CN106555137A - 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 PDFInfo
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- CN106555137A CN106555137A CN201611077695.9A CN201611077695A CN106555137A CN 106555137 A CN106555137 A CN 106555137A CN 201611077695 A CN201611077695 A CN 201611077695A CN 106555137 A CN106555137 A CN 106555137A
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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
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- 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
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- 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
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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
- C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
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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
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
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- 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
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- 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
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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
- C22C38/16—Ferrous alloys, e.g. steel alloys containing copper
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/12—Oxygen-containing compounds
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
- C23F11/141—Amines; Quaternary ammonium compounds
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/16—Sulfur-containing compounds
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/173—Macromolecular compounds
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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, LF stove refines, 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 is contacted with steel pipe inner wall, one layer of uniform protecting film can be formed in steel pipe inner wall, be improved the corrosion resistance of steel pipe inner wall；Sodium gluconate preferably realizes the absorption to metal ions such as aluminum present in steel pipe, copper, forms electro-ionic complex, it is to avoid electrochemical corrosion occurs；Make corrosion inhibiter there are various release mechanisms, preferably realize etch-proof effect；Corrosion inhibiter need not persistently be added during pipeline transportation crude oil, maintenance workload is little.
Description
Technical field
The present invention relates to petroleum pipeline manufacture field, more particularly to a kind of manufacture method of corrosion resisting alloy hot finished steel pipe.
Background technology
Corrosion is to perplex one of difficult problem of industrial gas oil development, according to "ball-park" estimate, is corroded to China's oil
The loss that industry is caused accounts for the 6% of the industry gross output value, and takes suitable anti-corrosion measure at least 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 of the corrosion resistance to petroleum pipeline, should meet the anti-of inner-walls of duct
Corrosion requirement, meets the requirement of atmospheric corrosion resistance again.
Sour gas corrosion is most common a kind of erosional forms for running in petroleum pipeline corrosion, the crude oil or original of oil
All contain substantial amounts of sulfur (S), the oxidized formation sulfur dioxide of sulfur (S) and sulfur trioxide in the extractive matter of oil, in dew point temperature and
Water vapour is combined and becomes sulphuric acid, and sulphuric 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.
It is domestic for the development and exploitation of corrosionproof steel against sulfuric acid at dew point are started late, component system and borrowed using Standard General
The steel grade of mirror Japan, wherein typically have the lOCu1Cu of the B485NL of In Baosteel, Anshan iron and steel plant, in addition with Jiangyin special steel
ND (09CuCuSb) steel, Ji steel one steel company of 12MnCuCu and Baosteel 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 acidic liquid from corroding, and in crude oil
Other types corrosive effect it is not good, oil field corrosion is with following feature:Gas and water, hydrocarbon, the Multiphase Flow for coexisting admittedly are situated between
Matter, existing general corrosion have local corrosion again, also including carbon dioxide and the acid liquid corrosion of formation, hydrogen sulfide corrosion, should
Power corrosion cracking and microbiologic(al) corrosion etc., in order to further improve the comprehensive corrosion resistance of petroleum pipeline inwall, can typically adopt
With pickling, but pickling cannot effectively prevent various 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, and 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 kind of technology is
Using galvanized pipe as petroleum transportation pipeline, but it is larger for caliber, for the longer pipeline of length, no corresponding size
Galvanizing equipment, and it is zinc-plated expensive.
At present in petrochemical industry, for the anti-corrosion inside conveyance conduit, can also be delayed using adding in a fluid
The method of erosion agent, corrosion inhibiter are referred to when being present in surrounding medium with appropriate concentration and form, can prevent or slow down material
The chemical substance or complex of corrosion, therefore corrosion inhibiter is referred to as corrosion inhibitor.Its consumption very little, but effect is aobvious
Write.Corrosion inhibiter is currently used primarily in neutral medium (boiler feed water, recirculated cooling water), acid medium (hydrochloric acid for descaling, plating
The acid dip solution of front plating piece rust cleaning) and gas medium (vapour phase inhibitor).A kind of adsorbed film type corrosion inhibiter tool in corrosion inhibiter
Polarized gene, 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.
But corrosion inhibiter needs to add in flow media at any time when in use, relatively complicated using process, therefore can be with
Consider a kind of corrosionproof steel against sulfuric acid at dew point containing non-ferrous metal of manufacture, and the inwall of the steel pipe is entered using special corrosion inhibiter
Row prewashing, makes steel pipe inner wall be reacted with corrosion inhibiter in advance, forms corrosion prevention film, so can replace pickling, so as to improve
The comprehensive decay resistance of corrosionproof steel against sulfuric acid at dew point pipe, it is also possible to reduce maintenance workload.
The content of the invention
For the problems referred to above, it is an object of the invention to provide a kind of acid resistance is good, comprehensive fine corrosion resistance resistance to
The manufacture method of resistant alloy hot finished steel pipe.
For achieving 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 multiple
Close blowing, LF stove refines, 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 with N doping mesoporous carbon at ambient temperature, is stirred；
B. in the mixed solution of step a add polyacrylic acid, citric acid, methyl butynol, surfactant, glucose
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 under the conditions of 400r/min and stirs, water bath with thermostatic control 2-3h, is then stood at room temperature under the conditions of 60 DEG C -75 DEG C
LOh-15h, obtains corrosion inhibiter 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 consumption 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, keep its rotating speed to be 600-650r/min, continue
5-8min；
E. distilled water is injected in steel duct, the water yield of injection is 3-5 times of corrosion inhibiter, horizontal type centrifuger rotating speed 550-
600r/min, continues 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, level
Formula centrifuge speed 100-120r/min, continues 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 made to be maintained between 10-50KPa.
Preferably, also include step g after described step f, the process of step g is：By steel duct injection pH value it is
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 1 to dredge base BTA and methyl benzotriazazole by weight proportion:
The mixture that 1 ratio is mixed；Or be 1 by weight proportion to dredge base BTA and BTA:1 ratio is mixed
The mixture for closing.
Preferably, described rhodanate is sodium rhodanate or potassium thiocyanate or ammonium thiocyanate.
Preferably, described organic amine be methyl diethanolamine, diisopropanolamine (DIPA), monoethanolamine, cetylamine, 18
Any one in amine, beautiful jade, diethanolamine or triethanolamine, or be 1 by weight proportion for monoethanolamine, beautiful jade, diethanol:
2:1.5 ratio is mixed.
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% are fragrant
Fragrant race's azole, 5%-15% rhodanates, 20%-28% organic amines, 10%-25% N doping mesoporous carbons, 15%-25% stones
Oily barium sulfonate, 0.5%-1% silica gel support perchloric acid, 10%-25% distilled water.
Preferably, after described converter top bottom blowing step, to the C in molten steel, Mo, Mn, Ni, Cu, Sb, V, Zr,
Als, Nb, Ti, W element carries out content analysis, then adds in molten steel in LF stove refinement steps as needed and closes accordingly
Golden dispensing so that the content of each element then carries out refine within the content range 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 process is carried out to steel tube surface then so as to which temperature drop is to 600 DEG C -650 DEG C, 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 in described tension force sizing step, the temperature of steel pipe blank is 935 DEG C -955
℃。
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%, balance of 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%, balance of 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 aluminum present in steel pipe, copper, forms electro-ionic complex, it is to avoid electricity occurs
Chemical attack；Make corrosion inhibiter there are various release mechanisms, preferably realize etch-proof effect；Need not during pipeline transportation crude oil
Persistently add corrosion inhibiter, maintenance workload is little.
Specific embodiment
A kind of corrosion resisting alloy hot finished steel pipe, the constituent of the steel pipe is 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%, balance of Fe and can not
The impurity for avoiding；
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, LF stove refines, continuous casting steel pipe blank, heating, perforation, tandem rolling, tension force sizing, correction, cooling；Prewashing.
After described converter top bottom blowing step, to the C in molten steel, Mo, Mn, Ni, Cu, Sb, V, Zr, Als, Nb,
Ti, W element carries out content analysis, and corresponding alloying ingredient is added in molten steel in LF stove refinement steps as needed then,
So that the content of each element then carries out refine within the content range in molten steel；
Preferably embodiment is：After described LF stove refinement steps, molten steel is carried out feeding the change of Ca-Mo lines sulphide inculsion
Property process, then carry out continuous casting steel pipe blank step, can so effectively improve the quality of steel pipe blank.
According to the steel pipe of above-mentioned manufacture method manufacture, its constituent is configured to embodiment 1 by weight percentage to enforcement
Example 4, in each embodiment, the constituent of steel pipe is as follows：
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%, balance of 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 process is carried out to steel tube surface then so as to temperature drop 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 in described tandem rolling step, the temperature of steel pipe blank is 1055
DEG C, in described tension force sizing step, the temperature of steel pipe blank is 955 DEG C.
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%, O≤0.001%, Ni 0.1%, Cu 0.8%, Sb 0.07%, V 0.12%,
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%, balance of 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 process is carried out to steel tube surface then so as to temperature drop 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 in described tandem rolling step, the temperature of steel pipe blank is 1055
DEG C, in described tension force sizing step, the temperature of steel pipe blank is 940 DEG C.
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%, balance of 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 process is carried out to steel tube surface then so as to temperature drop 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 in described tandem rolling step, the temperature of steel pipe blank is 1035
DEG C, in described tension force sizing step, the temperature of steel pipe blank is 935 DEG C.
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%, balance of 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 process is carried out to steel tube surface then so as to temperature drop 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 in described tandem rolling step, the temperature of steel pipe blank is 1035
DEG C, in described tension force sizing step, the temperature of steel pipe blank is 955 DEG C.
Steel duct embodiment of the present invention 1 is as shown in table 1 with the constituent percentage ratio contrast of contrast steel pipe to embodiment 4：
1 steel pipe constituent percentage composition table of table
According to the constituent shown in embodiment 1 to embodiment 4, the steel pipe of 1 1000 × 100 × 10mm is respectively made, and
The L360MCS seamless steel pipes for selecting percentage of total elongation to be close to up to the stress (Rt0.5) when 0.5%, tensile strength (Rm) with the present invention
Steel pipe, contrasts 1000 × 100 × 10mm of size of steel pipe, 5 steel pipes is put into 70 DEG C respectively, 20% H as a comparison2SO4It is molten
In liquid, the corrosion rate of each outer surface of steel tube is as shown in table 2：
2 embodiment 1 of table is to embodiment 4 and the comparison between corrosion of contrast steel pipe
| 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.Repeat experiment 2 times, 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 with N doping mesoporous carbon at ambient temperature, is stirred；
B. in the mixed solution of step a add polyacrylic acid, citric acid, methyl butynol, surfactant, glucose
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 under the conditions of 400r/min and stirs, water bath with thermostatic control 2-3h, is then stood at room temperature under the conditions of 60 DEG C -75 DEG C
LOh-15h, obtains corrosion inhibiter 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, then a certain amount of corrosion inhibiter is injected in steel duct, the consumption 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, keeps its rotating speed for 600-650r/min, lasting 5-8min；
E. distilled water is injected in steel duct, the water yield of injection is 3-5 times of corrosion inhibiter, horizontal type centrifuger rotating speed 550-
600r/min, continues 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, level
Formula centrifuge speed 100-120r/min, continues 8-10h；
Also include step g after described step f, the process of step g 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 the 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 doping mesoporous carbons, 15%-25% mahogany acids
Barium, 0.5%-1% silica gel support perchloric acid, 10%-25% distilled water.
Described aromatic series azole is 1 to dredge base BTA and methyl benzotriazazole by weight proportion:1 ratio
The mixture for mixing, or be 1 by weight proportion to dredge base BTA and BTA:1 ratio is mixed
Mixture；Described rhodanate is sodium rhodanate or potassium thiocyanate or ammonium thiocyanate；Described organic amine is methyl two
Any one in ethanolamine, diisopropanolamine (DIPA), monoethanolamine, cetylamine, 18-amine., beautiful jade, diethanolamine or triethanolamine,
Or for monoethanolamine, beautiful jade, diethanol by weight proportion be 1:2:1.5 ratio is mixed.
Different ratio is carried out according to the constituent of corrosion inhibiter embodiment 5 is formed to embodiment 8, the wherein composition of corrosion inhibiter
Composition quality fractional content is as shown in table 3：
3 corrosion inhibiter constituent mass fraction content of table
Embodiment 5
Described step b realizes prepolymerization under 80 DEG C of temperature conditionss；Fill under the conditions of rotating speed is 400r/min in step c
Mixing and stirring, the water bath with thermostatic control 3h under the conditions of 60 DEG C is divided then to stand l5h at room temperature；Steel pipe is heated in step d makes which
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
The use of the consumption of 2.8L corrosion inhibiter, i.e. 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 yield injected in step e is 7.5L/m2, horizontal
Centrifuge speed 550-600r/min, continues 2h；The distilled water injected in step f is 15L/m2, horizontal type centrifuger rotating speed
100-120r/min, continues 10h；Horizontal type centrifuger rotating speed 100-120r/min in step g, continues 10min；
Described aromatic series azole is 1 to dredge base BTA and methyl benzotriazazole by weight proportion:1 ratio
The mixture for mixing；Described rhodanate is sodium rhodanate；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, then the water bath with thermostatic control 3h under the conditions of 70 DEG C -75 DEG C stands 15h at room temperature；Heat in step d
Steel pipe makes its temperature be maintained between 87 DEG C -92 DEG C, and the consumption of corrosion inhibiter is 2.8L/m2, the pressure of steel pipe inner chamber is maintained at
Between 20KPa-30KPa；Start its rotating speed of horizontal type centrifuger for 600-650r/min, continue 8min；The water injected in step e
Measure as 14L/m2, horizontal type centrifuger rotating speed 550-600r/min, lasting 2h；The distilled water injected in step f is 42L/m2, water
Flat centrifuge speed 100-120r/min, continues 8h；Horizontal type centrifuger rotating speed 100-120r/min in step g, continues
10min；
Described aromatic series azole is 1 to dredge base BTA and BTA by weight proportion:1 ratio mixing
Mixture；Described rhodanate is potassium thiocyanate；Described organic amine is methyl diethanolamine.
Embodiment 7
Described step b realizes prepolymerization under 95 DEG C of temperature conditionss；Fill under the conditions of rotating speed is 200r/min in step c
Mixing and stirring, the water bath with thermostatic control 2.5h under the conditions of 75 DEG C is divided then to stand 12h at room temperature；Steel pipe is heated in step d to be made
Its temperature is maintained at 92 DEG C, and the consumption 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 yield injected in step e is 12L/m2, horizontal
Centrifuge speed 550-600r/min, continues 1.5h；The distilled water injected in step f is 36L/m2, horizontal type centrifuger rotating speed
100-120r/min, continues 9h；Horizontal type centrifuger rotating speed 100-120r/min in step g, continues 12min
Described aromatic series azole is 1 to dredge base BTA and BTA by weight proportion:1 ratio mixing
Mixture；Described rhodanate is ammonium thiocyanate；Described organic amine is diethanolamine.
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, then the water bath with thermostatic control 3h under the conditions of 60 DEG C stands 12h at room temperature；Steel pipe is heated in step d to be made
Its temperature is maintained at 92 DEG C, and the consumption 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 yield injected in step e is 10L/m2, horizontal
Centrifuge speed 550-600r/min, continues 1.5h；The distilled water injected in step f is 30L/m2, horizontal type centrifuger rotating speed
100-120r/min, continues 10h；Horizontal type centrifuger rotating speed 100-120r/min in step g, continues 15min；
Described aromatic series azole is 1 to dredge base BTA and methyl benzotriazazole by weight proportion:1 ratio
The mixture for mixing, described rhodanate are sodium rhodanate, and described organic amine is monoethanolamine, beautiful jade, diethyl
Alcohol is 1 by weight proportion:2:1.5 ratio is mixed.
Respectively the inner surface of the steel pipe of constituent in the employing embodiment 4 of 4 1000 × 100 × 10mm is carried out pre-
Wash, adopt the corrosion inhibiter in embodiment 5 to embodiment 8 during prewashing respectively to the inner surface of every steel pipe, then separately take 4 1000
The inner surface of the contrast steel pipe of the employing L360MCS of × 100 × 10mm is entered using the corrosion inhibiter described in embodiment 5 to embodiment 8
Row prewashing, and respectively the steel pipe after 8 prewashing is put in the transport pipeline for transporting crude oil, the internal diameter of transport pipeline is 220mm,
In transport pipeline, crude oil temperature is 32 DEG C -35 DEG C, 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, and measurement data is as shown in table 4：
Corrosion resistance test after 4 steel pipe inner wall prewashing of table
| Sequence number | Using corrosion inhibiter | Using steel pipe | Minimum wall thickness (MINI W.) before test | Minimum wall thickness (MINI W.) after test | 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 |
According to 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 is used makes
Pipe decay resistance is better than compared steel pipe.
Analysis understands that 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 have excellent acid resistance, while the various non-ferrous metal elements added in No. 4 steel pipes can be with
Corrosion inhibiter acts on forming electron ion complex, it is to avoid its inwall occurs chemical attack；After corrosion inhibiter is contacted 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 aluminum present in steel pipe, copper, forms the complex of above-mentioned ion, it is to avoid occur
Electrochemical corrosion；Make corrosion inhibiter there are various release mechanisms, preferably realize etch-proof effect.
Claims (10)
1. a kind of 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 for carrying out：The pre- desulfurization of blast furnace ironmaking, molten steel, converter top bottom blowing, LF stove refines, 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 with N doping mesoporous carbon at ambient temperature, is stirred；
B. in the mixed solution of step a add polyacrylic acid, citric acid, methyl butynol, surfactant, gluconic acid
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 under the conditions of min and stirs, then the water bath with thermostatic control 2-3h under the conditions of 60 DEG C -75 DEG C stands 10h- at room temperature
15h, obtains corrosion inhibiter 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
Corrosion inhibiter is injected inside pipe, the relation between the consumption 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, its rotating speed is kept for 600-650r/min, lasting 5-
8min；
E. distilled water is injected in steel duct, the water yield of injection is 3-5 times of corrosion inhibiter, horizontal type centrifuger rotating speed 550-
600r/min, continues 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, continues 8-10h.
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 make the pressure of steel pipe inner chamber be maintained at 10-
Between 50KPa.
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, the process of step g is：Steel duct is injected into pH value for the subacidity distilled water between 7.6-8.0, water
Flat centrifuge speed 100-120r/min, continues 10-15min.
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 1 to dredge base BTA and methyl benzotriazazole by weight proportion:The mixture that 1 ratio is mixed, or
It is 1 by weight proportion to dredge base BTA and BTA:The mixture that 1 ratio is mixed.
5. the manufacture method of corrosion resisting alloy hot finished steel pipe according to claim 1, it is characterised in that：Described Hydrogen thiocyanate
Salt is sodium rhodanate or potassium thiocyanate or ammonium thiocyanate.
6. the manufacture method of corrosion resisting alloy hot finished steel pipe according to claim 1, it is characterised in that：Described organic amine
During class is methyl diethanolamine, diisopropanolamine (DIPA), monoethanolamine, cetylamine, 18-amine., beautiful jade, diethanolamine or triethanolamine
Any one, or for monoethanolamine, beautiful jade, diethanol by weight proportion be 1:2:1.5 ratio is mixed.
7. the manufacture method of a kind of corrosion resisting alloy hot finished steel pipe according to claim 1, it is characterised in that：Described step
The constituent of the corrosion inhibiter in rapid 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 azoles, 5%-15% Hydrogen thiocyanates
Salt, 20%-28% organic amines, 10%-25% N doping mesoporous carbons, 15%-25% barium mahogany sulfonates, 0.5%-1% silica gel
Support perchloric acid, 10%-25% distilled water.
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 are 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 in molten steel in LF stove refinement steps as needed so that the content of each element in molten steel
Within the content range, then carry out refine；
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 process is carried out to steel tube surface then so as to temperature drop to 600 DEG C -650 DEG C, last air cooling；Institute
1080 DEG C -1090 DEG C laggard eleven punch 11 steps, steel in described tandem rolling step are heated in the heating stepses stated to steel pipe blank
The temperature of pipe blank is 1035 DEG C -1055 DEG C, and in described tension force sizing step, the temperature of steel pipe blank is 935 DEG C -955 DEG C.
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
Into composition it 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%, balance of Fe and inevitable impurity.
10. a kind of corrosion resisting alloy hot finished steel pipe according to claim 9 manufacture method it 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%, O≤0.001%, Ni 0.12%, Cu 0.75%, Sb 0.1%, V 0.15%, Zr 0.35%, Al s
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%, balance of Fe and inevitable impurity.
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Cited By (2)
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| CN109267068A (en) * | 2018-11-22 | 2019-01-25 | 中石化炼化工程（集团）股份有限公司 | A kind of stress corrosion cracking inhibitor, preparation method and application |
| CN114231854A (en) * | 2021-11-22 | 2022-03-25 | 深圳市波尔顿科技有限公司 | High-strength high-corrosion-resistance stainless steel for antibacterial cutter |
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| CN114231854A (en) * | 2021-11-22 | 2022-03-25 | 深圳市波尔顿科技有限公司 | High-strength high-corrosion-resistance stainless steel for antibacterial cutter |
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