil field output water, and experimental temperature is 80 DEG C, and test material is N80 steel, inhibition
Agent concentration is 50mg/L.Evaluation result is shown in Table 2.
The corrosion inhibition of the granular solids corrosion inhibiter of 2 Examples 1 to 5 of table
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Corrosion inhibition rate/% | 87.20 | 81.75 | 90.61 | 85.69 | 86.97 |
| Corrosion rate (mm/a) | 0.0169 | 0.0241 | 0.0124 | 0.0189 | 0.0172 |
Experimental example 3
Experimental example 3 is the granular solids corrosion inhibiter field application to embodiment 1:
Zhao1-3Jing is the east Zhongyuan Oil Field Pu oil recovery factory CO2Corresponding a bite oil well is driven, in January, 2016 is total to 2 months 2017
It lies well operations 4 times, CO2Gas content rises to 90.88% current, CO by 65% at the beginning of 20162Gas content is at 65%
Well period of lying is 150 days, CO2Gas content is lain the well period 65 days at 90.88%.
The granular solids corrosion inhibiter of embodiment 1 is added within 14 days 2 months within 2017 by casing annulus, which ended to 2018
March 18 has operated normally 399 days, has extended 334 days, and continuous and effective duty cycle.Before corrosion rate is by implementing
0.0945mm/a is minimum to be down to 0.0012mm/a, the maximum range of decrease 98.7%, and the corrosion of pit shaft has obtained greatly inhibiting.
Claims (5)
1. a kind of granular solids corrosion inhibiter, it is characterised in that: the component including following parts by weight: 50~55 parts of inhibition host agent,
5~10 parts of synergist, 2.5~21 parts of film forming agent, 4~11 parts of adhesive, 3~5 parts of lubricant, nonionic surfactant 5~8
Part and 20~25 parts of heavy weight additive；The inhibition host agent is imidazoline quaternary ammonium salt；The nonionic surfactant is poly alkyl alcohol
At least one of ethylene oxide ether, alkyl phenol polyoxyethylene ether；The synergist be hexamethylenetetramine, in sodium nitrite extremely
Few one kind；Described adhesive is at least one of Petropols, polyvinyl alcohol；The lubricant is polyethylene glycol, talcum powder
At least one of；The film forming agent is at least one of pregelatinized starch, sodium carboxymethyl starch.
2. granular solids corrosion inhibiter according to claim 1, it is characterised in that: including corrosion inhibiter particle and be coated on inhibition
The coating material of agent particle surface；The corrosion inhibiter particle is mainly composed of the following parts by weight: inhibition host agent 50~
55 parts, 5~10 parts of synergist, 2.5~21 parts of film forming agent, 4~11 parts of adhesive, 3~5 parts of lubricant, non-ionic surface active
5~8 parts and 20~25 parts of heavy weight additive of agent；The mass ratio of the coating material and corrosion inhibiter particle is 1:30~100.
3. granular solids corrosion inhibiter according to claim 1 or 2, it is characterised in that: the heavy weight additive is sodium chloride.
4. granular solids corrosion inhibiter according to claim 2, it is characterised in that: the coating material includes basis material；
Described matrix material is acrylic resin or carboxylic propyl methocel.
5. a kind of preparation method of granular solids corrosion inhibiter as described in claim 1, it is characterised in that: the following steps are included:
1) at 80~100 DEG C, synergist is uniformly mixed with inhibition host agent, keeps the temperature, obtains intermediate M1；
2) by nonionic surfactant and intermediate M1It mixes, obtains intermediate M2；
3) by adhesive, film forming agent, lubricant, heavy weight additive and intermediate M2It mixes, obtains intermediate M3；
4) by intermediate M3Be made corrosion inhibiter particle to get.
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| CN111257408B (en) * | 2020-02-18 | 2022-08-30 | 广东省特种设备检测研究院珠海检测院 | Effervescent tablet containing nano magnetic powder and application thereof |
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| CN111154470A (en) * | 2020-02-21 | 2020-05-15 | 四川振邦石油科技有限公司 | Slow-release solid corrosion inhibitor, preparation method and application |
| CN114350336B (en) * | 2022-03-21 | 2022-06-07 | 胜利油田新海兴达实业集团有限责任公司 | Composite corrosion inhibitor for oil field and preparation method thereof |
| CN114875412B (en) * | 2022-05-19 | 2023-03-10 | 西安交通大学 | Preparation method of polynuclear amorphous solid corrosion inhibitor |
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