CN108286017B - A kind of think gauge Q420 rank high temperature high voltage resistant corrosion of sulfuric acid at dew point steel plate and its production method - Google Patents
A kind of think gauge Q420 rank high temperature high voltage resistant corrosion of sulfuric acid at dew point steel plate and its production method Download PDFInfo
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- CN108286017B CN108286017B CN201810128052.5A CN201810128052A CN108286017B CN 108286017 B CN108286017 B CN 108286017B CN 201810128052 A CN201810128052 A CN 201810128052A CN 108286017 B CN108286017 B CN 108286017B
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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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- 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
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- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
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- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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- C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
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- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
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- 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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Abstract
The invention discloses a kind of manufacturing technique methods of think gauge Q420 rank high temperature high voltage resistant corrosion of sulfuric acid at dew point steel plate, and wherein the ingredient of steel and weight percent content are；C:0.10~0.15%, Si:0.20~0.40%, Mn:0.60~1.00%, P :≤0.015%, S :≤0.010%, Cu:0.25~0.40%, Cr:0.40~0.80%, Sb:0.02~0.07%, Ni:0.08~0.15%, Nb:0.015~0.035%, Ti:0.015~0.035%, Al:0.020~0.040%, and control CEV≤0.40%, Ni/Cu >=0.3, remaining is Fe and is inevitably mingled with.Steel grade produced by the invention provides advantageous technical support for the development of relevant industries.
Description
Technical field
The invention belongs to technical field of low-alloy steel production, and in particular to a kind of think gauge Q420 rank high temperature resistant sulfuric acid dew
Spot corrosion steel plate and its production method.
Background technique
Currently, the meager lean coal that China mostly uses sulfur content that can reach 3% using coal as the enterprise of main fuel, considerably beyond
2.5% highest corrosivity standard in China GB 50051-2002 " Code for design of chimneys ".In works such as metallurgy, electric power, petrochemical industry
In industry field with heavy oil or it is coal-fired be main fuel smoke processing system, can generally encounter because in fuel higher sulfur content due to produce
Raw " corrosion of sulfuric acid at dew point " in turn results in equipment etching problem.Meanwhile China continues to increase environmental improvement dynamics, to each hair
Electricity, chemical industry, petroleum, iron and steel enterprise propose the new environmental requirement of addition desulfurizer.But the desulfurization of the country about 95% at present
Device uses wet desulphurization, and dilute sulphuric acid content has certain journey instead in unit volume in the flue gas after using this method desulfurization
The increase of degree, so the flue gas environment after desulfurization may be such that the corrosion condition of smoke processing system further deteriorates.In a variety of solutions
Certainly in the scheme of such corrosion of sulfuric acid at dew point problem, most effective method is exactly using with compared with highly resistance corrosion of sulfuric acid at dew point
The corrosionproof steel against sulfuric acid at dew point plate of ability.
With the development of relevant industries, corrosionproof steel against sulfuric acid at dew point plate has a vast market prospect increasingly, and towards low
Cost, high corrosion resistance against sulfuric acid, high-strength plasticity and good welds direction develop.Currently, such domestic steel plate executes GB/T
28907-2012 " corrosionproof steel against sulfuric acid at dew point plate and steel band " standard is only provided with two boards of Q315NS and Q345NS in the standard
Number, what the relevant industries that intensity rank have not been able to satisfy gradually developed uses steel high strengthening demand；And about steel plate in the standard
Limitation of the thickness specification no more than 40mm has also been unable to satisfy actual application demand.
Before making the present invention, according to it is relevant authorized and published patented technology look into it is new as a result, have it is following it is related specially
Benefit, in which:
Chinese patent CN200680006324.X is disclosed a kind of " steel of excellent in resistance to sulfuric acid dew point corrosion ", system cold-rolled
Steel smelts 50kg steel ingot using vacuum smelting furnace in laboratory, then carries out hot rolling, cold rolling and annealing and obtains coiled sheet；It is Chinese special
Sharp CN201010116893.8 discloses a kind of " corrosionproof steel against sulfuric acid at dew point KNS and its milling method ", is related to a kind of thin rule of 4mm
Lattice coil of strip does not provide the specific performance and corrosion resistance to sulfuric acid dew point of steel；Chinese patent CN201110268721.7 is disclosed
A kind of " tensile strength >=800MPa grades of corrosionproof steel against sulfuric acid at dew point and preparation method thereof ", is related to a kind of coiled sheet, at setting up separately
Nb and Sb element is not added in meter, produced coil of strip elongation percentage is lower and does not provide impact property, only provides 20 DEG C, 20% sulfuric acid item
Part corrosion resistance to sulfuric acid dew point；Chinese patent CN201310568537.3 discloses a kind of " wear-resisting resistant to sulfuric acid dew point corrosion heat
Tandem rolling steel and its manufacturing method " is related to a kind of wear-resisting resistant to sulfuric acid dew point corrosion hot continuous rolling steel band (volume) and its manufacturing method, uses
The mode of hot tandem produces the hot continuous rolling steel band (volume) for meeting wear-resisting property and resistant to sulfuric acid dew point corrosion, ingredient design
In be not added with Cr, Ni element, only provide 30 DEG C, acid resistance under the conditions of 20% sulfuric acid, do not provide its mechanical property；Chinese CN
201310595866.7 disclosing a kind of " a kind of low cost resistant to sulfuric acid dew point corrosion low-alloy steel and its production technology and use
On the way ", it is related to a kind of round steel of hot continuous rolling process production, ingredient design uses low-carbon, low manganese, Gao Ge, is not added with niobium element, by force
Degree rank is Q320-340, only provides 70 DEG C, acid resistance under the conditions of 50% sulfuric acid.Outside the steel product of above five patents
Seeing pattern is respectively thin gauge coiled sheet/steel band and round steel, and coiled sheet, which is difficult to do width, does thickness, and application is relatively narrow；Its production technology
Larger with " think gauge Q420 rank high-temperature sulfuric acid dew point corrosion resistance hot rolled steel plate " difference of the application, ingredient design aspect also has
It is different.
Chinese patent CN200910187512.2 discloses a kind of " a kind of low-alloy steel resisting dew-point corrosion of sulfuric acid plate and its system
Make method ", ingredient design in be added to Bi element, be not added with Sb element, embodiment is the 80kg completed in laboratory
The smelting and rolling of steel ingot, intensity are Q370-420 rank, only provide 70 DEG C, acid resistance under the conditions of 50% sulfuric acid；China
Patent CN 201010211471.9 discloses a kind of " a kind of rare earth low alloy steel of high-temperature sulfuric acid dew point corrosion resistance ", in alloy
Design aspect adds RE (La, Ce), is not added with Sb element, but do not provide production technology, exterior appearance and the mechanical property of product；
Chinese patent CN 201110418531.9 discloses " one kind plate of corrosionproof steel against sulfuric acid at dew point containing Zr and its manufacturing method ", closes
Golden design aspect is added to rare Zr element, and embodiment is completed to smelt in the lab and be rolled, only provide 20 DEG C,
20% sulfuric acid condition corrosion resistance to sulfuric acid dew point.Above-mentioned three referred to kind patent is added to rare Bi, RE (La, Ce) respectively
With Zr element, production cost and organization of production difficulty will definitely increase；And its embodiment is completed in laboratory, industrial production
Feasibility it is on the knees of the gods.
Herein, be also additionally provided with biggish four patent applications of the application patent degree of association, distinguish it is as follows:
Chinese patent application CN 201510272614.X discloses a kind of " the high-performance steel plate of resistance to sulphuric acid dew point and its manufacture
Method ", but difference is larger compared with this is applied for a patent in the design of its ingredient and production technology: it is used in its design of alloy
Low-carbon, high-copper, nickelic, Gao Ge, cost of alloy is higher, and using controlled rolling+tempering process production, increases tempering process gesture
Production cost must be increased；Its thickness specification > 30mm steel plate intensity and low-temperature impact work are lower, and it only gives corruption relatively
Rate is lost, does not provide etching condition and comparison steel grade.
Chinese patent application CN 201510870140.9 discloses a kind of " a kind of inexpensive without the resistance to sulfuric acid dew of Nb thin gauge
Spot corrosion steel and its production method " is only related to the 8-12mm steel plate of thin gauge, is added to V element in ingredient design aspect, not
Add Nb element；And its intensity is lower, does not provide impact property and corrosion resistance to sulfuric acid dew point.
Chinese patent application CN 201610499180.1 discloses a kind of a kind of " resistance to sulphuric acid dew point of modified 09GrCuSb
Corrosion steel and its manufacturing method ", intensity and low-temperature impact work are lower, under the conditions of only providing temperature 70 C, 50% sulfuric acid
Corrosion resistance.
Chinese patent application CN 201410551555.5 discloses a kind of " a kind of corrosionproof steel against sulfuric acid at dew point plate and its system
Make method ", which is not added with Sb element in alloy design aspect, but is added to V element, and uses opposite low-carbon
And Gao Meng；Its thickness maximum is only capable of reaching 32mm, only provides the corrosion resistance under the conditions of temperature 70 C, 50% sulfuric acid.
In steel in the prior art and there is no sulfuric acid dew resistance under low cost, comprehensive mechanical property, high-temperature and high-pressure conditions
The excellent high-level corrosionproof steel against sulfuric acid at dew point plate of spot corrosion performance, welding performance, forming property.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of low costs, comprehensive mechanical property, resistant to sulfuric acid dew point corrosion
The excellent Q420 rank corrosionproof steel against sulfuric acid at dew point plate of performance, welding performance, forming property and its production method.
Present invention firstly provides a kind of Q420 rank corrosionproof steel against sulfuric acid at dew point plate, the chemical composition contents of the steel plate
Content by weight percentage are as follows: C:0.10~0.15%, Si:0.20~0.40%, Mn:0.60~1.00%, P :≤
0.015%, S :≤0.010%, Cu:0.25~0.40%, Cr:0.40~0.80%, Sb:0.02~0.07%, Ni:0.08~
0.15%, Nb:0.015~0.035%, Ti:0.015~0.035%, Al:0.020~0.040%, CEV≤0.40%, Ni/
Cu >=0.3 remaining Fe and to be inevitably mingled with.
As a kind of better choice of above-mentioned steel plate, Ti/N >=3.4, preferably 4.0~4.5.
As a kind of better choice of above-mentioned steel plate, the chemical component and weight percent content of the steel plate are as follows: C:
0.13%, Si:0.25%, Mn:0.75%, P:0.010%, S:0.005%, Cu:0.30%, Ni:0.13%, Cr:0.60%,
Nb:0.025%, Ti:0.025%, Al:0.025%, remaining is Fe and is inevitably mingled with.
As a kind of better choice of above-mentioned steel plate, in the practical military service operating condition of corrosionproof steel against sulfuric acid at dew point plate: temperature 130
DEG C, sulfuric acid concentration 30%, pressure 8-9KPa, under conditions of full leaching for 24 hours, corrosion rate≤52mm/a, relatively corrosive rate is
≤ 10%.
Invention further provides the production methods of the steel plate, and steps are as follows:
It smelts: using converter smelting, during which use double slag operation to reduce P content；It is refined by LF+RH, reduces O, H, N
Equal pernicious gases and S content, [N]≤0.0040%；[H]≤0.0002%；[O]≤0.0025%, [S] :≤0.005%.
Continuous casting: carrying out full guard casting using weather-proof mould flux, cooperates slighter compress technique, and slighter compress amount is controlled 5
~6mm, drawing speed control guarantees molten steel overheat≤20 DEG C during casting in 1.1~1.3m/min, and continuous casting billet is offline slow
Cold 48h or more.
Heating: the atmosphere in control heating furnace guarantees it for reproducibility or neutrality.Preferably, this step is burnt using low temperature
Steel, soaking time are no less than 40min to guarantee that steel billet burns even grill thoroughly；Tapping temperature is controlled between 1080~1130 DEG C, simultaneously
Accelerate the heating rate in 1100 DEG C or more high temperature sections in 9-10min/cm, to shorten in the residence time of the temperature range,
Guarantee, which is come out of the stove, rolls, to reduce the generation of " copper brittleness " defect as far as possible.
Rolling mill practice: using Stand Mill two stages controlled rolling process, and roughing mill carries out > 1000 DEG C of perfect recrystallization rolling,
It is 2.5~4.5 times of finished product thicknesses to temperature thickness, finish rolling start rolling temperature controls at 880~950 DEG C, rolls rear steel plate and added immediately
But, cooling rate controls between 600~650 DEG C quickly cooling in 6~10 DEG C/s, final cooling temperature.
Preferably, smelting process control Ca content is 0.0008-0.0030%, Ca/S >=1.0, to improve field trash shape
State；Ti/N >=3.4, Ti/N numberical range are preferably 4.0~4.5.
Steel grade relative inexpensiveness of the invention, simple process is easily operated, is suitble to continuous mass production.Steel plate is comprehensive
Can be good, and have and meet for using coal or heavy oil as the smoke processing system high temperature of the industries such as the metallurgy of main fuel, electric power, petrochemical industry
Under corrosion resistance to sulfuric acid dew point and welding performance.
Think gauge Q420 rank high-temperature sulfuric acid dew point corrosion resistance steel plate of the present invention can effectively support relevant industries
Development, be rotten by the resistance to sulphuric acid dew point of the smoke processing system of the industries such as the metallurgy of main fuel, electric power, petrochemical industry of coal or heavy oil
It loses performance boost and technical support is provided
Detailed description of the invention
Fig. 1, Fig. 2 are the microscopic structure of 3 steel plate of invention example (at 1/4,1/2 thickness).
Specific embodiment
It the following is the embodiment of the present invention, be only used as explanation of the invention and not limit.
Technique is designed and produced according to ingredient provided by the invention, Examples 1 to 3 presses following technique production, the master of steel
Chemical component is wanted to be shown in Table 1, actual production technique is shown in Table 2, and the mechanical property of steel is shown in Table 3.
The production method of the steel plate, steps are as follows:
It smelts: using converter smelting, during which use double slag operation to reduce P content；It is refined by LF+RH, reduces O, H, N
Equal pernicious gases and S content.
Continuous casting: carrying out full guard casting using weather-proof mould flux, cooperates slighter compress technique, and slighter compress amount is controlled 5
~6mm, drawing speed control reinforces that continuous casting process one is cold, two cold technology controlling and process in 1.1~1.3m/min, and continuous casting billet is offline
Slow cooling 48h or more.
Heating: the atmosphere in control heating furnace guarantees it for reproducibility or neutrality.Preferably, this step is burnt using low temperature
Steel, soaking time are no less than 40min to guarantee that steel billet burns even grill thoroughly；Tapping temperature is controlled between 1080~1130 DEG C, simultaneously
Accelerate the heating rate in 1100 DEG C or more high temperature sections to shorten the residence time in the temperature range, guarantee, which is come out of the stove, rolls,
To reduce the generation of " copper brittleness " defect as far as possible.
Rolling mill practice: using Stand Mill two stages controlled rolling process, and roughing mill carries out > 1000 DEG C of perfect recrystallization rolling,
It is 2.5~4.5 times of finished product thicknesses to temperature thickness, finish rolling start rolling temperature controls at 880~950 DEG C, rolls rear steel plate and added immediately
But, cooling rate controls between 600~650 DEG C quickly cooling in 6~10 DEG C/s, final cooling temperature.
The characteristics of in order to preferably reflect corrosionproof steel against sulfuric acid at dew point plate high-temperature sulfuric acid dew point corrosion resistance performance of the present invention,
The atmospheric corrosion resistance testing result that present implementation provides 1 group of steel plate is shown in Table 4.Experimental standard is in addition to referring to GB/T 28907-
Two experiment conditions specified in 2012 " corrosionproof steel against sulfuric acid at dew point plate and steel band " appendix As: experiment condition 1: 20 DEG C of temperature, sulphur
Acid concentration 20%, full leaching is for 24 hours；Experiment condition 2: temperature 70 C, sulfuric acid concentration 50%, full leaching is outer for 24 hours, also according to resistance to sulphuric acid dew point
Corrode the practical service condition during steel plate industrial application, it is determined that experiment condition 3: 130 DEG C of temperature, sulfuric acid concentration 30%, pressure
Strong 8-9KPa, full leaching is for 24 hours.The rate of corrosion under the conditions of the total immersion test of different experiments room is obtained after analyzing the data obtained, is seen
Table 4.
It is easily operated to can be seen that the simple process for data from the above table, is suitble to large-scale industrial production；Produced steel plate
With corrosion resistance to sulfuric acid dew point under good comprehensive mechanical property and high-temperature and high-pressure conditions.
The steel plate chemical component example of the present invention of table 1
The steel plate actual production craft embodiment of the present invention of table 2
The mechanical property of steel plate example of the present invention of table 3
Rate of corrosion (mm/a) under the conditions of the steel plate difference total immersion test of the present invention of table 4
The invention is not limited to examples detailed above, according to component requirements provided by the invention and manufacturing technique requirent,
Implement.
It should be noted last that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting.Although ginseng
It is described the invention in detail according to embodiment, those skilled in the art should understand that, to technical side of the invention
Case is modified or replaced equivalently, and without departure from the spirit and scope of technical solution of the present invention, should all be covered in the present invention
Scope of the claims in.
Claims (6)
1. a kind of think gauge Q420MPa rank high temperature high voltage resistant corrosion of sulfuric acid at dew point steel plate, it is characterised in that: the change of the steel plate
Learn component content content by weight percentage are as follows: C:0.10~0.15%, Si:0.20~0.40%, Mn:0.60~1.00%,
P :≤0.015%, S :≤0.010%, Cu:0.25~0.40%, Cr:0.40~0.80%, Sb:0.02~0.07%, Ni:
0.08~0.15%, Nb:0.015~0.035%, Ti:0.015~0.035%, Al:0.020~0.040%, CEV≤
0.40%, Ni/Cu >=0.3, remaining is Fe and is inevitably mingled with；In the practical military service work of corrosionproof steel against sulfuric acid at dew point plate
Condition, i.e. 130 DEG C of temperature, sulfuric acid concentration 30%, pressure 8-9kPa, under conditions of full leaching for 24 hours, corrosion rate < 52mm/a, phase
It is < 10% to corrosion rate.
2. steel plate according to claim 1, it is characterised in that: Ti/N >=3.4.
3. the production method of any steel plate of claim 1-2, includes the following steps:
1) it smelts: using converter smelting, during which use double slag operation to reduce P content；Refined by LF+RH, reduce O, H, N and
S content；
2) continuous casting: carrying out full guard casting using weather-proof mould flux, cooperates slighter compress technique, the control of slighter compress amount 5~
6mm, drawing speed control guarantee molten steel overheat≤20 DEG C during casting, and the offline slow cooling of continuous casting billet in 1.1~1.3m/min
48h or more；
3) heat: the atmosphere in control heating furnace guarantees it for reproducibility or neutrality；
4) rolling mill practice: using Stand Mill two stages controlled rolling process, and roughing mill carries out > 1000 DEG C of perfect recrystallization rolling, to
Temperature thickness is 2.5~4.5 times of finished product thicknesses, and finish rolling start rolling temperature controls at 880~950 DEG C, rolls rear steel plate and accelerated immediately
Cooling, cooling rate controls between 600~650 DEG C in 6~10 DEG C/s, final cooling temperature；
Step 2) soaking time is no less than 40min to guarantee that steel billet burns even grill thoroughly；Control tapping temperature 1080~1130 DEG C it
Between, while accelerating in the heating rate in 1100 DEG C or more high temperature sections to be 9-10 DEG C/min.
4. production method according to claim 3, it is characterised in that: step 1) controls [N]≤0.0040%；[H]≤
0.0002%；[O]≤0.0025%, [S] :≤0.005%.
5. production method according to claim 3, it is characterised in that: Ca content be 0.0008-0.0030%, Ca/S >=
1.0, to improve inclusion morphology；Ti/N≥3.4.
6. production method according to claim 3, which is characterized in that in smelting process Ti/N numberical range be 4.0~
4.5。
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| CN110551947A (en) * | 2019-10-21 | 2019-12-10 | 攀钢集团攀枝花钢铁研究院有限公司 | Weather-resistant steel and preparation method thereof |
| CN111172463A (en) * | 2020-02-17 | 2020-05-19 | 本钢板材股份有限公司 | Acid corrosion resistant BGNS440 steel hot-rolled coil and preparation method thereof |
| CN115011876B (en) * | 2022-05-30 | 2023-07-14 | 鞍钢股份有限公司 | Steel for high-temperature sulfuric acid dew point corrosion resistance and manufacturing method |
| CN115652194A (en) * | 2022-09-29 | 2023-01-31 | 首钢集团有限公司 | Sulfuric acid dew point corrosion resistant steel and preparation method thereof |
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| JPH0925536A (en) * | 1995-07-06 | 1997-01-28 | Sumitomo Metal Ind Ltd | Acid dew point corrosion resistant steel |
| JP3760534B2 (en) * | 1996-12-13 | 2006-03-29 | 住友金属工業株式会社 | Usage of austenitic stainless steel components in sulfuric acid dew point environment |
| JPH11106872A (en) * | 1997-09-30 | 1999-04-20 | Nkk Corp | Stainless steel for sulfuric acid dew point corrosion resistance excellent in hot workability |
| CN104357754B (en) * | 2014-10-17 | 2016-06-22 | 江阴兴澄特种钢铁有限公司 | A kind of corrosionproof steel against sulfuric acid at dew point plate and manufacture method thereof |
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