CN117004901A - Corrosion-resistant and hydrogen-embrittlement-resistant surface treatment method for oil casing thread - Google Patents
Corrosion-resistant and hydrogen-embrittlement-resistant surface treatment method for oil casing thread Download PDFInfo
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- CN117004901A CN117004901A CN202210465606.7A CN202210465606A CN117004901A CN 117004901 A CN117004901 A CN 117004901A CN 202210465606 A CN202210465606 A CN 202210465606A CN 117004901 A CN117004901 A CN 117004901A
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- 238000005260 corrosion Methods 0.000 title claims abstract description 67
- 230000007797 corrosion Effects 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000004381 surface treatment Methods 0.000 title claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000001257 hydrogen Substances 0.000 claims abstract description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 29
- 239000000243 solution Substances 0.000 claims abstract description 29
- 238000000576 coating method Methods 0.000 claims abstract description 28
- 239000011248 coating agent Substances 0.000 claims abstract description 27
- 230000005496 eutectics Effects 0.000 claims abstract description 21
- 238000005255 carburizing Methods 0.000 claims abstract description 19
- 239000002131 composite material Substances 0.000 claims abstract description 18
- 238000007747 plating Methods 0.000 claims abstract description 16
- 238000005238 degreasing Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- QDWJUBJKEHXSMT-UHFFFAOYSA-N boranylidynenickel Chemical compound [Ni]#B QDWJUBJKEHXSMT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 210000001503 joint Anatomy 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 8
- 238000012545 processing Methods 0.000 claims abstract description 8
- 150000002500 ions Chemical class 0.000 claims description 20
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 18
- 238000007789 sealing Methods 0.000 claims description 15
- 238000001514 detection method Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 238000004321 preservation Methods 0.000 claims description 11
- 239000012459 cleaning agent Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- -1 DES ion Chemical class 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 238000007733 ion plating Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000012495 reaction gas Substances 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 238000005256 carbonitriding Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 230000008595 infiltration Effects 0.000 claims description 3
- 238000001764 infiltration Methods 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 230000008878 coupling Effects 0.000 abstract description 28
- 238000010168 coupling process Methods 0.000 abstract description 28
- 238000005859 coupling reaction Methods 0.000 abstract description 28
- 238000009713 electroplating Methods 0.000 abstract description 11
- 230000007547 defect Effects 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 238000004070 electrodeposition Methods 0.000 abstract description 3
- 230000006698 induction Effects 0.000 abstract description 3
- 239000007769 metal material Substances 0.000 abstract description 2
- 238000005299 abrasion Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 9
- 210000002445 nipple Anatomy 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 6
- 235000011187 glycerol Nutrition 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 239000002608 ionic liquid Substances 0.000 description 3
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 2
- 238000005202 decontamination Methods 0.000 description 2
- 230000003588 decontaminative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000005121 nitriding Methods 0.000 description 2
- 239000003129 oil well Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- OGSYQYXYGXIQFH-UHFFFAOYSA-N chromium molybdenum nickel Chemical compound [Cr].[Ni].[Mo] OGSYQYXYGXIQFH-UHFFFAOYSA-N 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
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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
- 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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/36—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases using ionised gases, e.g. ionitriding
- C23C8/38—Treatment of ferrous surfaces
-
- 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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/02—Pretreatment of the material to be coated
-
- 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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/80—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/18—Electroplating using modulated, pulsed or reversing current
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Electrochemistry (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention belongs to the technical field of metal material surface treatment, and particularly relates to a corrosion-resistant and hydrogen embrittlement-resistant surface treatment method for oil casing threads. The surface treatment method for corrosion and hydrogen embrittlement resistance of the oil casing thread specifically comprises the following steps: carrying out thread processing on the oil sleeve joint; deoiling, degreasing and detecting defects; carburizing the inner surface and the outer surface; the inner surface and the outer surface of the butt joint hoop are deposited by adopting a double-pulse power supply in the deep eutectic base ion mixed solution to form a nickel-boron composite coating; and cleaning the oil sleeve joint with clear water, drying and warehousing. The invention can form compact nickel-boron composite coating on the inner and outer surfaces of the oil sleeve joint, not only strengthens the high-temperature oxidation resistance, corrosion resistance and abrasion resistance of the coupling, but also solves the problems of corrosion of oil pipes, such as pitting corrosion, flow induction corrosion, crevice corrosion and the like, which are easy to generate in corrosive medium-containing environment, the electroplating solution does not contain water, hydrogen is avoided in electrodeposition, the hydrogen embrittlement phenomenon of the plating layer is avoided, and the coupling is easy to regenerate and can be recycled.
Description
Technical Field
The invention belongs to the technical field of metal material surface treatment, and particularly relates to a corrosion-resistant and hydrogen embrittlement-resistant surface treatment method for oil casing threads.
Background
In recent years, china increases the development strength of unconventional oil and gas resources such as compact oil, compact gas and the like, and the oil and gas wells have higher requirements on the air tightness, the connection strength, the corrosion resistance and the like of threaded connection, and the traditional API circular threads and trapezoidal and buttress threads can not meet the requirements of the conditions or the environment. For example, special threaded oil well tubing has been commonly used for shale oil and gas recovery in southwest and Xinjiang areas of China.
The coupling is one of important parts for connecting oil casings, and the quality of the coupling can seriously affect the success or failure of drilling and production operations. Through investigation, 64% of foreign oil casing failure accidents occur at the threaded joint, and the domestic proportion is up to 86%. It follows that the threaded joint is the weakest part of the oil casing and that the quality of the threads is directly related to the life of the oil and gas well. The threaded joint is used as a connecting part of an oil casing, and is corroded more easily under the action of complex loads such as stretching, compression, bending, internal pressure, external pressure and the like under the well together with a tubular column, and common failure modes such as pitting corrosion, mesa corrosion, flow induction corrosion, crevice corrosion and the like can cause the occurrence of faults such as sealing, screw thread failure, oil pipe falling and the like, so that larger economic loss is caused. It is therefore desirable for a particular thread configuration to maintain long-term seal integrity and structural integrity at downhole atmospheric pressures, as well as to have high corrosion resistance.
Patent No. 201110007593.0 filed in 2012, 01 and 14 relates to a chromium-nickel-key composite electroplating method for the threaded surface of a special pipe joint for an oil well pipe, and finally, a chromium-nickel-molybdenum composite coating is obtained on the threaded surface of the pipe joint by using an electroplating process. The corrosion resistance of the threads of the special pipe joint is improved. However, the patent adopts a three-layer composite coating, which does not relate to the problems that the plating coating is easy to generate a hydrogen embrittlement site in the water solution plating and the joint is easy to generate crevice corrosion under the action of the load applied to the underground, and does not consider the pollution problem of the plating solution to the industrial production and the environment. Patent number 201911048508.8 of 31 in 2019, 10 and 31 relates to a tungsten plating and corrosion preventing treatment process for a tubing coupling, wherein a tungsten composite coating is finally obtained on the plating surface of the tubing coupling by using an electroplating process, and the tubing coupling is subjected to heat treatment at 200 ℃ after being dried, and tempered, dehydrogenized and tungsten-infiltrated for 8 hours to obtain the corrosion preventing tubing coupling. However, this patent considers the hydrogen embrittlement factor of the coating, but does not consider the environmental and crevice corrosion problems.
Disclosure of Invention
Aiming at the problems of the prior oil casing thread surface treatment method, the invention aims to provide a surface treatment method for corrosion and hydrogen embrittlement resistance of oil casing threads, which can form compact nickel-boron composite coatings on the inner and outer surfaces of the oil casing threads, not only strengthen the high-temperature oxidation resistance, corrosion resistance and wear resistance of couplings, solve the weakness of oil pipe corrosion such as pitting, flow induction corrosion, crevice corrosion and the like which are easy to occur in corrosive medium-containing environments, but also prevent hydrogen from being generated in electrodeposition because deep eutectic-based ion plating solution generally does not contain water, thereby avoiding the occurrence of hydrogen embrittlement phenomenon of plating layers, being easy to regenerate, being capable of being recycled and meeting the requirements of green sustainable industrial production.
The technical scheme of the invention is as follows: a surface treatment method for corrosion and hydrogen embrittlement resistance of oil casing threads comprises the following steps:
s1: carrying out thread processing on the oil sleeve joint, wherein the thread depth is the designed tooth height, and the tolerance range is +/-0.15 mm;
s2: after the threads are machined, deoiling and degreasing the oil sleeve joint by using a cleaning agent at room temperature, and performing flaw detection;
s3: carburizing the inner and outer surfaces of the oil sleeve joint;
s4: placing the carburized oil sleeve joint into a deep eutectic base ion mixed solution, and adopting a double-pulse power supply to deposit the inner surface and the outer surface of the joint to form a nickel-boron composite coating;
s5: and cleaning the oil sleeve joint with clear water, drying and warehousing to finish the surface treatment of the oil sleeve thread with corrosion resistance and hydrogen embrittlement resistance.
And in the step S1, the roughness value Ra of the thread surface of the thread processing is less than or equal to 3.2, and the roughness plating value Ra of the surface of the sealing surface is less than or equal to 1.6.
And in the step S2, deoiling and degreasing the oil sleeve joint at least twice by using a cleaning agent, wherein the cleaning agent is low in alkalinity, the PH range is 7-8, the inner surface and the outer surface of the joint are cleaned by using hot water washing and water washing respectively after deoiling and degreasing, the hot water temperature range of the hot water washing is 50-60 ℃, and the water temperature range of the water washing is 20-25 ℃.
The flaw detection method in the step S2 is a color flaw detection method or a wet magnetic flaw detection method.
The carburizing treatment in the step S3 is carried out in an industrial plasma carburizing furnace, and specific parameters of the carburizing treatment are as follows: the voltage of a power supply system of the industrial plasma infiltration furnace is 200-650V, the duty ratio is 50-64%, and the heat preservation time is 3-7 h; reaction gas H introduced during plasma carbonitriding 2 The flow rate is 300-450 ml/min, CO 2 The flow is 10-25 ml/min; the air pressure is 100-200 Pa, the temperature is 300-500 ℃, and the reaction is cooled along with the furnace after the completion.
In the step S4, a deep eutectic base ion mixed solution is adopted, and the specific preparation process is as follows: uniformly mixing 0.3-0.6 part of 2-hydroxyethyl trimethyl ammonium chloride and 0.6-1.2 parts of glycerin according to a molar ratio to form a chlorine eutectic ion solution ChCl-2 GlyDES, and respectively adding 2-3 parts of 0.5mol/l NiCl into the ChCl-2 GlyDES ion solution 2 .6H 2 O, 2-5 parts of 0.6mol/l WCl 6 .2H 2 O, chCl-2Gly-NiCl formation 2 .6H 2 O-WCl 6 .2H 2 O deep eutectic ion plating solution.
In the step S4, the inner surface and the outer surface of the butt joint hoop are deposited by adopting a double-pulse power supply, and the specific control parameters are as follows: double pulse power supply voltage: 200-400V, 500-999 pulses, duty ratio 40-60%, current density 7A/dm 2 Pulse wave control frequency: 100 to 3000Hz.
And the thickness of the nickel-boron composite coating formed in the step S4 is 15-45 mu m.
The specific preparation process of the ChCl-2Gly DES ion solution comprises the following steps: and uniformly stirring 2-hydroxyethyl trimethyl ammonium chloride and glycerol to form a mixture, heating and melting the mixture in a sealed state at 70-80 ℃, continuously stirring the mixture in the heating process until the mixture becomes colorless clear liquid, drying the obtained colorless clear liquid for at least 12 hours to form a ChCl-2Gly DES ion solution, and vacuum sealing and storing.
The invention has the technical effects that:
1. after plasma carburization treatment is adopted for the special thread oil casing coupling, the oxidation film can be removed, so that the threads, shoulders and the surface of the coupling can be effectively controlled to harden, the deformation is reduced, meanwhile, a growth node is provided for epitaxial growth of a coating phase, and the bonding strength of the coating film/base is improved.
2. The ChCl-2Gly-NiCl adopted by the invention 2 .6H 2 O-WCl 6 .2H 2 Compared with the traditional electroplating solution, the O deep eutectic ion electroplating solution generally does not contain water, and can avoid hydrogen generation in electrodeposition, so that the phenomenon of hydrogen embrittlement of a coating is avoided, no wastewater is discharged, the ionic liquid almost has no steam generation, is easy to regenerate, can be recycled, and can truly realize green production.
3. According to the invention, the surfaces of the oil casing thread, the shoulder and the coupling are modified by a plasma carburization process, and the parameters of the electroplating process are adjusted to enhance the binding force between the material and the coating, so that the coating is wide in coverage rate, thereby forming a nickel-tungsten composite coating with uniform compactness, electrical insulation, wear resistance and corrosion resistance, improving the high-temperature oxidation resistance, corrosion resistance (crevice corrosion and pitting corrosion) and wear resistance of the special threaded coupling, and prolonging the service life of the special threaded coupling.
Detailed Description
The disclosure of the present invention will be further understood in conjunction with the following detailed description of the preferred embodiments of the invention, including examples. Unless defined otherwise, all 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. If the definition of a particular term disclosed in the prior art is inconsistent with any definition provided in the present invention, the definition of the term provided in the present invention controls.
It should be noted that the implementation conditions used in the examples may be further adjusted according to the specific experimental environment, and the implementation conditions that are not noted are generally conditions in the conventional experiments. The preparation methods mentioned in the present invention are all conventional methods unless otherwise specified.
A surface treatment method for corrosion and hydrogen embrittlement resistance of oil casing threads comprises the following steps:
s1: carrying out thread processing on the oil sleeve joint, wherein the thread depth is the designed tooth height, and the tolerance range is +/-0.15 mm;
s2: after the threads are machined, deoiling and degreasing the oil sleeve joint by using a cleaning agent at room temperature, and performing flaw detection;
s3: carburizing the inner and outer surfaces of the oil sleeve joint;
s4: placing the carburized oil sleeve joint into a deep eutectic base ion mixed solution, and adopting a double-pulse power supply to deposit the inner surface and the outer surface of the joint to form a nickel-boron composite coating;
s5: and cleaning the oil sleeve joint with clear water, drying and warehousing to finish the surface treatment of the oil sleeve thread with corrosion resistance and hydrogen embrittlement resistance.
And in the step S1, the roughness value Ra of the thread surface of the thread processing is less than or equal to 3.2, and the roughness plating value Ra of the surface of the sealing surface is less than or equal to 1.6. The roughness value Ra of the thread surface is less than or equal to 3.2, and the roughness plating value Ra of the surface of the sealing surface is less than or equal to 1.6, so that the optimal sealing effect can be achieved when the coupling is in interference fit with the thread of the pipe body in a sealing manner, and the plating layer can be better attached to the surface of the coupling base body of the oil sleeve pipe.
And in the step S2, deoiling and degreasing the oil sleeve joint at least twice by using a cleaning agent, wherein the cleaning agent is low in alkalinity, the PH range is 7-8, the inner surface and the outer surface of the joint are cleaned by using hot water washing and water washing respectively after deoiling and degreasing, the hot water temperature range of the hot water washing is 50-60 ℃, and the water temperature range of the water washing is 20-25 ℃. The low alkaline cleaning agent is subjected to deoiling and degreasing treatment for multiple times, and the inner and outer surfaces of the coupling are cleaned by hot water washing and water washing, so that the cleanliness of the inner and outer surfaces of the coupling of the oil sleeve is ensured, and the subsequent carburization treatment and electroplating treatment are facilitated.
The flaw detection method in the step S2 is a color flaw detection method or a wet magnetic flaw detection method. And (3) checking the part to be treated by adopting a dye-sensitized flaw detection method or a wet magnetic flaw detection method, wherein the part to be treated is required to have no cracks, pores and inclusion defects.
The carburizing treatment in the step S3 is carried out in an industrial plasma carburizing furnace, and specific parameters of the carburizing treatment are as follows: the voltage of a power supply system of the industrial plasma infiltration furnace is 200-650V, the duty ratio is 50-64%, and the heat preservation time is 3-7 h; reaction gas H introduced during plasma carbonitriding 2 The flow rate is 300-450 ml/min, CO 2 The flow is 10-25 ml/min; the air pressure is 100-200 Pa, the temperature is 300-500 ℃, and the reaction is cooled along with the furnace after the completion.
In the step S4, a deep eutectic base ion mixed solution is adopted, and the specific preparation process is as follows: uniformly mixing 0.3-0.6 part of 2-hydroxyethyl trimethyl ammonium chloride and 0.6-1.2 parts of glycerin according to a molar ratio to form a chlorine eutectic ion solution ChCl-2 GlyDES, and respectively adding 2-3 parts of 0.5mol/l NiCl into the ChCl-2 GlyDES ion solution 2 .6H 2 O, 2-5 parts of 0.6mol/l WCl 6 .2H 2 O, chCl-2Gly-NiCl formation 2 .6H 2 O-WCl 6 .2H 2 O deep eutectic ion plating solution.
In the step S4, the inner surface and the outer surface of the butt joint hoop are deposited by adopting a double-pulse power supply, and the specific control parameters are as follows: double pulse power supply voltage: 200-400V, 500-999 pulses, duty ratio 40-60%, current density 7A/dm 2 Pulse wave control frequency: 100 to 3000Hz.
And the thickness of the nickel-boron composite coating formed in the step S4 is 15-45 mu m.
The specific preparation process of the ChCl-2Gly DES ion solution comprises the following steps: and uniformly stirring 2-hydroxyethyl trimethyl ammonium chloride and glycerol to form a mixture, heating and melting the mixture in a sealed state at 70-80 ℃, continuously stirring the mixture in the heating process until the mixture becomes colorless clear liquid, drying the obtained colorless clear liquid for at least 12 hours to form a ChCl-2Gly DES ion solution, and vacuum sealing and storing.
Example 1
The special threaded oil pipe thread of N80 steel grade 88.9mm multiplied by 7.34mm is corrosion-resistant and hydrogen embrittlement-resistant, and the specific process is as follows:
s1, firstly, cutting out two sections of pipe blanks of an N80 steel grade oil pipe, wherein the lengths of the two sections of pipe blanks are 1m, the sizes of coupling materials are 107.9mm multiplied by 20mm, and the pipe blanks are respectively processed into internal and external threads by an OKUMA numerical control horizontal machine tool;
s2, after the thread is machined, performing decontamination degreasing treatment twice by using low-alkaline cleaning liquid at room temperature, cleaning the inner surface and the outer surface of the butt joint hoop by respectively performing hot water washing and water washing, drying for later use, and inspecting the part to be machined by using a dye check method, wherein the part to be machined is required to have no cracks, air holes and inclusion defects, the roughness value of the thread surface is Ra=3.0, and the roughness plating Ra=1.0 of the surface of the sealing surface;
s3, placing the prepared sample into an industrialized bell-type plasma carburizing furnace for carburizing treatment, wherein the control voltage is 450V, the duty ratio is 50% in the carburizing process, and H with the flow rate of 400ml/min and 20ml/min is respectively introduced 2 And CO 2 As reaction gas, the air pressure is 150Pa in the heat preservation process, the nitriding temperature is 500 ℃, the heat preservation time is 6h, and the heat preservation is cooled along with the furnace after the heat preservation is finished;
s4, placing the coupling subjected to carburization treatment into a deep eutectic base ion mixed solution, adopting a double-pulse power supply to deposit the inner surface and the outer surface of the butt joint coupling at the temperature of 65-70 ℃ of the electroplating solution, and controlling parameters: voltage: 200-400V, 500-999 pulses, duty ratio 40-60%, current density 7A/dm 2 Pulse wave control frequency: 100-3000 Hz; deep eutectic base ion mixed solution: mixing 2-hydroxyethyl trimethyl ammonium chloride and glycerol at a molar ratio of 0.5:1 in a 1000mL glass conical flask, stirring with a magnetic stirrer at 80deg.C under sealed condition, heating to melt until the magneton is stirred to give colorless clear liquid, drying the obtained ionic liquid for 12 hr, vacuum sealing, and vacuum preserving 0.5mol NiCl 2 .6H 2 O，0.6molWCl 6 .2H 2 O is added therein to form ChCl-2Gly-NiCl 2 .6H 2 O-WCl 6 .2H 2 O deep eutectic ion plating solution; finally forming the compact nickel-tungsten composite coating with the thickness of 10-20 mu mA layer.
The binding force between the plating layer and the matrix is quantitatively inspected by using a file method, and the result shows that the surface of the composite coating is bright and smooth, has no pinholes or cracks, and has no peeling or falling after the file test; wear resistance test was carried out on a German SST-ST pin-disc frictional wear tester with a friction coefficient of 0.12; the surface roughness is Ra10 or more; the stratum solution of a certain oil field is simulated, the components are shown in table 1, a coupling coating hanging piece sample and a configuration solution are put into a 15L high-temperature high-pressure kettle, sample data are shown in table 2, the temperature is 60 ℃, the rotating speed is 0.5m/s, the hanging piece sample is taken out after 120h, and the calculation is carried out according to the following formula:
wherein CR represents a uniform corrosion rate in mm/a; w is mass loss, and the unit is mg; a is the surface area of the sample in mm 2 The method comprises the steps of carrying out a first treatment on the surface of the D is the density of the material in mg/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the t is the experimental time in h.
The corrosion rate is calculated to be 0.04mm/a, the corrosion resistance is good according to NACE SP0775-2018-SG standard, no pitting corrosion occurs on the surface, and the coating integrity is good.
TABLE 1 ion composition of aqueous solutions of certain oilfield formations (mg/l)
| Cl - | SO 4 2- | CO 3 2- | HCO 3 - | Ca 2+ | Na + | S 2- |
| 1339.0 | 163.0 | 310.1 | 221.3 | 132.6 | 870.1 | 57.6 |
Table 2 laboratory Corrosion Rate calculation data (mm/a)
| Sample number | Weight/g before test | Post test weight/g | Length/mm | Width/mm | Thickness/mm | Surface area/mm 2 | TestTime/h | Corrosion Rate/(mm/a) |
| 1 | 11.2281 | 11.2227 | 50.26 | 10.08 | 3.06 | 1382.5224 | 120 | 0.0362 |
| 2 | 11.1958 | 11.1907 | 49.93 | 10.00 | 2.98 | 1355.7828 | 120 | 0.0365 |
| 3 | 11.2092 | 11.2038 | 50.03 | 10.00 | 3.09 | 1371.5854 | 120 | 0.0343 |
The whole pipe body is subjected to corrosion evaluation by adopting full-size corrosion object evaluation equipment, an N80 steel grade oil pipe nipple is put into the full-size corrosion object evaluation equipment, the underground load condition is simulated, an axial load 678KN is applied to the pipe nipple, the bending degree is 15 degrees, the prepared stratum aqueous solution is introduced to take out the pipe nipple after 96 hours, the pipe nipple is tripped, and the inner surface of a coupling and the outer surface of the pipe body are observed to be free from corrosion.
Example 2
The special threaded sleeve thread of P110 steel grade 114.3mm x 8.56mm is subjected to corrosion-resistant and hydrogen embrittlement-resistant surface treatment, and the specific process is as follows:
s1, firstly, cutting out two sections of pipe blanks of a P110 steel grade sleeve with the length of 1m, the size of a coupling material being 254.6mm multiplied by 22mm, and respectively processing internal and external threads by adopting an OKUMA numerical control horizontal machine tool;
s2, after the thread is machined, performing decontamination degreasing treatment twice by using low-alkaline cleaning liquid at room temperature, cleaning the inner surface and the outer surface of the butt joint hoop by respectively performing hot water washing and water washing, drying for later use, and inspecting the part to be machined by using a dye check method, wherein the part to be machined is required to have no cracks, air holes and inclusion defects, the roughness value Ra of the thread surface is=2.5, and the roughness plating value Ra of the surface of the sealing surface is=1.1;
s3, placing the prepared sample into an industrialized bell-type plasma carburizing furnace for carburizing treatment, wherein the control voltage is 550V, the duty ratio is 60% in the carburizing process, and H with the flow rate of 450ml/min and 25ml/min is respectively introduced 2 And CO 2 As reaction gas, the air pressure is 150Pa in the heat preservation process, the nitriding temperature is 500 ℃, the heat preservation time is 8 hours, and the heat preservation is cooled along with the furnace after the heat preservation is completed;
s4, placing the coupling subjected to carburization treatment into a deep eutectic base ion mixed solution, adopting a double-pulse power supply to deposit the inner surface and the outer surface of the butt joint coupling at the temperature of 65-70 ℃ of the electroplating solution, and controlling parameters: voltage: 200-400V, 500-999 pulses, duty ratio 40-60%, current density 7A/dm 2 Pulse wave control frequency: 100-3000 Hz; deep eutectic base ion mixed solution: mixing 2-hydroxyethyl trimethyl ammonium chloride and glycerol at a molar ratio of 0.5:1 in a 1000mL glass conical flask, stirring with a magnetic stirrer at 80deg.C under sealed condition, and heating to melt until the magnetic particles are stirred to give colorless clear solutionBright liquid, drying the obtained ionic liquid for 12 hours, vacuum sealing and preserving, and then drying 0.5mol of NiCl 2 .6H 2 O，0.6molWCl 6 .2H 2 O is added therein to form ChCl-2Gly-NiCl 2 .6H 2 O-WCl 6 .2H 2 And finally forming a 30-45 mu m compact nickel-tungsten composite coating by using the O deep eutectic ion electroplating solution.
The binding force between the plating layer and the matrix is quantitatively inspected by using a file method, and the result shows that the surface of the composite coating is bright and smooth, has no pinholes or cracks, and has no peeling or falling after the file test; wear resistance test was carried out on a German SST-ST pin-disc frictional wear tester with a friction coefficient of 0.09; the surface roughness is Ra10 or more; the stratum solution of a certain oil field is simulated, the components are shown in table 3, a coupling coating hanging piece sample and a configuration solution are put into a 15L high-temperature high-pressure kettle, sample data are shown in table 4, the temperature is 120 ℃, the rotating speed is 0.5m/s, the hanging piece sample is taken out after 120h, and the calculation is carried out according to the following formula:
wherein CR represents a uniform corrosion rate in mm/a; w is mass loss, and the unit is mg; a is the surface area of the sample in mm 2 The method comprises the steps of carrying out a first treatment on the surface of the D is the density of the material in mg/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the t is the experimental time in h.
The corrosion rate is calculated to be 0.06mm/a, the corrosion resistance is good according to NACE SP0775-2018-SG standard, no pitting corrosion appears on the surface, and the coating integrity is good.
TABLE 3 ion composition of aqueous solutions of certain oilfield formations (mg/l)
| Cl - | SO 4 2- | CO 3 2- | HCO 3 - | Ca 2+ | Na + | S 2- |
| 2339.0 | 163.0 | 310.1 | 221.3 | 132.6 | 870.1 | 57.6 |
Table 4 laboratory Corrosion Rate calculation data (mm/a)
| Sample number | Weight/g before test | Post test weight/g | Length/mm | Width/mm | Thickness/mm | Surface area/mm 2 | Test time/h | Corrosion Rate/(mm/a) |
| 4 | 8.3758 | 8.3731 | 40.17 | 10.01 | 2.91 | 1096.251 | 114 | 0.05 |
| 5 | 8.3293 | 8.3255 | 39.97 | 10.05 | 2.92 | 1095.5138 | 114 | 0.063 |
| 6 | 8.1813 | 8.1778 | 40.17 | 10.11 | 2.85 | 1098.8334 | 114 | 0.061 |
And (3) adopting full-size corrosion object evaluation equipment to perform corrosion evaluation on the whole pipe body, putting the P110 steel grade oil pipe nipple into the full-size corrosion object evaluation equipment, simulating underground load conditions, applying axial load 1978KN to the pipe nipple, applying bending degree of 15 degrees, introducing prepared stratum aqueous solution to take out the pipe nipple after 114 hours, and breaking out the pipe nipple to observe that no corrosion occurs on the inner surface of a coupling and the outer surface of the pipe body.
In summary, the method for surface treatment of oil casing threads with corrosion resistance and hydrogen embrittlement resistance of the present invention is suitable for the treatment of threaded joints of steel pipes and pipe fittings with complex shapes, which are composed of threads, sealing surfaces, shoulders, etc.
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention.
Claims (9)
1. A surface treatment method for corrosion resistance and hydrogen embrittlement resistance of oil casing threads is characterized by comprising the following steps: the method comprises the following steps:
s1: carrying out thread processing on the oil sleeve joint, wherein the thread depth is the designed tooth height, and the tolerance range is +/-0.15 mm;
s2: after the threads are machined, deoiling and degreasing the oil sleeve joint by using a cleaning agent at room temperature, and performing flaw detection;
s3: carburizing the inner and outer surfaces of the oil sleeve joint;
s4: placing the carburized oil sleeve joint into a deep eutectic base ion mixed solution, and adopting a double-pulse power supply to deposit the inner surface and the outer surface of the joint to form a nickel-boron composite coating;
s5: and cleaning the oil sleeve joint with clear water, drying and warehousing to finish the surface treatment of the oil sleeve thread with corrosion resistance and hydrogen embrittlement resistance.
2. A method of surface treatment for corrosion and hydrogen embrittlement resistance of oil casing threads according to claim 1, wherein: and in the step S1, the roughness value Ra of the thread surface of the oil sleeve thread processing is less than or equal to 3.2, and the roughness plating value Ra of the surface of the sealing surface is less than or equal to 1.6.
3. A method of surface treatment for corrosion and hydrogen embrittlement resistance of oil casing threads according to claim 1, wherein: and in the step S2, deoiling and degreasing the oil sleeve joint at least twice by using a cleaning agent, wherein the cleaning agent is low in alkalinity, the PH range is 7-8, the inner surface and the outer surface of the joint are cleaned by using hot water washing and water washing respectively after deoiling and degreasing, the hot water temperature range of the hot water washing is 50-60 ℃, and the water temperature range of the water washing is 20-25 ℃.
4. A method of surface treatment for corrosion and hydrogen embrittlement resistance of oil casing threads according to claim 1, wherein: the flaw detection method in the step S2 is a color flaw detection method or a wet magnetic flaw detection method.
5. A method of surface treatment for corrosion and hydrogen embrittlement resistance of oil casing threads according to claim 1, wherein: the carburizing treatment in the step S3 is carried out in an industrial plasma carburizing furnace, and specific parameters of the carburizing treatment are as follows: the voltage of a power supply system of the industrial plasma infiltration furnace is 200-650V, the duty ratio is 50-64%, and the heat preservation time is 3-7 h; reaction gas H introduced during plasma carbonitriding 2 The flow rate is 300-450 ml/min, CO 2 The flow is 10-25 ml/min; the air pressure is 100-200 Pa, the temperature is 300-500 ℃, and the reaction is cooled along with the furnace after the completion.
6. A method of surface treatment for corrosion and hydrogen embrittlement resistance of oil casing threads according to claim 1, wherein: in the step S4, a deep eutectic base ion mixed solution is adopted, and the specific preparation process is as follows: according to the molar ratio, 0.3 to 0.6 part of 2-hydroxyethyl trimethyl ammonium chloride and 0.6 to 1.2 parts of glycerinUniformly mixing to form a chlorine eutectic ion solution ChCl-2 GlyDES, and respectively adding 2-3 parts of 0.5mol/l NiCl into the ChCl-2 GlyDES ion solution 2 .6H 2 O, 2-5 parts of 0.6mol/l WCl 6 .2H 2 O, chCl-2Gly-NiCl formation 2 .6H 2 O-WCl 6 .2H 2 O deep eutectic ion plating solution.
7. A method of surface treatment for corrosion and hydrogen embrittlement resistance of oil casing threads according to claim 1, wherein: in the step S4, the inner surface and the outer surface of the butt joint hoop are deposited by adopting a double-pulse power supply, and the specific control parameters are as follows: double pulse power supply voltage: 200-400V, 500-999 pulses, duty ratio 40-60%, current density 7A/dm 2 Pulse wave control frequency: 100 to 3000Hz.
8. A method of surface treatment for corrosion and hydrogen embrittlement resistance of oil casing threads according to claim 1, wherein: and the thickness of the nickel-boron composite coating formed in the step S4 is 15-45 mu m.
9. The surface treatment method for corrosion and hydrogen embrittlement resistance of oil casing threads according to claim 6, wherein: the specific preparation process of the ChCl-2Gly DES ion solution comprises the following steps: and uniformly stirring 2-hydroxyethyl trimethyl ammonium chloride and glycerol to form a mixture, heating and melting the mixture in a sealed state at 70-80 ℃, continuously stirring the mixture in the heating process until the mixture becomes colorless clear liquid, drying the obtained colorless clear liquid for at least 12 hours to form a ChCl-2Gly DES ion solution, and vacuum sealing and storing.
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