CN106555137B - A kind of manufacture method of corrosion resisting alloy hot finished steel pipe - Google Patents

A kind of manufacture method of corrosion resisting alloy hot finished steel pipe Download PDF

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Publication number
CN106555137B
CN106555137B CN201611077695.9A CN201611077695A CN106555137B CN 106555137 B CN106555137 B CN 106555137B CN 201611077695 A CN201611077695 A CN 201611077695A CN 106555137 B CN106555137 B CN 106555137B
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steel pipe
corrosion
steel
manufacture method
resisting alloy
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CN106555137A (en
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徐士祺
郝上京
王勇
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Xian Shiyou University
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Xian Shiyou University
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/10—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies
    • C21D8/105—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies of ferrous alloys
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/08—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for tubular bodies or pipes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/16—Ferrous alloys, e.g. steel alloys containing copper
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/12—Oxygen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/141—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/16—Sulfur-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/173—Macromolecular compounds

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  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Heat Treatment Of Articles (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

It is an object of the invention to provide a kind of manufacture method of the corrosion resisting alloy hot finished steel pipe of strong, the comprehensive fine corrosion resistance of acid resistance.The manufacture method of the steel pipe is：The pre- desulfurization of blast furnace ironmaking, molten steel, converter top bottom blowing, the refining of LF stoves, continuous casting steel pipe blank, heating, perforation, tandem rolling, tension force sizing, correction, cooling；Prewashing；Prewashing is carried out to steel pipe inner wall using corrosion inhibiter, after corrosion inhibiter contacts with steel pipe inner wall, one layer of uniform protecting film can be formed in steel pipe inner wall, improve the corrosion resistance of steel pipe inner wall；Sodium gluconate preferably realizes the absorption to metal ions such as aluminium present in steel pipe, copper, forms the complex compound of electron ion, avoids that electrochemical corrosion occurs；Corrosion inhibiter a variety of release mechanisms is present, preferably realize etch-proof effect；Addition corrosion inhibiter need not be continued during pipeline transportation crude oil, maintenance workload is small.

Description

A kind of manufacture method of corrosion resisting alloy hot finished steel pipe
Technical field
The present invention relates to petroleum pipeline manufacturing field, more particularly to a kind of manufacture method of corrosion resisting alloy hot finished steel pipe.
Background technology
Corrosion is one of problem for perplexing industrial gas oil development, according to "ball-park" estimate, is corroded to China's oil Loss accounts for the 6% of the industry gross output value caused by industry, and takes suitable anti-corrosion measure at least to retrieve 30%-40%'s Loss.The common mounting means of petroleum pipeline of China's transport at present is to be embedded in underground, and also some petroleum pipeline is to place In open-air atmosphere, this just further increases the requirement to the corrosion resistance of petroleum pipeline, should meet the anti-of inner-walls of duct Corrosion requires, meets the requirement of atmospheric corrosion resistance again.
Sour gas corrosion is most common a kind of erosional forms for running into petroleum pipeline corrosion, the crude oil or original of oil All contain substantial amounts of sulphur (S) in the extractive matter of oil, sulphur (S) is oxidized to form sulfur dioxide and sulfur trioxide, in dew-point temperature and Water vapour, which combines, becomes sulfuric acid, and sulfuric acid has strong corrosivity to the inwall of transport pipeline.Steel for resisting sulfuric acid dew point corrosion is A kind of not only resistant to sulfuric acid dew point corrosion but also the steel grade of atmospheric corrosion resistance.
Domestic development and exploitation for corrosionproof steel against sulfuric acid at dew point is started late, and component system and is borrowed using Standard General Reflect Japanese steel grade, wherein typically having the lOCu1Cu of the B485NL of In Baosteel, Anshan iron and steel plant, in addition with Jiangyin special steel ND (09CuCuSb) steel, help steel 12MnCuCu and the steel company of Baosteel one NS corrosionproof steel against sulfuric acid at dew point products.
But above-mentioned several corrosionproof steel against sulfuric acid at dew point only have the ability for preventing that acidic liquid from corroding, and in crude oil Other types corrosive effect it is bad, oil field corrosion there is following feature：Gas and water, hydrocarbon, Multiphase Flow Jie coexisted admittedly Matter, existing general corrosion have local corrosion, in addition to carbon dioxide and the acid liquid corrosion of formation, hydrogen sulfide corrosion, answered again Power corrosion cracking and microbiologic(al) corrosion etc., in order to further improve the synthesis corrosion resistance of petroleum pipeline inwall, it can typically adopt With pickling, but pickling can not effectively prevent a variety of corrosion of inner-walls of duct, and corrosion resistance is poor, and the bad control of pickling time System, causes inner-walls of duct pickling in uneven thickness, also a kind of technology is the brushing anticorrosive coat on inwall, but anticorrosive coat is not allowed Easily brush uniformly, and under the impact flow of crude oil, anticorrosive coat is easily split away off from petroleum pipeline inwall, another technology is Using galvanized pipe as petroleum transportation pipeline, but it is larger for caliber, for the longer pipeline of length, without corresponding size Galvanizing equipment, and it is zinc-plated expensive.
At present in petrochemical industry, for the anti-corrosion inside conveyance conduit, addition in a fluid can also be used slow Lose agent method, corrosion inhibiter refer to by appropriate concentration and in the form of be present in surrounding medium when, can prevent or slow down material The chemical substance or compound of corrosion, therefore corrosion inhibiter is referred to as corrosion inhibitor.Its dosage very little, but effect shows Write.Corrosion inhibiter is currently used primarily in neutral medium (boiler feed water, recirculated cooling water), acid medium (hydrochloric acid to descale, plating The acid dip solution of preceding plating piece derusting) and gas medium (vapour phase inhibitor).A kind of adsorbed film type corrosion inhibiter tool in corrosion inhibiter Polarized gene, it can be adsorbed by the surface charge of metal (especially non-ferrous metal, such as copper), in whole anode and cathode zone One layer of monomolecular film is formed, so as to prevent or slow down the reaction of corresponding electrochemistry.
It is relatively complicated using process but corrosion inhibiter needs to add in flow media at any time when in use, therefore can be with Consider to manufacture a kind of corrosionproof steel against sulfuric acid at dew point containing non-ferrous metal, and the inwall of the steel pipe is entered using special corrosion inhibiter Row prewashing, steel pipe inner wall is reacted in advance with corrosion inhibiter, form corrosion prevention film, pickling can be so replaced, so as to improve The synthesis decay resistance of corrosionproof steel against sulfuric acid at dew point pipe, can also reduce maintenance workload.
The content of the invention
In view of the above-mentioned problems, it is an object of the invention to provide a kind of the resistance to of good, the comprehensive fine corrosion resistance of acid resistance The manufacture method of resistant alloy hot finished steel pipe.
To achieve the above object, the technical solution adopted in the present invention is：A kind of manufacture of corrosion resisting alloy hot finished steel pipe Method, the manufacture method of the steel pipe include the following steps that order is carried out：The pre- desulfurization of blast furnace ironmaking, molten steel, converter top bottom are answered Close blowing, the refining of LF stoves, continuous casting steel pipe blank, heating, perforation, tandem rolling, tension force sizing, correction, cooling, prewashing；
Described prewashing technique is carried out in accordance with the following steps：
A. thiocyanate salt solution is mixed at ambient temperature with N doping mesoporous carbon, stirred；
B. polyacrylic acid, citric acid, methyl butynol, surfactant, glucose are added in step a mixed solution Sour sodium, aromatic series azole and organic amine, the water bath with thermostatic control 1-2h under 80 DEG C of -90 DEG C of temperature conditionss；
C. barium mahogany sulfonate and silica gel support perchloric acid are added in prepolymer prepared by step b, is 200- in rotating speed It is sufficiently mixed and stirs under the conditions of 400r/min, water bath with thermostatic control 2-3h, then stands at room temperature under the conditions of 60 DEG C -75 DEG C 10h-15h, corrosion inhibiter is obtained after bubble collapse；
D. steel pipe is fixed on horizontal type centrifuger, heating steel pipe makes its temperature be maintained between 85 DEG C -92 DEG C, then Corrosion inhibiter is injected in steel duct, the relation between the dosage and steel pipe inner wall surface area of corrosion inhibiter is inhibiter consumption 2.5- 3.0L/m2, steel pipe both sides are blocked using plug, start horizontal type centrifuger, it is 600-650r/min to keep its rotating speed, is continued 5-8min；
E. distilled water is injected in steel duct, the water of injection is 3-5 times of corrosion inhibiter, i.e. the dosage and steel pipe of corrosion inhibiter Relation between inner wall surface area is 2.5-3.0L/m2, the water of injection is 2.5-3.0L/m23-5 times；Horizontal type centrifuger Rotating speed 550-600r/min, continue 1.5-2h；
F. distilled water is re-injected in steel duct, the distilled water of injection is 2-3 times of injected water volume in step e, horizontal Formula centrifuge speed 100-120r/min, continue 8-10h；
Preferably, in described step d, after steel duct injects a certain amount of corrosion inhibiter, to steel pipe inner chamber inflated with nitrogen, and The pressure of steel pipe inner chamber is set to be maintained between 10-50kPa.
Preferably, step g is also included after described step f, step g process is：It is by steel duct injection pH value Subacidity distilled water between 7.6-8.0, horizontal type centrifuger rotating speed 100-120r/min, continue 10-15min.
Preferably, described aromatic series azole is that thin base BTA and methyl benzotriazazole are 1 by weight proportion: The mixture that 1 ratio mixes；Or mixed to dredge the ratio that base BTA and BTA are 1: 1 by weight proportion Close the mixture formed.
Preferably, described rhodanate is sodium sulfocyanate or potassium rhodanide or ammonium thiocyanate.
Preferably, described organic amine is methyl diethanolamine, diisopropanolamine (DIPA), MEA, cetylamine, 18 Any one in amine, beautiful jade, diethanol amine or triethanolamine, or be that MEA, beautiful jade, diethanol are 1 by weight proportion: 2: 1.5 ratio mixes.
Preferably, the constituent of the corrosion inhibiter in described step c is by weight percentage：1%-3% polyacrylic acid, 1%-2% citric acids, 1%-2% methyl butynols, 3%-9% surfactants, 5%-7% sodium gluconates, 1%-5% virtues Fragrant race's azole, 5%-15% rhodanates, 20%-28% organic amines, 10%-25% N dopings mesoporous carbon, 15%-25% stones Oily barium sulfonate, 0.5%-1% silica gel supports perchloric acid, 10%-25% distilled water.
Preferably, after described converter top bottom blowing step, to C, Mo in molten steel, Mn, Ni, Cu, Sb, V, Zr, Als, Nb, Ti, W element carry out content analysis, then add corresponding close into molten steel in LF stove refinement steps as needed Golden dispensing so that the content of each element is within the content range, then refined in molten steel；
Described cooling step is that the steel pipe after correction is placed in the vacuum cooled stove that pressure is 10-30kPa to cool down To 850-900 DEG C, water-spraying control processing then is carried out to steel tube surface, its temperature is dropped to 600 DEG C -650 DEG C, it is last empty It is cold；1080 DEG C -1090 DEG C laggard eleven punch 11 steps, described tandem rolling step are heated in described heating stepses to steel pipe blank The temperature of middle steel pipe blank is 1035 DEG C -1055 DEG C, and the temperature of steel pipe blank is 935 DEG C -955 in described tension force sizing step ℃。
Preferably, the constituent of the steel pipe is by weight percentage：C 0.05%-0.10%, Mo 0.1%- 0.3%, Mn 0.7%-1.1%, P≤0.01%, S≤0.005%, N≤0.005%, O≤0.001%, and contain Ni 0.08%-0.12%, Cu 0.7%-1.0%, Sb 0.04%-0.1%, V 0.1%-0.15%, Zr 0.15%-0.35%, Als 0.01%-0.05%, Nb 0.02%-0.07%, Ti 0.02%-0.08%, light rare earth LREE 0.01%-0.03%, W 0.05%-0.2%, and meet 1.0%≤Cu+Zr+Als+Ti≤1.4%, surplus is Fe and inevitable impurity；
Preferably, the constituent of described steel pipe is by weight percentage：C 0.1%, Mo 0.3%, Mn：0.9%, P ≤ 0.02%, S≤0.002%, N≤0.005%, O≤0.001%, Ni 0.12%, Cu 0.75%, Sb 0.1%, V 0.15%, Zr 0.35%, Als 0.05%, Nb 0.07%, Ti 0.02%, light rare earth LREE 0.03%, W 0.2%, and Meet 1.0%≤Cu+Zr+Als+Ti≤1.4%, surplus is Fe and inevitable impurity.
The invention has the advantages that：Prewashing, corrosion inhibiter and steel pipe inner wall are carried out to steel pipe inner wall using corrosion inhibiter After contact, one layer of uniform protecting film can be formed in steel pipe inner wall, preferably ensure the corrosion resistance of steel pipe inner wall；Gluconic acid Sodium preferably realizes the absorption to metal ions such as aluminium present in steel pipe, copper, forms the complex compound of electron ion, avoids that electricity occurs Chemical attack；Corrosion inhibiter a variety of release mechanisms is present, preferably realize etch-proof effect；Need not during pipeline transportation crude oil Corrosion inhibiter is persistently added, maintenance workload is small.
Embodiment
A kind of corrosion resisting alloy hot finished steel pipe, the constituent of the steel pipe are by weight percentage：C 0.05%- 0.10%, Mo 0.17%-0.37%, Mn 0.7%-1.1%, P≤0.02%, S≤0.002%, N≤0.005%, O≤ 0.001%, Ni 0.08%-0.12%, Cu 0.7%-1.0%, Sb 0.04%-0.1%, V 0.1%-0.15%, Zr 0.15%-0.35%, Als 0.01%-0.05%, Nb 0.02%-0.07%, Ti 0.02%-0.08%, light rare earth LREE 0.01%-0.03%, W 0.05%-0.2%, and meet 1.0%≤Cu+Zr+Als+Ti≤1.4%, surplus is Fe and can not The impurity avoided；
The manufacture method of the steel pipe includes the following steps that order is carried out：The pre- desulfurization of blast furnace ironmaking, molten steel, converter top bottom Top-bottom blowing, the refining of LF stoves, continuous casting steel pipe blank, heating, perforation, tandem rolling, tension force sizing, correction, cooling；Prewashing.
After described converter top bottom blowing step, to C, Mo in molten steel, Mn, Ni, Cu, Sb, V, Zr, Als, Nb, Ti, W element carry out content analysis, and corresponding alloying ingredient is then added into molten steel in LF stove refinement steps as needed, So that the content of each element is within the content range, then refined in molten steel；
Preferably embodiment is：After described LF stove refinement steps, molten steel is carried out to feed the change of Ca-Mo lines sulphide inculsion Property processing, then carry out continuous casting steel pipe blank step, can so effectively improve the quality of steel pipe blank.
The steel pipe manufactured according to above-mentioned manufacture method, its constituent are configured to embodiment 1 to implementation by weight percentage Example 4, the constituent of steel pipe is as follows in each embodiment：
Embodiment 1
The constituent of described steel pipe is by weight percentage：C 0.05%, Mo 0.1%, Mn：1.1%, P≤ 0.02%, S≤0.002%, N≤0.005%, O≤0.001%, Ni 0.08%, Cu 1.0%, Sb 0.04%, V 0.1%, Zr 0.2%, Als 0.01%, Nb 0.02%, Ti 0.08%, W 0.05%, light rare earth LREE 0.01%, and meet 1.0%≤Cu+Zr+Als+Ti≤1.4%, surplus are Fe and inevitable impurity；
Described cooling step is that the steel pipe after correction is placed in the vacuum cooled stove that pressure is 10kPa to be cooled to 850 DEG C, water-spraying control processing then is carried out to steel tube surface, its temperature is dropped to 650 DEG C, last air cooling.Described heating Step is heated to 1090 DEG C of laggard eleven punch 11 steps to steel pipe blank, and the temperature of steel pipe blank is 1055 in described tandem rolling step DEG C, the temperature of steel pipe blank is 955 DEG C in described tension force sizing step.
Embodiment 2
The constituent of described steel pipe is by weight percentage：C 0.07%, Mo 0.1%, Mn：1.1%, P≤ 0.02%, S≤0.002%, N≤0.005%, 0≤0.001%, Ni 0.1%, Cu 0.8%, Sb 0.07%, V0.12%, Zr 0.15%, Als 0.01%, Nb 0.05%, Ti 0.05%, W 0.1%, light rare earth LREE 0.01%, and meet 1.0%≤Cu+Zr+Als+Ti≤1.4%, surplus are Fe and inevitable impurity；
Described cooling step is that the steel pipe after correction is placed in the vacuum cooled stove that pressure is 15kPa to be cooled to 870 DEG C, water-spraying control processing then is carried out to steel tube surface, its temperature is dropped to 630 DEG C, last air cooling.Described heating Step is heated to 1090 DEG C of laggard eleven punch 11 steps to steel pipe blank, and the temperature of steel pipe blank is 1055 in described tandem rolling step DEG C, the temperature of steel pipe blank is 940 DEG C in described tension force sizing step.
Embodiment 3
The constituent of described steel pipe is by weight percentage：C 0.05%, Mo 0.15%, Mn：0.7%, P≤ 0.02%, S≤0.002%, N≤0.005%, O≤0.001%, Ni 0.12%, Cu 1.0%, Sb 0.1%, V 0.15%, Zr 0.2%, Als 0.02%, Nb 0.07%, Ti 0.05%, W 0.2%, light rare earth LREE 0.02%, and meet 1.0% ≤ Cu+Zr+Als+Ti≤1.4%, surplus are Fe and inevitable impurity；
Described cooling step is that the steel pipe after correction is placed in the vacuum cooled stove that pressure is 30kPa to be cooled to 900 DEG C, water-spraying control processing then is carried out to steel tube surface, its temperature is dropped to 600 DEG C, last air cooling.Described heating Step is heated to 1080 DEG C of laggard eleven punch 11 steps to steel pipe blank, and the temperature of steel pipe blank is 1035 in described tandem rolling step DEG C, the temperature of steel pipe blank is 935 DEG C in described tension force sizing step.
Embodiment 4
The constituent of described steel pipe is by weight percentage：C 0.1%, Mo 0.3%, Mn：0.9%, P≤ 0.02%, S≤0.002%, N≤0.005%, O≤0.001%, Ni 0.12%, Cu 0.75%, Sb 0.1%, V 0.15%, Zr 0.35%, Als 0.05%, Nb 0.07%, Ti 0.02%, W 0.2%, light rare earth LREE 0.03%, and Meet 1.0%≤Cu+Zr+Als+Ti≤1.4%, surplus is Fe and inevitable impurity.
Described cooling step is that the steel pipe after correction is placed in the vacuum cooled stove that pressure is 30kPa to be cooled to 900 DEG C, water-spraying control processing then is carried out to steel tube surface, its temperature is dropped to 650 DEG C, last air cooling.Described heating Step is heated to 1080 DEG C of laggard eleven punch 11 steps to steel pipe blank, and the temperature of steel pipe blank is 1035 in described tandem rolling step DEG C, the temperature of steel pipe blank is 955 DEG C in described tension force sizing step.
Steel duct embodiment 1 of the present invention is as shown in table 1 to embodiment 4 and the constituent percentage contrast of contrast steel pipe：
The steel pipe constituent percentage composition table of table 1
According to the steel pipe of the constituent shown in embodiment 1 to embodiment 4, respectively 1 1000 × 100 × 10mm of making, and Percentage of total elongation is selected up to the stress (Rt0.5) when 0.5%, tensile strength (Rm) the L360MCS seamless steel pipe close with the present invention Steel pipe as a comparison, 1000 × 100 × 10mm of size of steel pipe is contrasted, 5 steel pipes are put into 70 DEG C respectively, 20% H2SO4It is molten In liquid, the corrosion rate of each outer surface of steel tube is as shown in table 2：
The embodiment 1 of table 2 to embodiment 4 and contrast steel pipe comparison between corrosion
Rt0.5MPa Rm (MPa, Min) Corrosion rate (g/m2.h)
Embodiment 1 360-510 460 8.6
Embodiment 2 385-530 470 6.7
Embodiment 3 375-515 475 6.2
Embodiment 4 385-530 475 4.3
Contrast steel pipe (L360MCS) 360-510 460 12.0
As shown in Table 2, the steel pipe corrosion resistance to sulfuric acid in embodiment 4 is best.Experiment 2 times is repeated, acquired results are consistent.
The prewashing technique of the steel pipe is carried out in accordance with the following steps：
A. thiocyanate salt solution is mixed at ambient temperature with N doping mesoporous carbon, stirred；
B. polyacrylic acid, citric acid, methyl butynol, surfactant, glucose are added in step a mixed solution Sour sodium, aromatic series azole and organic amine, then realize prepolymerization under 80 DEG C of -110 DEG C of temperature conditionss；
C. barium mahogany sulfonate and silica gel support perchloric acid are added in prepolymer prepared by step b, is 200- in rotating speed It is sufficiently mixed and stirs under the conditions of 400r/min, water bath with thermostatic control 2-3h, then stands at room temperature under the conditions of 60 DEG C -75 DEG C 10h-15h, corrosion inhibiter is obtained after bubble collapse；
D. the steel pipe after air cooling is fixed on horizontal type centrifuger, heating steel pipe makes its temperature be maintained at 85 DEG C -92 DEG C Between, a certain amount of corrosion inhibiter then is injected in steel duct, the dosage of corrosion inhibiter is 2.5-3.0L/m2, steel pipe inner chamber is filled Nitrogen, and the pressure of steel pipe inner chamber is maintained between 10-50kPa；Steel pipe both sides are blocked using plug, start horizontal from Scheming, it is 600-650r/min to keep its rotating speed, continues 5-8min；
E. distilled water is injected in steel duct, the water of injection is 3-5 times of corrosion inhibiter, i.e. the dosage and steel pipe of corrosion inhibiter Relation between inner wall surface area is 2.5-3.0L/m2, the water of injection is 2.5-3.0L/m23-5 times；Horizontal type centrifuger Rotating speed 550-600r/min, continue 1.5-2h；
F. distilled water is re-injected in steel duct, the distilled water of injection is 2-3 times of injected water volume in step e, horizontal Formula centrifuge speed 100-120r/min, continue 8-10h；
Also include step g after described step f, step g process is：By steel duct injection pH value be 7.6-8.0 it Between subacidity distilled water, horizontal type centrifuger rotating speed 100-120r/min, continue 10-15min.
The constituent of corrosion inhibiter in described step c is by weight percentage：1%-3% polyacrylic acid, 1%-2% Citric acid, 1%-2% methyl butynols, 3%-9% surfactants, 5%-7% sodium gluconates, 1%-5% aromatic series azoles Class, 5%-15% rhodanates, 20%-28% organic amines, 10%-25% N dopings mesoporous carbon, 15%-25% mahogany acids Barium, 0.5%-1% silica gel supports perchloric acid, 10%-25% distilled water.
Described aromatic series azole is the ratio that thin base BTA and methyl benzotriazazole are 1: 1 by weight proportion The mixture mixed, or mixed to dredge the ratio that base BTA and BTA are 1: 1 by weight proportion Mixture；Described rhodanate is sodium sulfocyanate or potassium rhodanide or ammonium thiocyanate；Described organic amine is methyl two Any one in monoethanolamine, diisopropanolamine (DIPA), MEA, cetylamine, octadecylamine, beautiful jade, diethanol amine or triethanolamine, Or it is that MEA, beautiful jade, diethanol are that 1: 2: 1.5 ratio mixes by weight proportion.
Different ratio is carried out according to the constituent of corrosion inhibiter and forms embodiment 5 to the composition of embodiment 8, wherein corrosion inhibiter Composition quality fractional content is as shown in table 3：
The corrosion inhibiter constituent mass fraction content of table 3
Embodiment 5
Described step b realizes prepolymerization under 80 DEG C of temperature conditionss；Filled in step c under the conditions of rotating speed is 400r/min Divide and be mixed evenly, water bath with thermostatic control 3h, then stands 15h at room temperature under the conditions of 60 DEG C；Steel pipe is heated in step d makes it Temperature is maintained between 85 DEG C -87 DEG C, and the relation between corrosion inhibiter and steel pipe internal-surface area is every square metre of steel pipe internal-surface Using 2.8L corrosion inhibiter, i.e. the dosage of corrosion inhibiter is 2.5L/m2, the pressure of steel pipe inner chamber is maintained between 10-20kPa；Start Its rotating speed of horizontal type centrifuger is 600-650r/min, continues 85min；The water injected in step e is 7.5L/m2, horizontal Centrifuge speed 550-600r/min, continue 2h；The distilled water injected in step f is 15L/m2, horizontal type centrifuger rotating speed 100-120r/min, continue 10h；Horizontal centrifuge speed 100-120r/min in step g, continue 10min；
Described aromatic series azole is the ratio that thin base BTA and methyl benzotriazazole are 1: 1 by weight proportion The mixture mixed；Described rhodanate is sodium sulfocyanate；Described organic amine is methyl diethanolamine.
Embodiment 6
Described step b realizes prepolymerization under 110 DEG C of temperature conditionss；In step c under the conditions of rotating speed is 200r/min It is sufficiently mixed and stirs, water bath with thermostatic control 3h, then stands 15h at room temperature under the conditions of 70 DEG C -75 DEG C；Heated in step d Steel pipe makes its temperature be maintained between 87 DEG C -92 DEG C, and the dosage of corrosion inhibiter is 2.8L/m2, the pressure of steel pipe inner chamber is maintained at Between 20kPa-30kPa；Its rotating speed of startup horizontal type centrifuger is 600-650r/min, continues 8min；The water injected in step e Measure as 14L/m2, horizontal type centrifuger rotating speed 550-600r/min, continue 2h；The distilled water injected in step f is 42L/m2, water Flat centrifuge speed 100-120r/min, continue 8h；Horizontal centrifuge speed 100-120r/min in step g, continue 10min；
Described aromatic series azole is the ratio mixing that thin base BTA and BTA are 1: 1 by weight proportion The mixture formed；Described rhodanate is potassium rhodanide；Described organic amine is methyl diethanolamine.
Embodiment 7
Described step b realizes prepolymerization under 95 DEG C of temperature conditionss；Filled in step c under the conditions of rotating speed is 200r/min Divide and be mixed evenly, water bath with thermostatic control 2.5h, then stands 12h at room temperature under the conditions of 75 DEG C；Steel pipe is heated in step d to be made Its temperature is maintained at 92 DEG C, and the dosage of corrosion inhibiter is 3.0L/m2, the pressure of steel pipe inner chamber is maintained between 30kPa-50kPa；Open Its rotating speed of dynamic horizontal type centrifuger is 600-650r/min, continues 6min；The water injected in step e is 12L/m2, horizontal Centrifuge speed 550-600r/min, continue 1.5h；The distilled water injected in step f is 36L/m2, horizontal type centrifuger rotating speed 100-120r/min, continue 9h；Horizontal centrifuge speed 100-120r/min in step g, continue 12min
Described aromatic series azole is that thin base BTA and BTA are 1 by weight proportion：1 ratio mixing The mixture formed；Described rhodanate is ammonium thiocyanate；Described organic amine is diethanol amine.
Embodiment 8
Described step b realizes prepolymerization under 110 DEG C of temperature conditionss；In step c under the conditions of rotating speed is 200r/min It is sufficiently mixed and stirs, water bath with thermostatic control 3h, then stands 12h at room temperature under the conditions of 60 DEG C；Steel pipe is heated in step d to be made Its temperature is maintained at 92 DEG C, and the dosage of corrosion inhibiter is 2.8L/m2, the pressure of steel pipe inner chamber is maintained between 30kPa-50kPa；Open Its rotating speed of dynamic horizontal type centrifuger is 600-650r/min, continues 6min；The water injected in step e is 10L/m2, horizontal Centrifuge speed 550-600r/min, continue 1.5h；The distilled water injected in step f is 30L/m2, horizontal type centrifuger rotating speed 100-120r/min, continue 10h；Horizontal centrifuge speed 100-120r/min in step g, continue 15min；
Described aromatic series azole is the ratio that thin base BTA and methyl benzotriazazole are 1: 1 by weight proportion The mixture mixed, described rhodanate are sodium sulfocyanate, and described organic amine is MEA, beautiful jade, diethyl Alcohol mixes for 1: 2: 1.5 ratio by weight proportion.
4 1000 × 100 × 10mm inner surface using the steel pipe of constituent in embodiment 4 is carried out in advance respectively Wash, use the corrosion inhibiter in embodiment 5 to embodiment 8 during prewashing to the inner surface of every steel pipe respectively, then separately take 4 1000 The inner surface of × 100 × 10mm contrast steel pipe using L360MCS is entered using the corrosion inhibiter described in embodiment 5 to embodiment 8 Row prewashing, and the steel pipe after 8 prewashing is put into the transport pipeline to transport crude oil respectively, the internal diameter of transport pipeline is 220mm, Crude oil temperature is 32 DEG C -35 DEG C in transport pipeline, and the component content of crude oil is oil, gas and water and silt, and 8 steel pipes are placed After 12 months, the minimum wall thickness (MINI W.) of each steel pipe is measured, measurement data is as shown in table 4：
Corrosion resistance test after the steel pipe inner wall prewashing of table 4
Sequence number The corrosion inhibiter of use The steel pipe of use Minimum wall thickness (MINI W.) before experiment Minimum wall thickness (MINI W.) after experiment Crude oil flow velocity (m/s)
1 Embodiment 5 Embodiment 4 10.13 9.75 1.2
2 Embodiment 6 Embodiment 4 10.15 9.80 1.2
3 Embodiment 7 Embodiment 4 10.14 9.82 1.2
4 Embodiment 8 Embodiment 4 10.13 9.95 1.2
5 Embodiment 5 Contrast steel pipe 10.13 9.58 1.2
6 Embodiment 6 Contrast steel pipe 10.14 9.65 1.2
7 Embodiment 7 Contrast steel pipe 10.15 9.72 1.2
8 Embodiment 8 Contrast steel pipe 10.14 9.8 1.2
It can be seen from table 4, in 1-4 steel pipes, the decay resistance of No. 4 steel pipes is best, in 5-8 steel pipes, No. 8 steel pipes Decay resistance is best, and No. 4 steel pipes are stronger than the corrosion resistance of No. 8 steel pipes, illustrate the steel that the present invention that embodiment 4 uses makes Pipe decay resistance is better than compared steel pipe.
Analysis understands, No. 4 steel pipes with the addition of Zr relative to No. 8 steel pipes in its constituent, Cu, Als, Sb, Ni, light dilute The elements such as soil, make No. 4 steel pipes that there is excellent acid resistance, while a variety of non-ferrous metal elements added in No. 4 steel pipes can be with Corrosion inhibiter acts on forming electron ion complex compound, avoids its inwall that chemical attack occurs；After corrosion inhibiter contacts with No. 4 steel pipe inner walls, The uniform protecting film of a floor can be formed in No. 4 steel pipe inner walls, preferably ensure the corrosion resistance of No. 4 steel pipe inner walls；Gluconic acid Sodium preferably realizes the absorption to metal ions such as aluminium present in steel pipe, copper, forms the complex compound of above-mentioned ion, avoids occurring Electrochemical corrosion；Corrosion inhibiter a variety of release mechanisms is present, preferably realize etch-proof effect.

Claims (10)

  1. A kind of 1. manufacture method of corrosion resisting alloy hot finished steel pipe, it is characterised in that：The manufacture method of the steel pipe includes order The following steps of progress：The pre- desulfurization of blast furnace ironmaking, molten steel, converter top bottom blowing, the refining of LF stoves, continuous casting steel pipe blank, plus Heat, perforation, tandem rolling, tension force sizing, correction, cooling, prewashing；
    Described prewashing technique is carried out in accordance with the following steps：
    A. thiocyanate salt solution is mixed at ambient temperature with N doping mesoporous carbon, stirred；
    B. polyacrylic acid, citric acid, methyl butynol, surfactant, gluconic acid are added in step a mixed solution Sodium, aromatic series azole and organic amine, the water bath with thermostatic control 1-2h under 80 DEG C of -90 DEG C of temperature conditionss；
    C. barium mahogany sulfonate and silica gel support perchloric acid are added in prepolymer prepared by step b, is 200-400r/ in rotating speed It is sufficiently mixed and stirs under the conditions of min, water bath with thermostatic control 2-3h, then stands 10h- at room temperature under the conditions of 60 DEG C -75 DEG C 15h, corrosion inhibiter is obtained after bubble collapse；
    D. steel pipe is fixed on horizontal type centrifuger, heating steel pipe makes its temperature be maintained between 85 DEG C -92 DEG C, then in steel Injection corrosion inhibiter inside pipe, the relation between the dosage and steel pipe inner wall surface area of corrosion inhibiter is inhibiter consumption 2.5-3.0L/ m2, steel pipe both sides are blocked using plug, start horizontal type centrifuger, it is 600-650r/min to keep its rotating speed, continues 5- 8min；
    E. distilled water is injected in steel duct, the water of injection is 3-5 times of corrosion inhibiter, i.e. the dosage and steel pipe inner wall of corrosion inhibiter Relation between surface area is 2.5-3.0L/m2, the water of injection is 2.5-3.0L/m23-5 times；Horizontal type centrifuger rotating speed 550-600r/min, continue 1.5-2h；
    F. re-inject distilled water in steel duct, the distilled water of injection is 2-3 times of injected water volume in step e, horizontal from Scheming rotating speed 100-120r/min, continue 8-10h.
  2. 2. the manufacture method of corrosion resisting alloy hot finished steel pipe according to claim 1, it is characterised in that：Described step d In, after steel duct injects a certain amount of corrosion inhibiter, to steel pipe inner chamber inflated with nitrogen, and the pressure of steel pipe inner chamber is maintained at 10- Between 50kPa.
  3. 3. the manufacture method of corrosion resisting alloy hot finished steel pipe according to claim 1, it is characterised in that：Described step f Also include step g afterwards, step g process is：By subacidity distilled water of the steel duct injection pH value between 7.6-8.0, water Flat centrifuge speed 100-120r/min, continue 10-15min.
  4. 4. the manufacture method of corrosion resisting alloy hot finished steel pipe according to claim 1, it is characterised in that：Described aromatic series Azole is to dredge the mixture that the ratio that base BTA and methyl benzotriazazole are 1: 1 by weight proportion mixes, or The mixture mixed for the ratio that thin base BTA and BTA are 1: 1 by weight proportion.
  5. 5. the manufacture method of corrosion resisting alloy hot finished steel pipe according to claim 1, it is characterised in that：Described thiocyanic acid Salt is sodium sulfocyanate or potassium rhodanide or ammonium thiocyanate.
  6. 6. the manufacture method of corrosion resisting alloy hot finished steel pipe according to claim 1, it is characterised in that：Described organic amine Class is in methyl diethanolamine, diisopropanolamine (DIPA), MEA, cetylamine, octadecylamine, beautiful jade, diethanol amine or triethanolamine Any one, or be that MEA, beautiful jade, diethanol are that 1: 2: 1.5 ratio mixes by weight proportion.
  7. A kind of 7. manufacture method of corrosion resisting alloy hot finished steel pipe according to claim 1, it is characterised in that：Described step Suddenly the constituent of the corrosion inhibiter in c is by weight percentage：1%-3% polyacrylic acid, 1%-2% citric acids, 1%-2% first Base butynol, 3%-9% surfactants, 5%-7% sodium gluconates, 1%-5% aromatic series azole, 5%-15% thiocyanic acids Salt, 20%-28% organic amines, 10%-25% N dopings mesoporous carbon, 15%-25% barium mahogany sulfonates, 0.5%-1% silica gel Support perchloric acid, 10%-25% distilled water.
  8. 8. the manufacture method of corrosion resisting alloy hot finished steel pipe according to claim 1, it is characterised in that：Described converter top After the top-bottom blowing step of bottom, content analysis is carried out to C, Mo, Mn, Ni, Cu, Sb, V, Zr, Als, Nb, Ti, W element in molten steel, Then corresponding alloying ingredient is added into molten steel in LF stove refinement steps as needed so that the content of each element in molten steel Within the content range, then refined；
    Described cooling step is that the steel pipe after correction is placed in the vacuum cooled stove that pressure is 10-30kPa to be cooled to 850 DEG C -900 DEG C, water-spraying control processing then is carried out to steel tube surface, its temperature is dropped to 600 DEG C -650 DEG C, last air cooling；Institute It is heated to 1080 DEG C -1090 DEG C laggard eleven punch 11 steps in the heating stepses stated to steel pipe blank, steel in described tandem rolling step The temperature of pipe blank is 1035 DEG C -1055 DEG C, and the temperature of steel pipe blank is 935 DEG C -955 DEG C in described tension force sizing step.
  9. 9. the manufacture method of corrosion resisting alloy hot finished steel pipe according to claim 8, it is characterised in that：The group of the steel pipe It is by weight percentage into composition：C 0.05%-0.10%, Mo 0.1%-0.3%, Mn 0.7%-1.1%, P≤0.01%, S≤0.005%, N≤0.005%, 0≤0.001%, and contain Ni 0.08%-0.12%, Cu 0.7%-1.0%, Sb 0.04%-0.1%, V 0.1%-0.15%, Zr 0.15%-0.35%, Als 0.01%-0.05%, Nb 0.02%- 0.07%, Ti 0.02%-0.08%, light rare earth LREE 0.01%-0.03%, W 0.05%-0.2%, and satisfaction 1.0%≤ Cu+Zr+Als+Ti≤1.4%, surplus are Fe and inevitable impurity.
  10. 10. a kind of manufacture method of corrosion resisting alloy hot finished steel pipe according to claim 8 is characterized in that：Described steel The constituent of pipe is by weight percentage：C 0.1%, Mo 0.3%, Mn：0.9%, P≤0.02%, S≤0.002%, N≤ 0.005%, 0≤0.001%, Ni 0.12%, Cu 0.75%, Sb 0.1%, V 0.15%, Zr 0.35%, Als 0.05%, Nb 0.07%, Ti 0.02%, light rare earth LREE 0.03%, W 0.2%, and meet 1.0%≤Cu+Zr+Als+ Ti≤1.4%, surplus are Fe and inevitable impurity.
CN201611077695.9A 2016-11-30 2016-11-30 A kind of manufacture method of corrosion resisting alloy hot finished steel pipe Expired - Fee Related CN106555137B (en)

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CN102352501A (en) * 2011-10-09 2012-02-15 上海大学 Method for forming corrosion inhibiting film on steel and iron surface
CN103361664A (en) * 2013-07-31 2013-10-23 中国化学工程第三建设有限公司 Cleaning method of carbon steel pipeline and cleaning agents
CN103882437A (en) * 2014-04-01 2014-06-25 马杨洋 Corrosion inhibitor for oil-gas gathering and transportation pipeline and preparation method thereof

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CN102352501A (en) * 2011-10-09 2012-02-15 上海大学 Method for forming corrosion inhibiting film on steel and iron surface
CN103361664A (en) * 2013-07-31 2013-10-23 中国化学工程第三建设有限公司 Cleaning method of carbon steel pipeline and cleaning agents
CN103882437A (en) * 2014-04-01 2014-06-25 马杨洋 Corrosion inhibitor for oil-gas gathering and transportation pipeline and preparation method thereof

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