CN109680279A - A method of high-temperature resistant anti-corrosive scale inhibition coating is prepared in oil pipe steel surface - Google Patents

A method of high-temperature resistant anti-corrosive scale inhibition coating is prepared in oil pipe steel surface Download PDF

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CN109680279A
CN109680279A CN201910154580.2A CN201910154580A CN109680279A CN 109680279 A CN109680279 A CN 109680279A CN 201910154580 A CN201910154580 A CN 201910154580A CN 109680279 A CN109680279 A CN 109680279A
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oil
deionized water
coating
corrosion
oil pipe
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刘恩洋
胡锦辉
于思荣
吕哲馨
赵严
熊伟
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China University of Petroleum East China
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China University of Petroleum East China
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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
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/28—Acidic compositions for etching iron group metals
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • 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
    • C23F15/00—Other methods of preventing corrosion or incrustation
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C23G1/19—Iron or steel
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G3/00—Apparatus for cleaning or pickling metallic material
    • C23G3/04—Apparatus for cleaning or pickling metallic material for cleaning pipes

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

The invention discloses a kind of methods for preparing high-temperature resistant anti-corrosive scale inhibition coating in oil pipe steel surface, belong to metal surface properties modification field.This method first polishes to Oil Tube Steel, ultrasonic cleaning is handled, and then carries out alkali cleaning and pickling to Oil Tube Steel respectively；Deionized water cleaning tubing steel and rapid draing are used after the completion of alkali cleaning and pickling, then carries out chemical etching and sintering processes, with being furnace-cooled to room temperature after the completion of sintering；Oil Tube Steel is finally subjected to low energy modification, obtain the super-hydrophobic coat with high-temperature resistant anti-corrosive scale inhibition function, after measured, the coating and the contact angle of deionized water are up to 159.68 °, " 6.5 ° of roll angle, the coating has good heat-resisting quantity, corrosion resistance and scale inhibition performance, can play the role of anti-corrosion, scale-inhibiting to oil pipe in complex environment under oil well, the production efficiency of oil well greatly improved.Preparation method of the present invention is without expensive equipment, and simple process is easy to operate, low in cost, it is easy to accomplish industrialized production.

Description

A method of high-temperature resistant anti-corrosive scale inhibition coating is prepared in oil pipe steel surface
Technical field
The invention belongs to technical field of metal material surface modification, and in particular to a kind of to prepare high temperature resistant in oil pipe steel surface The method of anti-corrosion, scale-inhibiting coating.
Background technique
Oil pipe is chronically at containing H in oil well2S, CO2, O2, Cl-With the height of a variety of corrosive components such as sulfate reducing bacteria In warm high pressure multiphase flow environment, corrosion is caused to become its important failure mode.Tube corrosion easily lead to oil pipe leakage, squeeze it is flat, Disconnected phenomena such as falling, seriously affect the normal production of oil gas field.Further, since often containing iron, calcium, magnesium, barium etc. in Produced Liquid Ion easily generates carbonate or sulfate and is deposited on tube inner wall, causes scale formation.Fouling not only reduces inside oil pipe Effective cross-section, result in blockage, also result in underdeposit corrosion.The corrosion of oil pipe and scale problems not only reduce crude output, Workover treatment number is increased, the well workover period is shortened, sucker rod is also will cause when serious and breaks, oil well closing well causes huge Economic loss.Therefore, high-temperature resistant anti-corrosive scale inhibition coating is prepared in oil pipe steel surface to solve the corrosion of oil pipe and scale problems tool It is significant.
Dry CO2Itself does not have corrosivity, works as CO2Being dissolved in after water forms weak acid can make oil pipe that electrochemical corrosion occur. CO2Corrosion is an extremely complex process, since people are to CO2The understanding of corrosion intermediate product is not enough, and many scholars mention Different reaction mechanism models is gone out, such as Waard mechanism, Davies mechanism and Ogundele mechanism etc..Although these mechanism moulds Type is different, but all follows basic Electrochemical Corrosion Mechanism, basic process are as follows: anode reaction is Fe → Fe2++2e-；Cathode The essence of reaction is reduction process, and the substance being only reduced may have H+、H2CO3And H2O.It is reduced as which kind of substance, It is then related with many factors such as the pH value of liquid, temperature, the concentration of each substance.
H2The solubility of S in water is larger, it may have stronger corrosivity.H in aqueous solution2The dissociation of S can effectively increase yin Pole H+Concentration so that cathode reaction significantly increases, to promote the corrosion of oil pipe.H2S corrosion in varied situations difference compared with Greatly, not only with the pH value of solution, H2S concentration is related, also related with the Nomenclature Composition and Structure of Complexes for being formed by sulfide film.When corrosion produces Object FeS is fine and close and when being tightly combined with metallic matrix, has to corrosion and certain slows down effect.But when the FeS generated is not fine and close When, then galvanic couple can be formed with metallic matrix, promote the corrosion of parent metal instead.In addition, H2S corrosion can also cause hydrogen embrittlement, hydrogen Bubbling and sulfide-stress cracking etc..
Currently, tube corrosion protection frequently with method mainly have: (1) fill corrosion inhibiter.Its anti-corrosion effect is mainly and well The factors such as condition, type of inhibitor, injection period, injection rate are related.The technology initial investment is few, but complex process, to production shadow Sound is larger.In addition, different well's conditions require the type of corrosion inhibiter to be also not quite similar, corrosion inhibiter bad adaptability.(2) corrosion resistant alloy is used Steel.For example, CO can be resisted using ferrite stainless steel pipe containing Cr (9%~13%Cr)2Corrosion.The use of corrosion resistant alloy steel, it is right Oil well production operation is but expensive without influence, and applicability is not strong, is difficult to play protective action to other corrosive mediums.(3) it adopts With electrochemical protection technology.In oil well anti-corrosion, down-hole string is mainly protected using sacrificial anode protection, but operating procedure is multiple It is miscellaneous.(4) sealer is prepared using surface treatment or coating, coating technology.Sealer mainly includes that organic material applies Layer and metal coating.More metal coating is studied at present mainly to include spray coating, chemical deposit, reductive carbo-nitridation layer, seep gold Belong to layer etc..Surface covering corrosion resistance generally with higher, and preparation cost is cheap, simple process, has wide answer Use prospect.
The corrosion of metal material is usually electrochemical corrosion, and the presence of electrolyte is to constitute the precondition of primary battery, rotten The water in environment is lost generally as primary solvent.Possess a large amount of microns or nanoscale structures, water droplet (electrolysis on super hydrophobic surface Liquid) and metal surface can retain large quantity of air when contacting, to make water droplet and metal surface real contact area reduce, effectively Ground reduces the generation of redox reaction, to slow down the corrosion of metal material.Further, since the rolling of super hydrophobic surface Angle all very littles hardly stop on the surface after water droplet (electrolyte) touches super hydrophobic surface, in small tilt angle or It will be slid under the conditions of vibration, which also limits primary batteries to be formed on the surface of the material.From super hydrophobic surface ingredient, Duo Shuochao Hydrophobic surface will be modified by katakinetomere, and to reduce its surface energy, this layer of modified membrane being capable of effective protection lower metal material Material, hinders it directly to contact with External electrolytic liquid, thus improves corrosion resistance.
There are mainly three types of the mechanism of oil pipe fouling: (1) containing the easy fouling salt ion of high concentration in the water of oil field, in oil recovery process In, since original material balance has been broken in the variation of pressure, temperature or certain constituent content and dirt is formed, mainly with calcium carbonate scale Based on, in addition also it is mixed with magnesium carbonate, calcium sulfate/magnesium etc.；(2) incompatible injection water and water flooding mixing, in water it is incompatible from Son interacts and generates dirt, common are barium sulfate scale and strontium sulfate scale；(3) due to the dirt that corrosion generates, such as ferrous carbonate Dirt and ferrous sulfide scale.After oil pipe fouling, it is necessary to remove in time, otherwise will reduce crude oil production efficiency, or even cause production thing Therefore.Common descaling method mainly has: (1) chemical cleaning selects suitable chemical reagent according to the constituent of different dirts Carry out dissolution scale removal；(2) high-pressure water jet scale removal hits dirty layer using high pressure water, dirt is caused to fall off；(3) pipe cleaner is used Carry out mechanical descaling；(4) ultrasound wave descaling makes dirt fall off by the impact force of ultrasonic activation and cavitation effect.No matter adopt With which kind of descaling method, it can all interfere normally to produce, expend a large amount of manpower and material resources.Therefore, oil field drops in pre- preventing oil pipe fouling This synergy is of great significance.
Currently, the main method of pre- preventing oil pipe fouling has: (1) physical method antiscale is pressed down using ultrasonic wave or additional high-intensity magnetic field Make the formation of dirt；(2) antisludging agent is added in chemical method antiscale；(3) certain working technology conditions are modified or controlled in Process antiscale To reduce the generation chance of dirt, such as the injection water, control oil/gas well operation flow velocity and producing pressure differential of selection and stratum compatible Deng.Fouling is the process that solute crystallizes precipitation, agglomeration from supersaturated solution.According to the crystallization theory of dirt, due to heterogeneous Nucleating work needed for forming core is lower, and dirty nucleus is preferentially formed using the surface of solids as substrate, and nucleus then grows up to form dirty layer.Dirt Nucleating work it is directly related with contact angle size, contact angle is smaller, and nucleating work is also smaller, and nucleus is more easy to form.Super-hydrophobic table Face often has biggish contact angle, increases the nucleating work of dirt, dirty layer is made to be not easy to be formed.
Super hydrophobic surface refers to the static contact angle θ of water greater than 150 °, and surface of the roll angle less than 10 °, often has There is non wettability, ice-covering-proof, automatically cleaning, anti-corrosion anti-scale, reduce the effects of fluid resistance, in petroleum and petrochemical industry, communications and transportation, electric power The industries such as communication have broad prospect of application.
Environment temperature under oil well is up to 150 DEG C or more, and there are a variety of corrosive mediums and dirt, common super hydrophobic surfaces Due to heat-resisting quantity and durability is poor is unable to play the role of anti-corrosion, scale-inhibiting.Therefore how in such complicated oil well ring Under border, it is ensured that the corrosion-resistant of oil pipe, good antiscale property and high temperature resistance are just asked at those skilled in the art's technology urgently to be resolved One of topic.
Summary of the invention
Present invention aim to address oil pipes during military service because corrode and scale problems caused by service life it is short, The problems such as oil well productivity is low provides a kind of using chemical etching method combination sintering process preparation Oil Tube Steel surface refractory anti-corrosion, scale-inhibiting The technology of coating.
The present invention prepares micro-nano multi-scale micro-structure in oil pipe steel surface using chemical etching method combination sintering process, through low energy After modification, high-temperature resistant anti-corrosive scale inhibition coating is obtained, reaching prevents electrochemical corrosion, reduce dirt agglomeration, improve oil field production effect The purpose of rate.After measured, the coating and the contact angle of deionized water are up to 159.68 °, and less than 6.5 °, which has roll angle Good heat-resisting quantity, corrosion resistance and scale inhibition performance can play the work of anti-corrosion, scale-inhibiting in complex environment under oil well to oil pipe With the production efficiency of oil well greatly improved.Preparation method of the present invention is without expensive equipment, simple process, behaviour Facilitate, it is low in cost, it is easy to accomplish industrialized production.
In the prior art it is high found a state etc. (105413994 A of CN) using two-step etching in metal, inorganic non-metallic and poly- Object surface structure micron and nanometer composite structure is closed, by the modification of surface modifier, obtains super hydrophobic surface, then through potentiodynamic polarization The corrosion resistance on tracing analysis surface, the results showed that the super hydrophobic surface of preparation has excellent corrosion resistance.But its two step Method step is more cumbersome and higher cost, compared with this method, the present invention only pass through step etching can be obtained it is micro-nano compound Structure, experimental technique is simple, and super hydrophobic surface prepared by the present invention in addition to excellent corrosion resistance, be also equipped with compared with Good heat-resisting quantity and scale inhibition performance, can be applied to the changeable Service Environment of oil extraction in oil field system complex.(the CN such as full of beard honor 107267967 A) using the etching liquid etching aluminum substrate of copper ions and iron ion obtain featheriness microstructure, then through heat at Reason and low energy modification, obtain super hydrophobic surface, but do not state the performance of the super hydrophobic surface, those skilled in the art are difficult How to infer its specific effect.The present invention is compared with this method, prepared super-hydrophobic coat excellent combination property, examination used Agent is cheap, and environmental pollution is small, wide adaptation range.
Technical scheme is as follows:
To alkali cleaning, pickling is carried out after Oil Tube Steel ultrasonic cleaning, it is subsequently placed into etching liquid and carries out chemical etching, construction is provided There is the surface micronano coarse structure of certain roughness, be then placed in resistance furnace and be sintered, is most obtained after low energy is modified afterwards There must be the super-hydrophobic coat of high-temperature resistant anti-corrosive scale inhibition function.The wherein polishing, alkali cleaning, pickling and deionized water cleaning step Suddenly the prior art can be referred to, it can also be using the specific process step of the following offers of the present invention:
(1) grinding process is carried out to Oil Tube Steel using 600#-2000# silicon carbide waterproof abrasive paper first, makes its surface-brightening, so It is respectively put into acetone and dehydrated alcohol and is cleaned by ultrasonic afterwards, removed surface and oil contaminant and impurity, finally use deionized water Clean simultaneously rapid draing；
(2) alkali wash water, alkali wash water composition are as follows: sodium hydroxide 10-40g/L, sodium carbonate 10-30g/L, sodium phosphate 10- are prepared 30g/L, sodium metasilicate 5-15g/L, solvent are deionized water；
It is since the alkali wash water can efficiently remove Oil Tube Steel surface grease and dirt why with above-mentioned prescription configuration alkali wash water Object improves alkali cleaning efficiency, lays the foundation to prepare the surface covering of even compact, and improve the binding force of coating and matrix.
(3) it will be put into alkali wash water by the Oil Tube Steel of step (1) processing, the alkali cleaning 5-25min at 30-80 DEG C takes out Simultaneously rapid draing is cleaned with deionized water afterwards；
(4) pickling solution, pickling solution composition are as follows: hydrochloric acid 0.5-2.5mol/L, solvent are deionized water are prepared；
(5) it will be put into pickling 0.5-5min in pickling solution by the Oil Tube Steel of step (3) processing, removes surface oxide layer, Simultaneously rapid draing is cleaned with deionized water after taking-up；
Following step is the present invention and the maximum distinctive points of the prior art, for present invention oil pipe to be dealt with, invention People specifically provides following steps:
(6) etching liquid is prepared, etching liquid includes: Copper dichloride dihydrate 0.5-3.0mol/L, hydrochloric acid 0.2-1.5mol/L, molten Agent is deionized water；
The etching liquid performs etching oil pipe steel matrix by the chemical reaction of copper ion and the spot corrosion effect of chloride ion, Not only the problem that the incident etching of conventional acid etching liquid is insufficient or etching is excessive had been can solve in the concentration range, but also can be The layers of copper with micro nano structure is generated while etching in matrix surface, is convenient for subsequent sintering processes.It will etching and coppering It is combined together, simplifies processing step；
(7) it will be put into etching liquid, hung up Oil Tube Steel with hook, chemical etching by the Oil Tube Steel of step (5) processing 10-30min obtains micro-nano double scale coarse structures；
(8) it will be taken out by the Oil Tube Steel of step (7) processing, and be cleaned with deionized water, dry up, be put into 150-300 DEG C It is sintered in resistance furnace, sintering time 10-60min, then with being furnace-cooled to room temperature；
(9) by the tetradecylic acid ethanol solution for being put into 7-18g/L after Oil Tube Steel that step (8) is handled is taken out into The modification of row low energy, modification time are 15-48h, and drying box is put into after taking-up and is dried at 40-120 DEG C, can be in oil pipe steel surface Obtain the super-hydrophobic coat with high-temperature resistant anti-corrosive scale inhibition function.
Micro-nano compound coarse structure is constructed by chemical etching, then increases stability and heat-resisting quantity through high temperature sintering, Most modified afterwards through low energy and obtain super-hydrophobic coat, micro-nano double scale coarse structures of the coating, copper oxide resistant to high temperature and compared with Low surface free energy determines that it has excellent high-temperature resistant anti-corrosive scale inhibition performance.
The etching liquid being made of Copper dichloride dihydrate and hydrochloric acid both can effectively etch oil pipe steel matrix, keep matrix surface raw Long layers of copper, and can prevent from etching problem excessive or that etching is insufficient, micro-nano compound microcosmic knot is obtained after etched processing Structure, then microstructure is further improved so that layers of copper is reacted at high temperature generates copper oxide resistant to high temperature through sintering processes Roughness also improves the durability and heat-resisting quantity of coating.Most make its knot after the modification of organic acid soak of low-surface-energy afterwards Coating surface is closed, surface free energy is reduced, so that the coating be made to obtain super-hydrophobicity and anti-corrosion, scale-inhibiting.
Compared with prior art, the beneficial effects of the present invention are:
(1) present invention prepares anti-corrosion, scale-inhibiting coating, this method in oil pipe steel surface using chemical etching method combination sintering process Without expensive equipment, simple process is easy to operate, low in cost, it is easy to accomplish industrialized production；
(2) super-hydrophobic coat prepared by the present invention has preferable heat-resisting quantity, durability and stability, after measured, The coating and the contact angle of deionized water are up to 159.68 °, and roll angle is less than 6.5 °；It can be risen in complex environment under oil well To the effect of anti-corrosion, scale-inhibiting, the production efficiency in oil field can be greatly improved；
(3) preparation process of the present invention has broad applicability, can prepare in the Oil Tube Steel of the different trades mark resistance to High-temperature anticorrosion scale inhibition coating, such as J55, N80 and P110 Oil Tube Steel.
Detailed description of the invention
Fig. 1 is the SEM photograph for the Oil Tube Steel surface refractory anti-corrosion, scale-inhibiting coating that the present invention obtains,
Fig. 2 is the contact angle photo of Oil Tube Steel surface refractory anti-corrosion, scale-inhibiting coating and water droplet that the present invention obtains,
Fig. 3 is the polarization curve of the Oil Tube Steel surface covering of the invention obtained and oil pipe steel matrix,
Fig. 4 is the quality of the Oil Tube Steel and oil pipe steel matrix with anti-corrosion, scale-inhibiting coating with the change curve of soaking time,
Fig. 5 is contact angle change curve of the Oil Tube Steel surface covering of the invention obtained after high-temperature process；
Fig. 6 is that the Oil Tube Steel surface covering that the present invention obtains impregnates the contact angle change after different time in oil water mixture Change curve；
In figure, Fig. 1 is surface topography of the Oil Tube Steel after the modification of chemical etching, sintering and low energy, and the pattern is by micron Boss and nanoscale the dendritic structure composition of grade, meet the structural requirement of building super hydrophobic surface；Liquid as can be seen from Figure 2 Drop is spherical in coating surface, illustrates that prepared coating has super-hydrophobicity；In Fig. 3, the corrosion potential of oil pipe steel matrix It is respectively -0.47797V and 4.5022 × 10 with corrosion electric current density-6A/cm2, the corruption of the Oil Tube Steel with anti-corrosion, scale-inhibiting coating It loses current potential and corrosion electric current density is respectively -0.36107V and 2.606 × 10-7A/cm2, illustrate that the coating has preferable corrosion resistant Corrosion；From fig. 4, it can be seen that the quality of oil pipe steel matrix is significantly increased with the increase of soaking time, and there is scale inhibition coating Oil Tube Steel quality incrementss very little, illustrate the coating have preferable scale inhibition performance；From fig. 5, it can be seen that with heat preservation temperature The increase of degree, the contact angle reduction amount very little of the coating, illustrates it with preferable high temperature resistance；From fig. 6, it can be seen that should Anti-corrosion, scale-inhibiting coating still has biggish contact angle after impregnating 6 months, illustrates it with preferable durability.
Specific embodiment
Below in conjunction with specific embodiment, the present invention will be further described, involved in present embodiment Pretreatment it is as follows:
Grinding process first is carried out to oil pipe steel surface using 600#-2000# silicon carbide waterproof abrasive paper, makes its surface-brightening, so It is respectively put into acetone and dehydrated alcohol and is cleaned by ultrasonic afterwards, removed surface and oil contaminant and impurity, finally use deionized water Clean simultaneously rapid draing.
Then Oil Tube Steel is put into alkali wash water, alkali cleaning 5-25min, further removes surface in 30-80 DEG C of water-bath Grease and dirt clean simultaneously rapid draing with deionized water after taking-up；It then places into pickling solution, pickling 0.5-5min is gone Except surface film oxide, simultaneously rapid draing is cleaned with deionized water after taking-up.Wherein used alkali wash water composition are as follows: sodium hydroxide 10-40g/L, sodium carbonate 10-30g/L, sodium phosphate 10-30g/L, sodium metasilicate 5-15g/L, solvent are deionized water；
Used pickling solution is the hydrochloric acid of 0.5-2.5mol/L；
A kind of method for preparing high-temperature resistant anti-corrosive scale inhibition coating in oil pipe steel surface of embodiment 1
After above-mentioned pretreatment, the specific steps are as follows:
(1) prepare etching liquid, etching liquid includes: Copper dichloride dihydrate 1.5mol/L, hydrochloric acid 0.5mol/L, solvent be go from Sub- water；
(2) it will be put into etching liquid by pretreated Oil Tube Steel, be hung up with hook, and etch 15min, acquisition has certain The surface micronano coarse structure of roughness；
(3) Oil Tube Steel after etching is taken out, is cleaned with deionized water, dry up, be put into 200 DEG C of resistance furnace and burnt Knot, sintering time 30min, then with being furnace-cooled to room temperature；
(4) it is put into the tetradecylic acid ethanol solution of 15g/L after taking out the Oil Tube Steel after sintering processes and carries out low energy Modification, modification time are to be put into drying box for 24 hours, after taking-up to dry at 100 DEG C.
After above-mentioned processing, one layer of high-temperature resistant anti-corrosive scale inhibition super-hydrophobic coat, the table of the coating are obtained in oil pipe steel surface Face pattern is as shown in Figure 1, the contact angle of itself and deionized water is 159.68 °, and roll angle is less than 6 °, as shown in Figure 2.
Measurement has the Oil Tube Steel of anti-corrosion, scale-inhibiting coating and the polarization curve of matrix respectively in 3.5wt.%NaCl solution, As shown in Figure 3.Compared to oil pipe steel matrix, the corrosion electric current density of the Oil Tube Steel with anti-corrosion, scale-inhibiting coating is significantly reduced, rotten Erosion current potential significantly improves, and illustrates that the corrosion resistance of the Oil Tube Steel with anti-corrosion, scale-inhibiting coating is significantly better than not processed Oil Tube Steel.
By with anti-corrosion, scale-inhibiting coating Oil Tube Steel and oil pipe steel matrix be individually positioned in oil field mining liquid and impregnate, daily It takes out dry and weighs, measure its quality change rule, as shown in Figure 4.As can be seen that with the increase Oil Tube Steel of soaking time The amount of scale buildup of matrix gradually increases, and the amount of scale buildup of the Oil Tube Steel with anti-corrosion, scale-inhibiting coating is few, and it is good to illustrate that the coating has Good anti-scaling property.
Oil Tube Steel with anti-corrosion, scale-inhibiting coating is kept the temperature for 24 hours at different temperatures, its contact is measured after being cooled to room temperature Angle and roll angle.Contact angle change curve is as shown in figure 5, roll angle is almost unchanged.As can be seen that with the increasing of holding temperature Add, although contact angle is declined slightly, but remain super-hydrophobic feature at 155 ° or more, and it is good to illustrate that the coating has High temperature resistance.
By the Oil Tube Steel with anti-corrosion, scale-inhibiting coating be placed on oil water mixture (volume fraction be 98% deionized water+ 2% crude oil) in impregnate different time, every month take out dry up simultaneously measures its contact angle and roll angle.Contact angle change curve As shown in fig. 6, roll angle is almost unchanged.Although can be seen that as the contact angle for increasing the coating of soaking time slightly has Reduce, but at 155 ° or more, illustrates it with good durability.
Specific embodiment 2: the present embodiment from Copper dichloride dihydrate concentration is in step (1) unlike specific embodiment 1 1mol/L.Other are identical as specific embodiment 1.
Specific embodiment 3: the present embodiment from unlike specific embodiment 1 in step (1) concentration of hydrochloric acid be 0.4mol/L. Other are identical as specific embodiment 1.
Specific embodiment 4: the present embodiment from unlike specific embodiment 1 in step (2) etch period be 25min.Its He is identical as specific embodiment 1.
Specific embodiment 5: the present embodiment from unlike specific embodiment 1 in step (3) resistance furnace temperature be 230 ℃.Other are identical as specific embodiment 1.
Specific embodiment 6: the present embodiment from unlike specific embodiment 1 in step (3) sintering time be 40min.Its He is identical as specific embodiment 1.
Specific embodiment 7: the present embodiment and tetradecylic acid dehydrated alcohol concentration in step (4) unlike specific embodiment 1 For 10g/L.Other are identical as specific embodiment 1.
Specific embodiment 8: the present embodiment from unlike specific embodiment 1 in step (4) low energy modification the time be 18h. Other are identical as specific embodiment 1.
The embodiment 2-8 oil pipe steel coating obtained is detected accordingly, as a result as follows:
The contact angle and rolling angle value of prepared coating are as shown in table 1.As can be seen that coating prepared by each embodiment connects Feeler is all larger than 155 °, and roll angle is respectively less than 6.5 °, all has super-hydrophobicity.
The contact angle and rolling angle value of coating prepared by each embodiment of table 1
Embodiment Two Three Four Five Six Seven Eight
Contact angle/° 157.5 157.38 156.21 158.17 155.92 156.46 155.93
Roll angle/° 6.2 6.2 6.4 6.1 6.5 6.3 6.5
Oil Tube Steel with anti-corrosion, scale-inhibiting coating prepared by specific embodiment 2-8 is kept the temperature for 24 hours at 280 DEG C, is cooled to Its contact angle and roll angle are measured after room temperature.Contact angle reduction amount is as shown in table 2, and roll angle is almost unchanged.As can be seen that height After temperature processing, although each coating layer touch angle value slightly reduces, but still has biggish contact angle, illustrate it with good resistance to It is high temperatures.
The coating of each embodiment of table 2 preparation contact angle reduction amount after high-temperature process
Measure specific embodiment 2-8 preparation respectively in 3.5wt.%NaCl solution has anti-corrosion, scale-inhibiting coating tubing steel Polarization curve, obtain its corrosion potential and corrosion electric current density, as shown in table 3.As can be seen that compared to oil pipe steel matrix, The corrosion potential of coating prepared by each embodiment significantly improves, and corrosion electric current density significantly reduces, and illustrates it with good resistance to Corrosion.
The corrosion resistance of coating prepared by each embodiment of table 3
Embodiment Corrosion potential/V Corrosion electric current density/
Two -0.37259 3.02×10-7
Three -0.36912 2.63×10-7
Four -0.36867 2.77×10-7
Five -0.37236 2.85×10-7
Six -0.37983 2.89×10-7
Seven -0.38113 3.25×10-7
Eight -0.37721 2.76×10-7
The amount of scale buildup of coating prepared by each embodiment of table 4
Embodiment Quality/g before impregnating Quality/g after immersion Mass incremental/g
Two 13.1043 13.1422 0.0379
Three 14.9573 15.0083 0.051
Four 11.1202 11.1663 0.0461
Five 13.7242 13.7571 0.0329
Six 12.4309 12.4586 0.0277
Seven 15.4406 15.4712 0.0306
Eight 13.5188 13.5474 0.0286
Oil Tube Steel with anti-corrosion, scale-inhibiting coating prepared by specific embodiment 2-8, which is placed in oil field mining liquid, impregnates, It takes out dry after seven days and weighs, measure its mass change amount, as shown in table 4.Under same soaking conditions, space management The amount of scale buildup of oil pipe steel matrix is 0.2175g, hence it is evident that greater than the amount of scale buildup with anti-corrosion, scale-inhibiting coating tubing steel, illustrates each implementation Coating prepared by example has good scale inhibition performance.
Oil Tube Steel with anti-corrosion, scale-inhibiting coating prepared by specific embodiment 2-8, which is placed in oil water mixture, impregnates 6 It a month, takes out after-blow dry doubling and measures its contact angle and roll angle.Contact angle reduction amount is as shown in table 5, roll angle almost without Variation.As can be seen that although each coating layer touch angle value slightly reduces, but still having larger after being impregnated in oil water mixture Contact angle, illustrate it with good durability.
Contact angle reduction amount after the coating of each embodiment of table 5 preparation is soaking
In conclusion oil pipe steel coating prepared by specific embodiment 2-8 all have super-hydrophobicity, anti-corrosion, scale-inhibiting and Good high temperature resistant and durability.

Claims (4)

1. a kind of method for preparing high-temperature resistant anti-corrosive scale inhibition coating in oil pipe steel surface, including polishing, alkali cleaning, pickling and deionization Water cleaning, which is characterized in that further include following steps after deionized water cleaning-drying:
(1) Oil Tube Steel after being cleaned and dried deionized water is put into etching liquid, chemical etching 10-30min；
The etching liquid is Copper dichloride dihydrate 0.5-3.0mol/L, and hydrochloric acid 0.2-1.5mol/L, solvent is deionized water；
(2) step (1) treated Oil Tube Steel is taken out, is cleaned with deionized water, dry up, be put into 150-300 DEG C of resistance furnace In be sintered, sintering time 10-60min, then with being furnace-cooled to room temperature；
(3) it is put into the tetradecylic acid ethanol solution of 7-18g/L after taking out step (2) treated Oil Tube Steel and carries out low energy Modification, modification time are 15-48h, and drying box is put into after taking-up and is dried at 40-120 DEG C, can be obtained in oil pipe steel surface resistance to High-temperature anticorrosion scale inhibition coating.
2. a kind of method for preparing high-temperature resistant anti-corrosive scale inhibition coating in oil pipe steel surface according to claim 1, feature It is, in the polishing, alkali cleaning, pickling and deionized water cleaning step, alkali wash water that when alkali cleaning uses are as follows: sodium hydroxide 10-40g/L, sodium carbonate 10-30g/L, sodium phosphate 10-30g/L, sodium metasilicate 5-15g/L, solvent are deionized water.
3. a kind of method for preparing high-temperature resistant anti-corrosive scale inhibition coating in oil pipe steel surface according to claim 1, feature It is, the polishing, alkali cleaning, pickling and deionized water cleaning step are specific as follows:
(1) using 600#-2000# silicon carbide waterproof abrasive paper to Oil Tube Steel carry out grinding process, be then respectively put into acetone and It is cleaned by ultrasonic in dehydrated alcohol, removes surface and oil contaminant and impurity, finally cleans simultaneously rapid draing with deionized water；
(2) by step (1), treated, and Oil Tube Steel is put into alkali wash water, and the alkali cleaning 5-25min at 30-80 DEG C is spent after taking-up Ionized water cleaning and rapid draing；
(3) by step (2), treated that Oil Tube Steel is put into pickling 0.5-5min in pickling solution, is cleaned simultaneously after taking-up with deionized water Rapid draing.
4. a kind of method for preparing high-temperature resistant anti-corrosive scale inhibition coating in oil pipe steel surface according to claim 2, feature It is, pickling solution described in step (3) are as follows: hydrochloric acid 0.5-2.5mol/L, solvent are deionized water.
CN201910154580.2A 2019-02-28 2019-02-28 A method of high-temperature resistant anti-corrosive scale inhibition coating is prepared in oil pipe steel surface Pending CN109680279A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111690961A (en) * 2020-07-14 2020-09-22 四川轻化工大学 Preparation of nitrogen-doped MnCr on FeCrNi alloy surface2O4Method for coating
CN112828291A (en) * 2020-12-31 2021-05-25 宁波通导电子有限公司 Manufacturing method of high-temperature operation robot
CN113820241A (en) * 2021-11-01 2021-12-21 中国石油化工股份有限公司 Scale inhibitor performance evaluation device and method
CN114481108A (en) * 2022-01-19 2022-05-13 合肥矽迈微电子科技有限公司 Copper deposition process pretreatment method and chip packaging process
CN114719662A (en) * 2021-01-04 2022-07-08 中国石油化工股份有限公司 Method for reducing drag, preventing corrosion and inhibiting scale of heat exchanger tube bundle

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005126650A (en) * 2003-10-27 2005-05-19 E Ultimate Investments Ltd Transparent composition for cutting transparent ultraviolet rays and infrared rays
CN104846376A (en) * 2015-05-29 2015-08-19 清华大学 Preparation method of metal-based super-hydrophobic surface
CN105413994A (en) * 2015-12-15 2016-03-23 大连理工大学 Preparation method for super-hydrophobic surface with bionic micro-nano composite structure
CN109023319A (en) * 2018-09-18 2018-12-18 中国石油大学(华东) A method of preparing dendroid micro nano structure copper oxide super-hydrophobic coat

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005126650A (en) * 2003-10-27 2005-05-19 E Ultimate Investments Ltd Transparent composition for cutting transparent ultraviolet rays and infrared rays
CN104846376A (en) * 2015-05-29 2015-08-19 清华大学 Preparation method of metal-based super-hydrophobic surface
CN105413994A (en) * 2015-12-15 2016-03-23 大连理工大学 Preparation method for super-hydrophobic surface with bionic micro-nano composite structure
CN109023319A (en) * 2018-09-18 2018-12-18 中国石油大学(华东) A method of preparing dendroid micro nano structure copper oxide super-hydrophobic coat

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111690961A (en) * 2020-07-14 2020-09-22 四川轻化工大学 Preparation of nitrogen-doped MnCr on FeCrNi alloy surface2O4Method for coating
CN112828291A (en) * 2020-12-31 2021-05-25 宁波通导电子有限公司 Manufacturing method of high-temperature operation robot
CN114719662A (en) * 2021-01-04 2022-07-08 中国石油化工股份有限公司 Method for reducing drag, preventing corrosion and inhibiting scale of heat exchanger tube bundle
CN113820241A (en) * 2021-11-01 2021-12-21 中国石油化工股份有限公司 Scale inhibitor performance evaluation device and method
CN113820241B (en) * 2021-11-01 2024-04-26 中国石油化工股份有限公司 Device and method for evaluating performance of scale inhibitor
CN114481108A (en) * 2022-01-19 2022-05-13 合肥矽迈微电子科技有限公司 Copper deposition process pretreatment method and chip packaging process

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