CN108660385A - A kind of low-alloy steel of acid corrosion-resistant, steel pipe, steel plate and its manufacturing method - Google Patents
A kind of low-alloy steel of acid corrosion-resistant, steel pipe, steel plate and its manufacturing method Download PDFInfo
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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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- 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
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/26—Methods of annealing
- C21D1/28—Normalising
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- 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
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
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- 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
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0226—Hot rolling
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- 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
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0236—Cold rolling
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- 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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- 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
- C21D9/0081—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for slabs; for billets
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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
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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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
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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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
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/20—Ferrous alloys, e.g. steel alloys containing chromium with copper
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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
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/005—Ferrite
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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
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/009—Pearlite
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Abstract
The invention discloses a kind of low-alloy steel of acid corrosion-resistant, microstructure is ferrite+pearlite, and the chemical element mass percentage of the low-alloy steel of the acid corrosion-resistant is：0 ＜ C≤0.2%；Si：0.15~0.4%；Mn：0.15~0.75%；S：0.001~0.015%；Cr：0.15~0.95%；Cu：0.08~0.3%；Sb：0.005~0.08%；Surplus is Fe and other inevitable impurity；Wherein, (Sb+Cu)/3S is 5~35.In addition, the invention also discloses steel plate, steel pipe and its manufacturing methods made of a kind of low-alloy steel using above-mentioned acid corrosion-resistant.The low-alloy steel of acid corrosion-resistant of the present invention is designed using the alloying element of optimization and makes it have higher acid corrosion-resistant performance, and steel grade such as 2205 two phase stainless steels in economic value than in the prior art are more economical.
Description
Technical field
The present invention relates to a kind of steel, steel product and its manufacturing method more particularly to a kind of low-alloy steel, steel product and its systems
Make method.
Background technology
Petrochemical plant, coal-fired plant, smelting iron and steel factory etc. generate a large amount of flue gas throughout the year, wherein containing a large amount of such as SO3、SO2With
The sour gas such as HCl, SO2SO is further generated under catalytic action3.For energy-saving and emission-reduction and pollution is reduced, it is European from 20th century 80
Age coal-fired power plant of just laying down hard and fast rule will use flue gas desulfurization device (FGD), China's startup thermoelectricity desulfurization from the end of the 20th century
Project, first 20 years of the beginning of this century by be power plants desulfurization critical period.To improve desulfuration efficiency, low temperature is generally used
Sulfur removal technology.Furthermore the waste heat reclaiming process of energy-saving and emission-reduction is gradually lowered to 40 DEG C.When flue-gas temperature is less than its dew point temperature
Degree, at especially less than 70~80 DEG C, SO3It just condenses with HCl and forms sulfuric acid-hydrochloric acid nitration mixture dew point corrosion (hereinafter referred to as nitration mixture
Corrosion) environment.Although the new S-Ten1 of modified of the resistance to nitration mixture corrosion of certain iron company's promotion, has no industrial applicability case.Separately
Outside, investigation shows 80 DEG C or less low-temperature zones of flue gas processing device such as desulfurizer at present usually using 2205 two phase stainless steels
Corrode material as resistance to nitration mixture.
Fig. 1 to Fig. 4 shows spot corrosion shape of 2205 two phase stainless steels under optical microphotograph sem observation and under SEM observations
Looks.As seen from Figure 1, in smoke modelling liquid (dead green liquor) 11.4%H2SO4- 1.2%HCl-1.0%Fe3It is anti-corrosion in Cl
Although property assessment shows that the homogeneous corrosion rate of 2205 two phase stainless steels is minimum, spot corrosion, therefore 2205 occur for 2205 two phase stainless steels
Two phase stainless steel is easily potential to occur not expected random failure risk, influences the long-term Effec-tive Function of equipment.
Single resistant to sulfuric acid dew point corrosion generally relies on Cu or Cu-Sb systems and realizes its corrosion resistance, such as in the prior art
The single corrosionproof steel against sulfuric acid at dew point kind of the Cu-Sb-Si systems of addition element Si exploitations, is not directed to hcl corrosion, i.e., is not mixed
Acid corrosion material.Furthermore sulfuric acid corrosion experiment is only 60 DEG C -40% and 80 DEG C -50% to above-mentioned steel grade at low ambient temperatures, not
Strongest 70 DEG C -50% of useful generally acknowledged corrosivity is assessed, even if 140 DEG C -80% and 160 DEG C -90% under having hot environment
Corrosion resistance makes metal be passivated and slows down corrosion and be lost in, have as a result, it is well known that sulfuric acid shows oxidisability when 80~90%
Reproducibility not when low concentration causes metal fast erosion to be lost in.Therefore, although its rate of corrosion is only 60~99g/m2.h, but
Can it be used for 70 DEG C -50% of low-temperature dew point corrosion and need to be proved, needless to say its salt tolerant is acid.
The steel grade of resistance to nitration mixture corrosion is free of element sb in the prior art, some are the compound additions by element Cu, Cr, Mo
I.e. Cu-Cr-Mo systems and realize the corrosion of resistance to nitration mixture, some are then that the realization of P, S content is strictly controlled on the basis of add Cu is resistance to
Sulfuric acid corrosion resistance, then add micro Mo and realize that hydrochloric acid corrosion resistant, i.e. Cu-P-S-Mo systems realize nitration mixture corrosion.The two ingredient
Range all relies on individual sulfuric acid or hcl corrosion experiment, corrodes without reference to nitration mixture, is especially a lack of smoke modelling environment
Such as the corrosion resistance assessment in dead green liquor, the anti-corrosion result simple physical of one pack system acid cannot be used to be superimposed because nitration mixture corrodes.Separately
Outside, acid-resistant corrosion is larger with concentration and temperature change, as in 100 DEG C or less low temperature environments, sulfuric acid corrosion resistance at 70 DEG C -50%
It is most strong, and it is conclusion under weaker 60 DEG C -40% of corrosivity that above-mentioned steel grade, which relies on,.Moreover its rate of corrosion only limits≤
200g/m2.h, typical as 09CrCuSb and its tubing have already been less than 140g/ in resistant to sulfuric acid dew point corrosion steel alloy material
m2.h, even 80g/m2.h.So industrialization product of its corrosion resistance against sulfuric acid far away from last century.Similarly, only with 1%
Its hydrochloric acid corrosion resistant of low concentration evaluation certificate is good, unknown in the corrosion resistance of concentrated hydrochloric acid.
Invention content
One of the objects of the present invention is to provide a kind of low-alloy steel of acid corrosion-resistant, especially sharp by rationally designing
The acid-resistant corrosion of steel is realized with less alloy species, and obtained low-alloy steel is surveyed in each acid resistance
The lower performance of examination is excellent, cost-effective.
To achieve the goals above, the present invention proposes a kind of low-alloy steel of acid corrosion-resistant, and microstructure is iron element
The chemical element mass percentage of body+pearlite, the low-alloy steel of the acid corrosion-resistant is：
0 ＜ C≤0.2%；
Si：0.15~0.4%；
Mn：0.15~0.75%；
S：0.001~0.015%；
Cr：0.15~0.95%；
Cu：0.08~0.3%；
Sb：0.005~0.08%；
Surplus is Fe and other inevitable impurity；
Wherein, (Sb+Cu)/3S is 5~35.
The design principle of each chemical element is as described below in the low-alloy steel of acid corrosion-resistant of the present invention：
C：C is easily formed carbide, unfavorable to the corrosion resistance of steel, in principle should be more lower better；But C is to improve intensity again
Most economical element, and be objective reality, thus, the percentage composition for excessively reducing C be it is uneconomical, it is therefore, of the present invention
The mass percentage of C is limited in the low-alloy steel of acid corrosion-resistant in 0 ＜ C≤0.2%.
Si：Solution strengthening is conducive to improve the intensity of steel, and is advantageous to acid resistance, therefore, of the present invention resistance to
The mass percentage of Si is limited in the low-alloy steel of acid corrosion in Si：0.15~0.4%.
Mn：Mn is easy to be mingled with reduction corrosion resistance with S formation, that is, reduces the validity of S, but since the strong of steel can be improved in Mn
Degree, but when too high levels, microstructure segregation tendency aggravates, therefore the quality of Mn is limited in the steel of acid corrosion-resistant of the present invention
Percentage composition is in Mn：0.15%~0.75%.
S：S elements generally require stringent control in conventional steel, but to the low-alloy steel of acid corrosion-resistant of the present invention
It is beneficial element, the compound for inhibiting electrochemical corrosion can be formed with Cu, Sb element, therefore, in technology of the present invention
The mass percentage of S is controlled in S in scheme：0.001-0.015.
Cr：Cr is not only ferrite former, or improves corrosion proof important element, and can improve the quenching degree of steel
Intensity, but too high levels are improved, not only reduce the economy of steel, quenching degree is excessively high to be also unfavorable for producing, therefore institute of the present invention
The mass percentage of Cr is controlled in Cr in the technical solution stated：0.15~0.95%.
Cu：Cu is conventional relict element in steel, needs strictly to control in other steel grades, but to of the present invention acidproof
For the low-alloy steel of corrosion, addition Cu is conducive to improve the acid resistance of steel.To prevent rolling crack to be inclined to, of the present invention
Acid corrosion-resistant low-alloy steel in control Cu mass percentage 0.08~0.3%.
Sb：Addition Sb is conducive to improve the acid resistance of steel, but its too high levels can influence the processability of steel, therefore, at this
In the invention technical solution, the mass percentage of Sb is controlled 0.005~0.08%.
In order to integrate the collaboration acid resistance for playing the elements such as Cu, Sb and S, this case inventor has found Sb, Sn and S member
Element control is 5~35 in (Sb+Cu)/3S, to be formed to ensure that form acid resistance compound such as Cu, Sb and combine with S jointly
Acid resistance compound, and at the same time between reducing and even avoiding completely forming not corrosion proof compound for example Mn is combined with S
Compound, to improve the relatively compact property and uniformity of steel matrix surface sulfuric acid corrosion resistant film, and then improve steel
Corrosion resistance against sulfuric acid.
In order to improve the acid corrosion-resistant performance of steel, the mass percentage of inevitable impurity element should be controlled
It is more lower better, however by process conditions limited and from save production cost angle consider, by inevitable impurity element
Control exists：P≤0.012% further controls P≤0.010% in some preferred embodiments.
Further, in the low-alloy steel of acid corrosion-resistant of the present invention, grain size is 7 grades or more.
Further, in the low-alloy steel of acid corrosion-resistant of the present invention, Cu constituent contents are 0.15~0.25%.
Further, in the low-alloy steel of acid corrosion-resistant of the present invention, Sb constituent contents are 0.01~0.04%.
Further, in the low-alloy steel of acid corrosion-resistant of the present invention, (Sb+Cu)/3S is 9~21.
Further, it is 50% in 70 DEG C of mass concentrations in the low-alloy steel of acid corrosion-resistant of the present invention
Rate of corrosion ＜ 80g/m for 24 hours are impregnated in sulfuric acid solution2.h。
Further, in the low-alloy steel of acid corrosion-resistant of the present invention, rolled or normalizing state or normalizing+return
Yield strength >=300MPa of fiery state product, tensile strength >=420MPa, elongation percentage >=30%.
Further, in the low-alloy steel of acid corrosion-resistant of the present invention, cold rolling or the surrender of cold-drawn product are strong
Degree >=400MPa, tensile strength >=510MPa, elongation percentage >=25%.
In addition, another object of the present invention is to provide a kind of steel plate, the low-alloy steel of above-mentioned acid corrosion-resistant is used
It is made.
Correspondingly, another object of the present invention is to provide a kind of manufacturing method of above-mentioned steel plate, including step：
(1) it smelts and is cast as slab；
(2) it heats：1200-1350 DEG C of heating temperature, soaking time >=60min；
(3) hot rolling：Finishing temperature >=850 DEG C.
Further, the present invention also provides a kind of manufacturing methods of above-mentioned steel plate, including step：
(1) it smelts and is cast as slab；
(2) it heats：1200-1350 DEG C of heating temperature, soaking time >=60min；
(3) hot rolling；
(4) cold rolling；
(5) normalizing or normalizing+tempering is used to be heat-treated：Wherein normalizing temperature is 830-930 DEG C, soaking time >=
25min, it is then air-cooled；Temperature is 450-530 DEG C, and soaking time >=20min is then air-cooled.
It should be noted that when steel plate is hot-rolled product, it is not necessarily to subsequent heat treatment, state delivery can be rolled；When steel plate is
When cold-rolled products, then first hot rolling to interior thickness regards cold-rolled products thickness specification, product is cold rolled to through a time or multi-pass
Specification, product is thinner, and cold rolling pass is more, is not necessarily to subsequent heat treatment, can roll state delivery；It can also be used just after hot rolling or cold rolling
Fiery state or normalizing+tempering state use.In some preferred embodiments, normalizing temperature control is at 850~900 DEG C, heat preservation
Between be preferably controlled in >=45min, temperature is preferably controlled in 475-510 DEG C, and tempering insulation time >=30min is then air-cooled.
In addition, another object of the present invention is to provide a kind of steel pipe, the low-alloy steel of above-mentioned acid corrosion-resistant is used
It is made.
Correspondingly, another object of the present invention is to provide the manufacturing method of above-mentioned steel pipe, including step：
(1) it smelts and is cast as pipe；
(2) it heats：1200-1350 DEG C of heating temperature, soaking time >=60min；
(3) it perforates：Piercing temperature is 1070-1180 DEG C；
(4) it reheats：Relation reheating temperature is 920-1000 DEG C, soaking time >=30min；
(5) hot rolling：Finishing temperature >=850 DEG C.
Further, the present invention also provides a kind of manufacturing methods of above-mentioned steel pipe, including step：
(1) it smelts and is cast as pipe；
(2) it heats：1200-1350 DEG C of heating temperature, soaking time >=60min；
(3) it perforates：Piercing temperature is 1070-1180 DEG C；
(4) it reheats：Relation reheating temperature is 920-1000 DEG C, soaking time >=30min；
(5) hot rolling；
(6) cold rolling or cold-drawn；
(7) normalizing or normalizing+tempering is used to be heat-treated：Wherein normalizing temperature is 830-930 DEG C, soaking time >=
25min, it is then air-cooled；Temperature is 450-530 DEG C, and soaking time >=20min is air-cooled.
Further, in manufacturing method of the present invention, the step (3) further includes that sky subtracts and tandem rolling.
It should be noted that when steel pipe is hot-rolled product, it is not necessarily to subsequent heat treatment, state delivery can be rolled；When steel pipe is
When cold-rolled products, then first hot rolling regards cold rolling or cold-drawn product thickness specification, through a time or multi-pass cold rolling to intermediate main pipe
Or cold-drawn is to product specification, the thinner cold rolling of product or cold-drawn passage is more can cold rolling or the delivery of cold-drawn state；Hot rolling or cold rolling or
Normalizing state can also be used after cold-drawn or normalizing+tempering state uses.In some preferred embodiments, normalizing temperature control exists
850~900 DEG C, soaking time is preferably controlled in ＞ 45min, and temperature is preferably controlled in 475-510 DEG C, tempering insulation time
>=30min, it is then air-cooled.
The low-alloy steel of acid corrosion-resistant of the present invention is ensureing sulfuric acid corrosion resistant using the alloying element design of optimization
Property under the premise of, hydrochloric acid corrosion resistant test performance is good, i.e., steel grade of the present invention has resistance to nitration mixture corrosivity, has use
Acid corrosion-resistant performance in 80 DEG C or less flue gas environment, steel grade such as 2205 two-phases in economic value than in the prior art are not
The steel that becomes rusty is more economical, moreover verification shows that 2205 two phase stainless steels are existing in 80 DEG C or less smoke modelling liquid (dead green liquor) or power plant
The local corrosion phenomenons such as spot corrosion, crevice corrosion easily occur in the in-service assessment in 40 days of field, the unpredictability with failure damage.It adopts
Also have the advantages that with the steel plate of the low-alloy steel of the acid corrosion-resistant, steel pipe above-mentioned.
Description of the drawings
Fig. 1 is shown in 70 DEG C of smoke modelling liquid that light microscope is observed before the stripping of 2205 two phase stainless steels
Pit morphology.
Fig. 2 is shown in 70 DEG C of smoke modelling liquid that light microscope is observed after the stripping of 2205 two phase stainless steels
Pit morphology.
Fig. 3 shows that the artificial of 2205 two phase stainless steels collapses pattern in 70 DEG C of smoke modelling liquid that SEM is observed.
Fig. 4 shows the natual subside pattern of 2205 two phase stainless steels in 70 DEG C of smoke modelling liquid that SEM is observed.
Fig. 5 show 48 samples of embodiment 1-12 when corrosion resistance to sulfuric acid is tested obtained by rate of corrosion column system
Score Butut.
Obtained by Fig. 6 schematically shows embodiment 3 and steel grade in the prior art in hydrochloric acid corrosion resistant performance test
Rate of corrosion curve.
Fig. 7 schematically shows embodiment 6 and steel grade in the prior art in the corrosion of resistance to smoke modelling performance test
When obtained by rate of corrosion curve.
Fig. 8 schematically shows that annual corrosion rate is converted in 2205 two phase stainless steel spot corrosion.
Fig. 9 is the normalizing state metallographic structure figure of the low-alloy steel of the acid corrosion-resistant of embodiment 3.
Figure 10 is the rolled metallographic structure figure of the low-alloy steel of the acid corrosion-resistant of embodiment 3.
Specific implementation mode
Low-alloy steel, steel below in conjunction with Figure of description and specific embodiment to acid corrosion-resistant of the present invention
Pipe, steel plate and its manufacturing method make further explanation, however the explanation and illustration is not to the technical side of the present invention
Case constitutes improper restriction.
Embodiment 1-12
The low-alloy steel of the acid corrosion-resistant of embodiment 1-12 uses the mass percentage of each chemical element listed by table 1
It is smelted, wherein steel plate is made in the low-alloy steel of the acid corrosion-resistant of embodiment 1-6, by the acid corrosion-resistant of embodiment 7-12
Low-alloy steel steel pipe is made.
Table 1. (wt%, surplus are Fe and other inevitable impurity elements other than P)
| C | Si | Mn | P | S | Cr | Cu | Sb | (Cu+Sb)/3S | |
| Embodiment 1 | 0.20 | 0.38 | 0.15 | 0.009 | 0.008 | 0.75 | 0.25 | 0.035 | 12 |
| Embodiment 2 | 0.13 | 0.20 | 0.65 | 0.010 | 0.006 | 0.15 | 0.35 | 0.025 | 21 |
| Embodiment 3 | 0.15 | 0.18 | 0.45 | 0.009 | 0.001 | 0.35 | 0.1 | 0.005 | 35 |
| Embodiment 4 | 0.06 | 0.25 | 0.30 | 0.012 | 0.015 | 0.6 | 0.2 | 0.015 | 5 |
| Embodiment 5 | 0.08 | 0.30 | 0.50 | 0.008 | 0.013 | 0.45 | 0.3 | 0.037 | 9 |
| Embodiment 6 | 0.10 | 0.15 | 0.35 | 0.006 | 0.005 | 0.95 | 0.15 | 0.04 | 13 |
| Embodiment 7 | 0.09 | 0.40 | 0.75 | 0.007 | 0.004 | 0.5 | 0.08 | 0.08 | 13 |
| Embodiment 8 | 0.12 | 0.35 | 0.25 | 0.012 | 0.012 | 0.85 | 0.3 | 0.065 | 10 |
| Embodiment 9 | 0.07 | 0.36 | 0.70 | 0.008 | 0.010 | 0.82 | 0.23 | 0.019 | 8 |
| Embodiment 10 | 0.14 | 0.17 | 0.38 | 0.007 | 0.012 | 0.39 | 0.13 | 0.55 | 19 |
| Embodiment 11 | 0.11 | 0.28 | 0.47 | 0.012 | 0.009 | 0.57 | 0.18 | 0.009 | 7 |
| Embodiment 12 | 0.18 | 0.23 | 0.59 | 0.011 | 0.014 | 0.28 | 0.27 | 0.75 | 24 |
The manufacturing method of steel plate, including step is made in the low-alloy steel of the acid corrosion-resistant of embodiment 1-3：
(1) it smelts and is cast as slab；
(2) it heats：1200-1350 DEG C of heating temperature, soaking time >=60min；
(3) hot rolling：Finishing temperature >=850 DEG C.
Table 2 lists specific process parameter in the step involved by the manufacturing method of embodiment 1-3.
Table 2.
| Heating temperature (DEG C) | Soaking time (min) | Finishing temperature (DEG C) | |
| Embodiment 1 | 1340 | 60 | 950 |
| Embodiment 2 | 1200 | 90 | 880 |
| Embodiment 3 | 1290 | 70 | 900 |
The manufacturing method of steel plate, including step is made in the low-alloy steel of the acid corrosion-resistant of embodiment 4-6：
(1) it smelts and is cast as slab；
(2) it heats：1200-1350 DEG C of heating temperature, soaking time >=60min；
(3) hot rolling；
(4) cold rolling；
(5) normalizing or normalizing+tempering is used to be heat-treated：Wherein normalizing temperature is 830-930 DEG C, soaking time >=
25min, it is then air-cooled；Temperature is 450-530 DEG C, and soaking time >=20min is air-cooled.
Table 3 lists specific process parameter in the step involved by the manufacturing method of embodiment 4-6.
Table 3.
The manufacturing method of steel pipe, including step is made in the low-alloy steel of the acid corrosion-resistant of embodiment 7-9：
(1) it smelts and is cast as pipe；
(2) it heats：1200-1350 DEG C of heating temperature, soaking time >=60min；
(3) it perforates：Piercing temperature is 1070-1180 DEG C, and subsequent sky subtracts and tandem rolling；
(4) it reheats：Relation reheating temperature is 920-1000 DEG C, soaking time >=30min；
(5) hot rolling：Finishing temperature >=850 DEG C.
Table 4 lists specific process parameter in the step involved by the manufacturing method of embodiment 7-9.
Table 4.
The manufacturing method of steel pipe, including step is made in the low-alloy steel of the acid corrosion-resistant of embodiment 10-12：
(1) it smelts and is cast as pipe；
(2) it heats：1200-1350 DEG C of heating temperature, soaking time >=60min；
(3) it perforates：Piercing temperature is 1070-1180 DEG C, and subsequent sky subtracts and tandem rolling；
(4) it reheats：Relation reheating temperature is 920-1000 DEG C, soaking time >=30min；
(5) hot rolling；
(6) cold rolling or cold-drawn；
(7) normalizing or normalizing+tempering is used to be heat-treated：Wherein normalizing temperature is 830-930 DEG C, soaking time >=
25min, it is then air-cooled；Temperature is 450-530 DEG C, and soaking time >=20min is air-cooled.
Table 5 lists specific process parameter in the step involved by the manufacturing method of embodiment 10-12.
Table 5.
Microcosmic group of above-described embodiment is ferrite+pearlite, and 8 grades of grain size, is different from the prior art
2205 two phase stainless steel microstructures, 2205 two phase stainless steels are austenite+ferrite, and wherein austenite accounts for 50%.
Fig. 5 show 48 samples of embodiment 1-12 when corrosion resistance to sulfuric acid is tested obtained by rate of corrosion column system
Meter figure.Wherein what the longitudinal axis indicated is the number of samples or its accounting of corresponding abscissa rate of corrosion.
Totally 48 samples are made in the low-alloy steel of all embodiments, corrosion resistance to sulfuric acid survey has been carried out to above-mentioned sample
Examination, sample is in 70 DEG C of -50%H2SO4It is impregnated for 24 hours in solution, and test result is depicted as rate of corrosion column as shown in Figure 5 and is united
Score Butut.
As shown in figure 5, the rate of corrosion of 48 samples obtained by the low-alloy steel of each embodiment of this case is below 80g/
m2.h (position shown in LSL dotted lines in figure), average value 68.95g/m2.h, value improves 12.5% than expected.It can be seen that this
The low-alloy steel of the invention acid corrosion-resistant reaches resistant to sulfuric acid dew point corrosion tradition steel grade 09CrCuSb (being commonly called as ND steel) steel
Most tight class requirement, than inferior requirement≤140g/m2.h (position shown in upper specification limit dotted line in figure) improves about 50%, display
Go out the highly corrosion resistant of low-alloy steel of the present invention.
Hydrochloric acid corrosion resistant performance test has been carried out to the low-alloy steel of embodiment 3, sample made of embodiment 3 is placed in 60
DEG C when 5% and 10.5% hydrochloric acid in 6h, tested for 24 hours with 48h, it is bent that measured data are depicted as rate of corrosion as shown in FIG. 6
Line.As shown in fig. 6,304 Corrosion of Stainless Steel rates extend and reduce at any time, increases with concentration of hydrochloric acid and increase substantially, 10.5%
When 48h in always be far above low-alloy steel of the present invention, it can be seen that, 304 steel corrosion resistances are affected by concentration of hydrochloric acid,
Suitable in 5% equal low concentration of salt acid environment.And low-alloy steel rate of corrosion of the present invention extends and slightly increases at any time
Add, increases with concentration of hydrochloric acid and slightly increase, it can be seen that low-alloy steel corrosion resistance is influenced slightly by concentration of hydrochloric acid.S-Ten1-
L/H corrodes steel as the resistance to nitration mixture of low-alloy system that certain iron company develops, and increasing degree is followed successively by from small to large at any time
S-Ten1-L, low-alloy steel of the present invention and S-Ten1-H；With concentration increasing degree be followed successively by from small to large S-Ten1-H,
Low-alloy steel and S-Ten1-L of the present invention.In general, low-alloy steel of the present invention is in hydrochloric acid corrosion resistant
Better than each steel grade of the prior art.
When desulfurizer flue-gas temperature falls abruptly to 60 DEG C by 100 DEG C or more, temperature is less than flue gas dew point temperature, therein
SO3Water suction generates H2SO4, while Cl-Then association hydrochloric acid, to form nitration mixture corrosive environment, in engineering≤80 DEG C of temperature regions
Often select 2205 two phase stainless steels.As sulfur removal technology simulated solution, the ingredient of dead green liquor is 11.4%H2SO4- 1.2%HCl-
1.0%Fe3Cl, the corrosive environment in the fine reaction desulfuration tower of the simulation liquid energy are all used it for golden in flue gas desulfurization both at home and abroad
Belong to the corrosion resistance assessment of material.By embodiment 6, duplex stainless steel 2205 and S-Ten1-H/L in 50 DEG C, 60 DEG C and 70 DEG C death
Corrosion type and rate of corrosion in green liquor for 24 hours are listed in table 6.
Table 6.
Note：The sample of S-Ten1-L and S-Ten1-H is there is no surveying 60 DEG C of value in table, thus, S-Ten1- in the figure 7
L and S-Ten1-H is only two points, is not linked to be curve.
6 test result of table is plotted as Fig. 7, and is combined shown in Fig. 8, is increased with temperature, the rate of corrosion of each steel grade is in
Ascendant trend, weight-loss method rate of corrosion be followed successively by from high to low S-Ten1-H, S-Ten1-L, low-alloy steel of the present invention and
2205 two phase stainless steels.In addition, in 2 kinds of S-Ten1 (i.e. S-Ten1-L and S-Ten1-H), even if with preferable S-Ten1-
L is compared, and 7% and 25% is respectively increased in 70 DEG C and 50 DEG C in low-alloy steel corrosion resistance of the present invention, i.e. temperature is lower, this
The invention low-alloy steel corrosion resistance is more advantageous.In addition, low-alloy steel of the present invention and S-Ten1-H, S-Ten1-L
For homogeneous corrosion, local corrosion (i.e. spot corrosion) occurs for 2205 two phase stainless steels, that is to say, that 2205 two phase stainless steels and the present invention
The low-alloy steel corrosion mechanism is different.Although under 70 DEG C of temperature conditions, 2205 two phase stainless steel weight-loss method annual corrosion rates
γgIt is minimum to be less than 0.012mm/a, but the annual corrosion rate γ of spot corrosion and its conversion easily occurspUp to 360mm/a.Therefore, comprehensive next
It sees, low-alloy steel corrosion resistance of the present invention is optimal in the test of smoke modelling liquid, i.e., it is rotten to have excellent resistance to nitration mixture by the present invention
Erosion ability.
Room temperature tensile properties test is carried out to embodiment 3 and 4, the room temperature tensile properties result of gained is listed in table 7.
Table 7.
| Serial number | State | Rp0.2(MPa) | Rm(MPa) | A (%) |
| Embodiment 3 | Hot rolling | 289.5 | 430 | 36 |
| Embodiment 4 | Normalizing | 305 | 447.5 | 35.5 |
As can be seen from Table 7, the extension test of embodiment of this case 3 and 4 is it is found that rolled and normalizing state are generally in same
One is horizontal, and the surrender of normalizing state and tensile strength are slightly higher, and elongation percentage is slightly lower.
Fig. 9 is the normalizing state metallographic structure figure of the low-alloy steel of the acid corrosion-resistant of embodiment 3.
Figure 10 is the rolled metallographic structure figure of the low-alloy steel of the acid corrosion-resistant of embodiment 3.
Can be seen that microcosmic group of embodiment 3 in conjunction with Fig. 9 and Figure 10 is ferrite+pearlite, and 8 grades of grain size, no
It is same as 2205 two phase stainless steel microstructure in the prior art, 2205 two phase stainless steels are austenite+ferrite, wherein Ovshinsky
Body accounts for 50%.
It should be noted that the above list is only specific embodiments of the present invention, it is clear that the present invention is not limited to above real
Example is applied, there are many similar variations therewith.If those skilled in the art directly exported from present disclosure or
All deformations associated, are within the scope of protection of the invention.
Claims (15)
1. a kind of low-alloy steel of acid corrosion-resistant, which is characterized in that its microstructure is ferrite+pearlite,
The chemical element mass percentage of the low-alloy steel of the acid corrosion-resistant is：
0 ＜ C≤0.2%；
Si：0.15~0.4%；
Mn：0.15~0.75%；
S：0.001~0.015%；
Cr：0.15~0.95%；
Cu：0.08~0.3%；
Sb：0.005~0.08%；
Surplus is Fe and other inevitable impurity；
Wherein, (Sb+Cu)/3S is 5~35.
2. the low-alloy steel of acid corrosion-resistant as described in claim 1, which is characterized in that its grain size is 8 grades.
3. the low-alloy steel of acid corrosion-resistant as described in claim 1, which is characterized in that Cu constituent contents be 0.15~
0.25%.
4. the low-alloy steel of acid corrosion-resistant as described in claim 1, which is characterized in that Sb constituent contents be 0.01~
0.04%.
5. the low-alloy steel of acid corrosion-resistant as described in claim 1, which is characterized in that (Sb+Cu)/3S is 9~21.
6. the low-alloy steel of acid corrosion-resistant as described in claim 1, which is characterized in that it is 50% in 70 DEG C of mass concentrations
Rate of corrosion ＜ 80g/m for 24 hours are impregnated in sulfuric acid solution2.h。
7. the low-alloy steel of acid corrosion-resistant as described in claim 1 or 6, which is characterized in that its rolled or normalizing state or just
Yield strength >=300MPa of fire+tempering state product, tensile strength >=420MPa, elongation percentage >=30%.
8. the low-alloy steel of acid corrosion-resistant as described in claim 1 or 6, which is characterized in that its cold rolling or cold-drawn product are bent
Take intensity >=400MPa, tensile strength >=510MPa, elongation percentage >=25%.
9. a kind of steel plate, the low-alloy steel for adopting the acid corrosion-resistant as described in any one of claim 1-8 is made.
10. the manufacturing method of steel plate as claimed in claim 9, which is characterized in that including step：
(1) it smelts and is cast as slab；
(2) it heats：1200-1350 DEG C of heating temperature, soaking time >=60min；
(3) hot rolling：Finishing temperature >=850 DEG C.
11. the manufacturing method of steel plate as claimed in claim 9, which is characterized in that including step：
(1) it smelts and is cast as slab；
(2) it heats：1200-1350 DEG C of heating temperature, soaking time >=60min；
(3) hot rolling；
(4) cold rolling；
(5) normalizing or normalizing+tempering is used to be heat-treated：Wherein normalizing temperature is 830-930 DEG C, soaking time >=25min,
Then air-cooled；Temperature is 450-530 DEG C, and soaking time >=20min is air-cooled.
12. a kind of steel pipe, the low-alloy steel for adopting the acid corrosion-resistant as described in any one of claim 1-8 is made.
13. the manufacturing method of steel pipe as claimed in claim 12, which is characterized in that including step：
(1) it smelts and is cast as pipe；
(2) it heats：1200-1350 DEG C of heating temperature, soaking time >=60min；
(3) it perforates：Piercing temperature is 1070-1180 DEG C；
(4) it reheats：Relation reheating temperature is 920-1000 DEG C, soaking time >=30min；
(5) hot rolling：Finishing temperature >=850 DEG C.
14. the manufacturing method of steel pipe as claimed in claim 12, which is characterized in that including step：
(1) it smelts and is cast as pipe；
(2) it heats：1200-1350 DEG C of heating temperature, soaking time >=60min；
(3) it perforates：Piercing temperature is 1070-1180 DEG C；
(4) it reheats：Relation reheating temperature is 920-1000 DEG C, soaking time >=30min；
(5) hot rolling；
(6) cold rolling or cold-drawn；
(7) normalizing or normalizing+tempering is used to be heat-treated：Wherein normalizing temperature is 830-930 DEG C, soaking time >=25min,
Then air-cooled；Temperature is 450-530 DEG C, and soaking time >=20min is air-cooled.
15. manufacturing method according to claim 13 or 14, which is characterized in that the step (3) further includes that sky subtracts and tandem rolling.
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| CN113564481A (en) * | 2021-08-04 | 2021-10-29 | 马鞍山钢铁股份有限公司 | Low-cost sulfate acid dew point corrosion resistant steel plate and manufacturing method thereof |
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