CN108660384A - A kind of low-alloy steel of sulfuric acid corrosion resistant, steel pipe, steel plate and its manufacturing method - Google Patents
A kind of low-alloy steel of sulfuric acid corrosion resistant, steel pipe, steel plate and its manufacturing method Download PDFInfo
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- CN108660384A CN108660384A CN201710202577.4A CN201710202577A CN108660384A CN 108660384 A CN108660384 A CN 108660384A CN 201710202577 A CN201710202577 A CN 201710202577A CN 108660384 A CN108660384 A CN 108660384A
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- sulfuric acid
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- alloy steel
- corrosion resistant
- acid corrosion
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
- B21C37/00—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
- B21C37/02—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
- B21C37/00—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
- B21C37/06—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of tubes or metal hoses; Combined procedures for making tubes, e.g. for making multi-wall tubes
-
- 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
- C21D1/18—Hardening; Quenching with or without subsequent tempering
-
- 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
- C21D8/02—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
-
- 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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/008—Ferrous alloys, e.g. steel alloys containing tin
-
- 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
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
-
- 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
-
- 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
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/005—Ferrite
-
- 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
Abstract
The invention discloses a kind of low-alloy steel of sulfuric acid corrosion resistant, microstructure is ferrite+pearlite, and the chemical element mass percentage of the low-alloy steel of the sulfuric acid corrosion resistant is：0 ＜ C≤0.15%；Si：0.1~0.4%；Mn：0.28~0.85%；S：0.004~0.02%；Cr：0.25~0.9%；Cu：0.02~0.35%；Sb：0.01~0.04%；Sn：0.01~0.03；Surplus is Fe and other inevitable impurity；Wherein, (Sb+Sn)/S is 1~15.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 sulfuric acid corrosion resistant.The low-alloy steel of sulfuric acid corrosion resistant of the present invention is resistance to sulfuric acid while can be high, has higher hardness and intensity, abrasive wear resistance ability strong.
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、SO2Deng
Sour gas, SO2SO is further generated under catalytic action3, when flue-gas temperature is less than sulphuric acid dew point, just condensation and dewfall is formed
Corrosion of sulfuric acid at dew point.For energy-saving and emission-reduction and pollution is reduced, generally uses low-temp desulfurization technique, sulphuric acid dew point corruption certainly will just occur
Erosion.
Single resistant to sulfuric acid dew point corrosion generally relies on Cu or Cu-Sb systems and realizes its corrosion resistance.For example, 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
The corrosion-resistant material of acid.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, and
Not with strongest 70 DEG C of -50% assessment of corrosivity is generally acknowledged, even if 140 DEG C -80% under having hot environment and 160 DEG C -90%
Corrosion resistance as a result, it is well known that sulfuric acid shows oxidisability when 80~90%, so that metal is passivated and slow down corrosion and be lost in,
Reproducibility when being different from 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, sour corrosion is larger with concentration and temperature change, and as in 100 DEG C or less low temperature environments, at 70 DEG C -50%, sulfuric acid corrosion resistance is most
By force, what above-mentioned steel grade relied on is the conclusion under weaker 60 DEG C -40% of corrosivity.Moreover its rate of corrosion only restriction≤200g/
m2H, it is typical as 09CrCuSb and its tubing have already been less than 140g/m in resistant to sulfuric acid dew point corrosion steel alloy material2.h,
Even 80g/m2.h.So industrialization product of its corrosion resistance against sulfuric acid far away from last century.Similarly, only with 1% it is low dense
Its hydrochloric acid corrosion resistant of degree evaluation certificate is good, unknown in the corrosion resistance of concentrated hydrochloric acid.
In addition, contain a large amount of particle in flue gas, and wind speed is larger, causes the abrasive wear of material serious, such as Yantai
Company is failed due to just perforation because wearing within about 3~4 months using the device of tradition 09CrCuSb steel makings.And above-mentioned material is substantially
Normalizing or normalizing+tempering heat treatment is all needed to use, intensity is relatively low, the proportional relationship based on intensity and hardness, wearability
It is relatively low.
Invention content
One of the objects of the present invention is to provide a kind of low-alloy steel of sulfuric acid corrosion resistant, the low-alloy steel do not add Mo,
Al, Ni, Ti, V, B element realize good resistance to sulfuric acid by optimized alloy element, especially Cu, Sb, Sn element and its proportioning
Corrosion, in addition, the low-alloy steel intensity of gained is high, hardness is good, effectively reduces production cost.
To achieve the goals above, the present invention proposes a kind of low-alloy steel of sulfuric acid corrosion resistant, and microstructure is iron
The chemical element mass percentage of ferritic+pearlite, the low-alloy steel of the sulfuric acid corrosion resistant is：
0 ＜ C≤0.15%；
Si：0.1~0.4%；
Mn：0.28~0.85%；
S：0.004~0.02%；
Cr：0.25~0.9%；
Cu：0.02~0.35%；
Sb：0.01~0.04%；
Sn：0.01~0.03；
Surplus is Fe and other inevitable impurity；
Wherein, (Sb+Sn)/S is 1~15.
The design principle of each chemical element in the low-alloy steel of sulfuric acid corrosion resistant of the present invention is：
C：C is easily formed carbide, unfavorable to corrosion resistance, and the lower its mass percent should be the better in principle；But C is carried again
The most economical element of high hardness of steel, and be objective reality, the mass percent for excessively reducing C is uneconomical, therefore, in this hair
The mass percent of control C is in 0 ＜ C≤0.15% in the low-alloy steel of the bright sulfuric acid corrosion resistant.
Si：Si solution strengthening is conducive to improve the intensity of steel, and is advantageous to the corrosion resistance against sulfuric acid of steel, therefore, this
The mass percentage of Si is limited in the low-alloy steel of the invention sulfuric acid corrosion resistant in Si：0.1~0.4%.
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 is limited in the low-alloy steel of sulfuric acid corrosion resistant of the present invention
The mass percentage of Mn is in Mn：0.28~0.85%.
S：S elements generally require stringent control in conventional steel, but to the low-alloy of sulfuric acid corrosion resistant of the present invention
Steel is beneficial element, the compound for inhibiting electrochemical corrosion can be formed with Cu, Sb element, therefore, in skill of the present invention
The mass percentage of S is controlled 0.004~0.02% in art scheme.
Cr：In technical solutions according to the invention, Cr is not only to improve the corrosion proof important element of steel, and improves steel
The important element of quenching degree, that is to say, that addition Cr is conducive to improve the intensity of steel.However, the mass percent of Cr is excessively high, no
The economy of steel is only reduced, quenching degree is excessively high to be also unfavorable for producing, therefore to the quality of Cr in technical solutions according to the invention
Percentage composition is controlled in Cr：0.25~0.90%.
Cu：Cu is conventional relict element in steel, needs strictly to control in other steel grades, but to resistant to sulfur of the present invention
For the low-alloy steel of acid corrosion, addition Cu is conducive to improve the acid resistance of steel.To prevent rolling crack to be inclined to, in institute of the present invention
The mass percentage of Cu is controlled in the low-alloy steel for the sulfuric acid corrosion resistant stated 0.02~0.35%.
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 0.01~0.04%.
Sn：Addition Sn is conducive to improve the resistance to sulfuric acid of steel, but excessive addition Sn is unfavorable for the hot rolling of steel, therefore, at this
The mass percentage of control Sn is 0.01~0.03 in the low-alloy steel of the invention sulfuric acid corrosion resistant.
In order to integrate the collaboration corrosion resistance against sulfuric acid for playing Sb, Sn and S element, inventor has found Sb, Sn and S member
Element control is 1~15 in (Sb+Sn)/S, and acid resistance compound such as Sb and S, Sn and S, even Sb- are formed to ensure that
Sn is combined with S jointly, 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 improves the resistance to of steel
Sulfuric acid corrosion resistance.
In order to improve the corrosion resistance to sulfuric acid of steel, the mass percentage of inevitable impurity element should be controlled
The lower that makes is the better, however is limited by process conditions and considered from production cost angle is saved, by inevitable impurity member
Element control exists：P≤0.012% further controls P≤0.010% in some preferred embodiments.
Further, in the low-alloy steel of sulfuric acid corrosion resistant of the present invention, the Phase Proportion of the pearlite≤
8%.
Further, in the low-alloy steel of sulfuric acid corrosion resistant of the present invention, the Phase Proportion of the pearlite≤
5%.
Further, in the low-alloy steel of sulfuric acid corrosion resistant of the present invention, grain size is 6 grades or more.
Further, in the low-alloy steel of sulfuric acid corrosion resistant of the present invention, Cu constituent contents be 0.05~
0.3%.
Further, in the low-alloy steel of sulfuric acid corrosion resistant of the present invention, Sb constituent contents be 0.02~
0.032%.
Further, in the low-alloy steel of sulfuric acid corrosion resistant of the present invention, Sn constituent contents be 0.015~
0.025%.
Further, in the low-alloy steel of sulfuric acid corrosion resistant of the present invention, (Sb+Sn)/S is 2~7.
Further, it is 50% in 70 DEG C of mass concentrations in the low-alloy steel of sulfuric acid corrosion resistant of the present invention
Sulfuric acid solution in impregnate rate of corrosion≤60g/m for 24 hours2.h。
Further, in the low-alloy steel of sulfuric acid corrosion resistant of the present invention, rolled or normalizing state product
Yield strength >=310MPa, tensile strength >=430MPa, elongation percentage >=35%.
Further, in the low-alloy steel of sulfuric acid corrosion resistant of the present invention, cold rolling or the surrender of cold-drawn product
Intensity >=560MPa, tensile strength >=760MPa, elongation percentage >=10%.
Further, in the low-alloy steel of sulfuric acid corrosion resistant of the present invention, the yield strength of quenching state product
>=700MPa, tensile strength >=880MPa, elongation percentage >=10%.
In addition, another object of the present invention is to provide a kind of steel plate, the low-alloy of above-mentioned sulfuric acid corrosion resistant is used
Steel 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 >=840 DEG C.
Further, further include step (4) in the manufacturing method of steel plate of the present invention：Cold rolling.
Further, in the manufacturing method of steel plate of the present invention, also there is quenching after hot rolling or cold rolling step
Heat treatment step：Hardening heat is 820-930 DEG C, then soaking time >=5min cools down, and cooling velocity is >=5 DEG C/s.
It should be noted that can also carry out in some preferred embodiments, after hot rolling or cold rolling step just burning hot
Processing step, normalizing temperature are 840~920 DEG C, heat preservation >=15min, more preferably in embodiment, normalizing temperature 860
~895 DEG C, heat preservation >=20min.But production cost is generally reduced, is used instead of normalizing state using rolled in technique.
In addition, in order to further increase the intensity and wearability of steel, the hardening heat of quenching heat treatment can preferably be controlled
At 850~890 DEG C, soaking time can preferably be controlled in >=10min system, and room temperature may be used when with postcooling or low temperature is situated between
Matter such as water is cooled down.In addition, another object of the present invention is to provide a kind of steel pipe, above-mentioned sulfuric acid corrosion resistant is used
Low-alloy steel be made.
Correspondingly, another object of the present invention is to provide a kind of 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) hot rolling：Finishing temperature >=840 DEG C.
Further, further include step (5) cold rolling or cold-drawn in manufacturing method of the present invention.
Further, in manufacturing method of the present invention, also there is quenching after hot rolling or cold rolling or cold-drawn step
Heat treatment step：Hardening heat is 820-930 DEG C, then soaking time >=5min cools down, and cooling velocity is >=5 DEG C/s.
It should be noted that can also carry out in some preferred embodiments, after hot rolling or cold rolling step just burning hot
Processing step, normalizing temperature are 840~920 DEG C, heat preservation >=15min, more preferably in embodiment, normalizing temperature 860
~895 DEG C, heat preservation >=20min.But production cost is generally reduced, is used instead of normalizing state using rolled in technique.
In addition, in order to further increase the intensity and wearability of steel, the hardening heat of quenching heat treatment can preferably be controlled
At 850~890 DEG C, soaking time can preferably be controlled in >=10min system, and room temperature may be used when with postcooling or low temperature is situated between
Matter such as water is cooled down.Further, in manufacturing method of the present invention, the step (3) further includes that sky subtracts and connects
It rolls.
Further, also have in manufacturing method of the present invention, between the step (3) and step (4) and add again
Hot step：920-1000 DEG C of relation reheating temperature, soaking time >=30min.
The low-alloy steel of acid corrosion-resistant of the present invention is designed using reasonable alloying element, is ensureing corrosion resistance against sulfuric acid
Under the premise of, there is preferable mechanical property, such as compared with 09CrCuSb in the prior art, bearing identical allowable answer
Power is improved under the premise of identical pressure-bearing wall thickness and projected life based on corrosion resistance low-alloy steel of the present invention
25%, thus, corrosion allowance thickness of the consumptive material just than 09CrCuSb can be reduced when using low-alloy steel of the present invention
25.0% or more.In addition, the rolled of low-alloy steel of the present invention is higher than traditional 09CrCuSb intensity, and it is of the present invention
Low-alloy steel cold rolling or cold-drawn state or quenching state intensity significantly improved than traditional 09CrCuSb, thus, use is of the present invention
Manufacturing method can not only improve the wearability of steel, can also reduce wall thickness and improve material cost performance.And use the resistance to sulfuric acid
Steel plate, the steel pipe of the low-alloy steel of corrosion also have the advantages that above-mentioned.
Description of the drawings
Fig. 1 show 60 samples of embodiment 1-12 when corrosion resistance to sulfuric acid is tested obtained by rate of corrosion column system
Meter figure.
Fig. 2 is the normalizing state metallographic structure figure of the low-alloy steel of the sulfuric acid corrosion resistant of embodiment 6.
Fig. 3 is the rolled metallographic structure figure of the low-alloy steel of the sulfuric acid corrosion resistant of embodiment 6.
Specific implementation mode
Below in conjunction with Figure of description and specific embodiment to the low-alloy steel of sulfuric acid corrosion resistant of the present invention
It makes further explanation, however should explanation and description do not unduly limit the technical scheme of the present invention.
Embodiment 1-12
The low-alloy steel of the sulfuric acid corrosion resistant of embodiment 1-12 is contained using the quality percentage of each chemical element listed by table 1
Amount is smelted, wherein steel plate is made in the low-alloy steel of the sulfuric acid corrosion resistant of embodiment 1-6, by the resistant to sulfur of embodiment 7-12
Steel pipe is made in the low-alloy steel of acid corrosion.
Table 1. (wt%, surplus are Fe and other inevitable impurity elements other than P)
The manufacturing method of steel plate, including step is made in the low-alloy steel of the sulfuric 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 >=840 DEG C, not normalizing after hot rolling.
(4) hardening heat is 820-930 DEG C, then soaking time >=5min cools down, and cooling velocity is >=5 DEG C/s
Table 2 lists specific process parameter in the step involved by the manufacturing method of embodiment 1-3.
Table 2.
The manufacturing method of steel plate, including step is made in the low-alloy steel of the sulfuric 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, not normalizing after hot rolling；
(4) cold rolling；
(5) hardening heat is 820-930 DEG C, then soaking time >=5min cools down, and cooling velocity is >=5 DEG C/s.
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 sulfuric 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 progress sky subtracts and tandem rolling；
(3a) reheats step：920-1000 DEG C of relation reheating temperature, soaking time >=30min.
(4) hot rolling：Finishing temperature >=840 DEG C, not normalizing after hot rolling.
(5) quenching Step：Hardening heat is 820-930 DEG C, then soaking time >=5min cools down, and cooling velocity is >=5
℃/s。
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 sulfuric 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 progress sky subtracts and tandem rolling；
(3a) reheats step：920-1000 DEG C of relation reheating temperature, soaking time >=30min.
(4) hot rolling：Finishing temperature >=840 DEG C, not normalizing after hot rolling.
(5) cold rolling or cold-drawn.
(6) quenching Step：Hardening heat is 820-930 DEG C, then soaking time >=5min cools down, and cooling velocity is >=5
℃/s。
Table 5 lists specific process parameter in the step involved by the manufacturing method of embodiment 10-12.
Table 5.
Table 6 lists the rolled tensile property of embodiment 3,5,6.
Table 6.
As can be seen from Table 6, the low-alloy steel yield strength, tensile strength of the sulfuric acid corrosion resistant of each embodiment of this case and prolong
The rate of stretching is superior to the intensity index required by 09CrCuSb.
The tensile property that table 7 lists embodiment 2 (quenching state), 4 (cold rolling states), 8 (quenching states) and 10 (cold-drawn states) is surveyed
Test result.
Table 7.
As can be seen from Table 7, the tensile strength of each embodiment is 782~905.5MPa, the significantly larger than 09CrCuSb upper limits,
According to the direct proportion correspondence of hardness and tensile strength, it can thus be seen that the cold rolling state of each embodiment of this case, cold-drawn state and
The normalizing state wearability of steel significantly improves quenching state than in the prior art.
Fig. 1 show embodiment 1-12 when corrosion resistance to sulfuric acid is tested obtained by rate of corrosion column statistical chart.Wherein
What the longitudinal axis indicated is the number of samples or its accounting of corresponding abscissa rate of corrosion.
60 samples are made in 70 DEG C of -50%H in the low-alloy steel of the sulfuric acid corrosion resistant of each embodiment2SO4It is soaked in solution
Bubble for 24 hours, tests the rate of corrosion drafting pattern 1 of gained.As shown in Figure 1, the rate of corrosion of the sample obtained by each embodiment of this case is equal
Less than 80g/m2.h (position shown in LSL dotted lines in figure), the average value for being computed gained are 48.165g/m2.h, sample maximum
≤60g/m2.h.It can be seen that the biography that the low-alloy steel of sulfuric acid corrosion resistant of the present invention is more optimal than resistant to sulfuric acid dew point corrosion
Most tight grade≤80g/m of system steel grade 09CrCuSb steel2.h 25% or more is improved, than inferior requirement≤140g/m2.h it (is advised in figure
Position shown in lattice upper limit dotted line) 57.1% or more is improved, it can be seen that low-alloy steel of the present invention has height resistance to
Sulfuric acid corrosion resistance.
Fig. 2 is the normalizing state metallographic structure figure of the low-alloy steel of the acid corrosion-resistant of embodiment 6.
Fig. 3 is the rolled metallographic structure figure of the low-alloy steel of the acid corrosion-resistant of embodiment 6.
It is generally known that component system is corrosion proof determinant.Therefore, it advocates in the prior art through crystal grain thinning degree
Corrosion resistance is improved, since material needs weld, and weld seam and its crystal grain of heat affected area are larger, although pass through weldering
After be heat-treated and can suitably improve to a certain extent, but differ larger with base material grain size, the corrosion resistance phase of base material and weld seam
Difference is just big, i.e., weld dimensions position corrosion resistance is weak.
And microcosmic group that combination Fig. 2 and Fig. 3 can be seen that embodiment 6 is ferrite+pearlite, and pearlite is compared
Example≤5%, 6~7 grades of grain size, to ensure that corrosion resistance against sulfuric acid and mechanics of the embodiment 6 in rolled and normalizing state
The consistency of performance.
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 (22)
1. a kind of low-alloy steel of sulfuric acid corrosion resistant, which is characterized in that its microstructure is ferrite+pearlite, the resistant to sulfur
The chemical element mass percentage of the low-alloy steel of acid corrosion is：
0 ＜ C≤0.15%；
Si：0.1~0.4%；
Mn：0.28~0.85%；
S：0.004~0.02%；
Cr：0.25~0.9%；
Cu：0.02~0.35%；
Sb：0.01~0.04%；
Sn：0.01~0.03；
Surplus is Fe and other inevitable impurity；
Wherein, (Sb+Sn)/S is 1~15.
2. the low-alloy steel of sulfuric acid corrosion resistant as described in claim 1, which is characterized in that the Phase Proportion of the pearlite≤
8%.
3. the low-alloy steel of sulfuric acid corrosion resistant as claimed in claim 2, which is characterized in that the Phase Proportion of the pearlite≤
5%.
4. the low-alloy steel of sulfuric acid corrosion resistant as described in claim 1, which is characterized in that its grain size is 6 grades or more.
5. the low-alloy steel of sulfuric acid corrosion resistant as described in claim 1, which is characterized in that Cu constituent contents be 0.05~
0.3%.
6. the low-alloy steel of sulfuric acid corrosion resistant as described in claim 1, which is characterized in that Sb constituent contents be 0.02~
0.032%.
7. the low-alloy steel of sulfuric acid corrosion resistant as described in claim 1, which is characterized in that Sn constituent contents be 0.015~
0.025%.
8. the low-alloy steel of sulfuric acid corrosion resistant as described in claim 1, which is characterized in that (Sb+Sn)/S is 2~7.
9. the low-alloy steel of sulfuric acid corrosion resistant as described in claim 1, which is characterized in that it is 50% in 70 DEG C of mass concentrations
Sulfuric acid solution in impregnate rate of corrosion≤60g/m for 24 hours2.h。
10. the low-alloy steel of the sulfuric acid corrosion resistant as described in claim 1 or 9, which is characterized in that its rolled or the production of normalizing state
Yield strength >=310MPa of product, tensile strength >=430MPa, elongation percentage >=35%.
11. the low-alloy steel of the sulfuric acid corrosion resistant as described in claim 1 or 9, which is characterized in that its cold rolling or cold-drawn product
Yield strength >=560MPa, tensile strength >=760MPa, elongation percentage >=10%.
12. the low-alloy steel of the sulfuric acid corrosion resistant as described in claim 1 or 9, which is characterized in that the surrender of its quenching state product
Intensity >=700MPa, tensile strength >=880MPa, elongation percentage >=10%.
13. a kind of steel plate, the low-alloy steel for adopting the sulfuric acid corrosion resistant as described in any one of claim 1-12 is made.
14. the manufacturing method of steel plate as claimed in claim 13, 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 >=840 DEG C.
15. the manufacturing method of steel plate as claimed in claim 14, which is characterized in that further include step (4)：Cold rolling.
16. the manufacturing method of the steel plate as described in claims 14 or 15, which is characterized in that also have after hot rolling or cold rolling step
There is quenching heat treatment step：Hardening heat be 820-930 DEG C, then soaking time >=5min cools down, cooling velocity be >=5 DEG C/
s。
17. a kind of steel pipe, the low-alloy steel for adopting the sulfuric acid corrosion resistant as described in any one of claim 1-12 is made.
18. the manufacturing method of steel pipe as claimed in claim 17, 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) hot rolling：Finishing temperature >=840 DEG C.
19. manufacturing method as claimed in claim 18, which is characterized in that further include step (5) cold rolling or cold-drawn.
20. the manufacturing method as described in claim 18 or 19, which is characterized in that also have after hot rolling or cold rolling or cold-drawn step
There is quenching heat treatment step：Hardening heat be 820-930 DEG C, then soaking time >=5min cools down, cooling velocity be >=5 DEG C/
s。
21. manufacturing method as claimed in claim 18, which is characterized in that the step (3) further includes that sky subtracts and tandem rolling.
22. manufacturing method as claimed in claim 18, which is characterized in that also have again between the step (3) and step (4)
Heating stepses：920-1000 DEG C of relation reheating temperature, soaking time >=30min.
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