CN105908195B - A kind of hot rolling 409L ferritic stainless steels are without nitric acid acidwashing method - Google Patents
A kind of hot rolling 409L ferritic stainless steels are without nitric acid acidwashing method Download PDFInfo
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- CN105908195B CN105908195B CN201610387005.3A CN201610387005A CN105908195B CN 105908195 B CN105908195 B CN 105908195B CN 201610387005 A CN201610387005 A CN 201610387005A CN 105908195 B CN105908195 B CN 105908195B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/08—Iron or steel
- C23G1/081—Iron or steel solutions containing H2SO4
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Abstract
The present invention relates to a kind of hot rolling 409L ferritic stainless steels without nitric acid acidwashing method, this method is to carry out pre- pickling, first paragraph successively to strip without nitric acid acidwashing and second segment without nitric acid acidwashing, wherein, two sections use (H without nitric acid acidwashing2SO4+Fe3++Fe2++H2O2) mixing pickle.The present invention is using the concentrated sulfuric acid, the mixing pickle of hydrogen peroxide, the pickling requirement of hot rolling 409L ferritic stainless steel strip steels can be met, realize strip without nitric acid acidwashing, avoid producing the nitrogen oxides and nitrogenous effluent of high pollution during using nitration mixture pickling containing nitric acid, so as to mitigate environmental pollution.
Description
Technical field
The invention belongs to acid-washing stainless steel technical field, and in particular to a kind of hot rolling 409L ferritic stainless steels are without nitric acid acid
Washing method.
Background technology
At present, hot rolling 409L ferritic stainless steel strip steels are all after annealing, and mechanical scale breading (scale breading is carried out to strip
Machine+dry type shot-blasting machine), nitration mixture (HNO is then carried out again3+ HF) pickling.But in acid cleaning process, sour consumption is larger, while
The nitrogen oxides of a large amount of high pollutions can be produced and containing nitrate wastewater, natural environment and human being's production, active belt can be given to come seriously
Harm, and purification of nitrogen oxides cost and processing cost containing nitrate wastewater are also higher.
2012, State Ministry of Environmental Protection formulated strict nitrogen pollutant discharge standard, wherein roller for steel industry
Industry nitric acid mist highest allows concentration of emission by original 420mg/m3Fall below 150mg/m3, sewage discharge is not originally to total nitrogen
Concentration limits, and new standard limitation sewage discharge total nitrogen concentration need to be less than 15mg/L, and in the higher local total nitrogen of environmental requirement
Concentration need to be less than 5mg/L, cause nitrous oxides exhaust gas caused by stainless steel nitration mixture pickling and the increase of nitrogenous effluent treatment cost.
The content of the invention
The embodiment of the present invention provides a kind of hot rolling 409L ferritic stainless steels without nitric acid acidwashing method, can at least solve existing
The segmental defect of technology.
The present embodiments relate to a kind of hot rolling 409L ferritic stainless steels without nitric acid acidwashing method, it includes following step
Suddenly：
Pre- acid pickling step：Strip immerses pickling in pre- pickle；
First paragraph is without nitric acid acidwashing step：Strip after pre- pickling step process immerses first without in nitric acid acidwashing liquid,
Described first without in nitric acid acidwashing liquid, H2SO4Concentration is 10~30g/L, Fe3+Concentration is 20~50g/L, Fe2+Concentration be 0~
50g/L, H2O2Concentration is 3~7g/L；
Second segment is without nitric acid acidwashing step：Second is immersed without nitric acid without the strip after nitric acid acidwashing step process through first paragraph
In pickle, described second without in nitric acid acidwashing liquid, H2SO4Concentration is 10~30g/L, Fe3+Concentration is 0~20g/L, Fe2+It is dense
Spend for 0~40g/L, H2O2Concentration is 2~5g/L.
As one of embodiment, in the pre- acid pickling step, the pre- pickle is sulfuric acid pickling solution；The sulfuric acid washing
In liquid, H2SO4Concentration is 150~170g/L, and concentration of metal ions is 30~40g/L.
As one of embodiment, the temperature of the sulfuric acid pickling solution is 75~85 DEG C, and pickling time is 25~50s.
As one of embodiment, the first paragraph without nitric acid acidwashing step and second segment without in nitric acid acidwashing step, pickling
The temperature of liquid is 25~35 DEG C.
As one of embodiment, the first paragraph without nitric acid acidwashing step and second segment without in nitric acid acidwashing step, pickling
Time is 25~50s.
As one of embodiment, in the pre- acid pickling step, in the sulfuric acid pickling solution, H2SO4Concentration is 155~165g/
L, concentration of metal ions are 33~37g/L；The temperature of the sulfuric acid pickling solution is 77~83 DEG C, and pickling time is 35~42.5s.
As one of embodiment, the first paragraph is without in nitric acid acidwashing step, and described first without in nitric acid acidwashing liquid, H2SO4
Concentration is 15~20g/L, Fe3+Concentration is 30~40g/L, Fe2+Concentration is 0~35g/L, H2O2Concentration is 4~6g/L；Described
One temperature without nitric acid acidwashing liquid is 28~33 DEG C, and pickling time is 35~42.5s.
As one of embodiment, the second segment is without in nitric acid acidwashing step, and described second without in nitric acid acidwashing liquid, H2SO4
Concentration is 15~20g/L, Fe3+Concentration is 0~10g/L, Fe2+Concentration is 10~30g/L, H2O2Concentration is 3~5g/L；Described
Two temperature without nitric acid acidwashing liquid are 28~33 DEG C, and pickling time is 35~42.5s.
As one of embodiment, described first uses such as lower section without nitric acid acidwashing liquid and described second without nitric acid acidwashing liquid
Method is prepared：The concentrated sulfuric acid and water are added into complex acid tank to prepare to obtain prefabricated mixed acid liquid, the prefabricated mixed acid liquid supplies in pickle
Answer in pipeline and be mixed to get no nitric acid acidwashing liquid with the hydrogen peroxide added by branch line.
As one of embodiment, cleaned through second segment without the strip after nitric acid acidwashing step process into cleaning section, cleaning
Medium is hydrogen peroxide.
As one of embodiment, in cleansing medium, H2O2Concentration is 2~5g/L, and the temperature of cleansing medium is 25~35 DEG C.
As one of embodiment, before the pre- acid pickling step, strip is pre-processed；Preprocess method is included to band
Steel carries out annealing and the processing of mechanical scale breading.
The embodiment of the present invention at least realizes following beneficial effect：The present invention uses the mixing pickling of the concentrated sulfuric acid, hydrogen peroxide
Liquid, the pickling requirement of hot rolling 409L ferritic stainless steel strip steels can be met, realize strip without nitric acid acidwashing, avoid using containing nitre
The nitrogen oxides and nitrogenous effluent of high pollution are produced during the nitration mixture pickling of acid, so as to mitigate environmental pollution.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the required accompanying drawing used in technology description to be briefly described, it should be apparent that, drawings in the following description are only this
Some embodiments of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can be with
Other accompanying drawings are obtained according to these accompanying drawings.
Fig. 1 is flow signal of the hot rolling 409L ferritic stainless steels provided in an embodiment of the present invention without nitric acid acidwashing method
Figure；
Fig. 2 is the structural representation for the stainless steel strip acid dip pickle that the embodiment of the present invention two provides；
Fig. 3 is the structural representation for the cleaning device that the embodiment of the present invention three provides；
Fig. 4 is the structural representation for the preheating device that the embodiment of the present invention four provides.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation describes, it is clear that described embodiment is only part of the embodiment of the present invention, rather than whole embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art obtained on the premise of creative work is not made it is all its
Its embodiment, belongs to the scope of protection of the invention.
Embodiment one
Such as Fig. 1, the present embodiments relate to a kind of hot rolling 409L ferritic stainless steels without nitric acid acidwashing method, including following
Step：
(1) S101, pre- acid pickling step：Strip immerses pickling in pre- pickle.Wherein, pre- pickle is preferably to use sulfuric acid
Pickle, certainly, it can also use other acid solutions, such as nitric acid, or mixed acid solution of sulfuric acid and nitric acid etc..Using sulfuric acid washing as
, in sulfuric acid pickling solution, H2SO4Concentration is 150~170g/L, and concentration of metal ions is 30~40g/L.Wherein, sulfuric acid pickling solution
Temperature be preferably control in the range of 75~85 DEG C, preferable sulfuric acid washing effect can be obtained.Pickling time is preferably to control
In the range of 25~50s, overpickling situation does not occur for controllable strip, can be according to field working conditions (including belt steel thickness, pickle
Temperature etc.) it is adjusted flexibly.
(2) S102, first paragraph is without nitric acid acidwashing step：Strip after pre- acid pickling step S101 processing immerses first without nitre
In sour pickle, described first without in nitric acid acidwashing liquid, H2SO4Concentration is 10~30g/L, Fe3+Concentration is 20~50g/L, Fe2+
Concentration is 0~50g/L, H2O2Concentration is 3~7g/L.Wherein, the above-mentioned first temperature without nitric acid acidwashing liquid is preferably to control 25
In the range of~35 DEG C, preferable pickling effect can be obtained.Pickling time is preferably to control in the range of 25~50s, it is ensured that band
Steel does not occur to owe pickling or overpickling situation.
(3) S103, second segment is without nitric acid acidwashing step：Through first paragraph without the strip leaching after nitric acid acidwashing step S102 processing
Enter second without in nitric acid acidwashing liquid, described second without in nitric acid acidwashing liquid, H2SO4Concentration is 10~30g/L, Fe3+Concentration be 0~
20g/L, Fe2+Concentration is 0~40g/L, H2O2Concentration is 2~5g/L.Wherein, the above-mentioned second temperature without nitric acid acidwashing liquid is preferred
To control in the range of 25~35 DEG C, preferable pickling effect can be obtained.Pickling time is preferably to control in 25~50s scopes
It is interior, it is ensured that strip does not occur to owe pickling or overpickling situation.
Further, before above-mentioned pre- acid pickling step S101, strip is pre-processed, preprocess method is included to band
Steel carries out annealing and the processing of mechanical scale breading.Pretreatment operation can effectively improve follow-up pickling effect and pickling efficiency before pickling, subtract
Few pickling time, reduces the consumption of pickle.
In addition, during stainless steel strip pickling, typically all without preheating, direct passband carries out acid into the pre- descaling bath of sulfuric acid
Wash, i.e., when strip has just enter into acid tank, belt steel surface temperature is generally normal temperature, and temperature only has 25 DEG C；Temperature is general during sulfuric acid washing
Need to be maintained at 75~85 DEG C, pickling effect can be only achieved most preferably, and time of the strip in the pre- descaling bath of sulfuric acid only has tens
Second, the time is shorter, and belt steel surface temperature is extremely difficult to 75~85 DEG C within a short period of time, and this will make pickling effect undesirable.
And strip, when just having entered pre- descaling bath, belt steel surface is relatively dry not to be moistened, and acid solution can be made to contact inequality with belt steel surface
It is even, it is bad to will also result in pickling effect.In addition, strip, after shot-blasting machine de-scaling, belt steel surface still remains a part of oxide skin
Chip, when it brings pre- descaling bath into, it can also consume acid solution.Therefore, in the present embodiment, above-mentioned preprocess method is also included to warp
The strip of annealing and the processing of mechanical scale breading carries out the pre-heat treatment；Preferably, strip is preheated to 50~60 DEG C.
Above-mentioned first paragraph is without the operation principle of nitric acid acidwashing step S102 and second segment without nitric acid acidwashing step S103：
Hydrogen peroxide (H2O2) by Fe2+It is oxidized to Fe3+, make Fe in solution3+Concentration is kept within the specific limits, H2SO4And Fe3+
Combination is equivalent to HNO in acid with strong oxidizing property, with nitration mixture3Effect it is suitable, oxide skin underbead crack and hole can be passed through and permeated
To iron scale internal layer and chromium depleted layer surface, belt steel surface oxide skin is set to be shelled quickly with metallic matrix by dissolving chromium depleted layer
From with come off, H2SO4Also it can be reacted with Fe, Mn in chromium depleted layer and produce a large amount of hydrogen, the release effect of hydrogen can also make oxygen
It is peeling-off and come off to change skin and metallic matrix.When chromium depleted layer has dissolved, Fe3+Strong oxidation can make belt steel surface generate one
The fine and close passivating film of layer, the main component of passivating film is Cr2O3, metallic matrix can be prevented further to be etched.
By above-mentioned pre- acid pickling step S101, the most oxide skin of belt steel surface is can remove, while make remaining oxide skin
Structure become more loose and be easy to come off.By above-mentioned first paragraph without nitric acid acidwashing step S102 and second segment without nitric acid acid
Step S103 is washed, can remove belt steel surface residue oxide skin and chromium depleted layer, and belt steel surface is produced one layer of uniform passivating film.
In the present embodiment, because chromium content is relatively low in hot rolling 409L ferritic stainless steels so that belt steel surface oxide skin ratio
More loose, passivating film is not also fine and close caused by belt steel surface during pickling, is easily caused overpickling phenomenon, and therefore, pickle is (mainly
First without nitric acid acidwashing liquid and second without nitric acid acidwashing liquid) in each sour concentration it is relatively lower, to avoid overpickling, band in addition
The redox reaction potential that steel surface passivation needs is not also high, so the Fe needed3+Concentration is relatively lower, Fe3+/Fe2+Than
Example is also low.It is preferred embodiment below：
As one of preferred embodiment, in above-mentioned pre- acid pickling step S101, by taking sulfuric acid washing as an example, the sulfuric acid pickling solution
In, H2SO4Concentration is 155~165g/L, and concentration of metal ions is 33~37g/L；The temperature of the sulfuric acid pickling solution is 77~83
DEG C, pickling time is 35~42.5s, can obtain preferable sulfuric acid washing effect.
As one of preferred embodiment, above-mentioned first paragraph is without in nitric acid acidwashing step S102, and described first without nitric acid acidwashing
In liquid, H2SO4Concentration is 15~20g/L, Fe3+Concentration is 30~40g/L, Fe2+Concentration is 0~35g/L, H2O2Concentration be 4~
6g/L；Described first temperature without nitric acid acidwashing liquid is 28~33 DEG C, and pickling time is 35~42.5s.Control above-mentioned parameter model
Preferable oxide skin and chromium depleted layer removal effect can be obtained by enclosing.
As one of preferred embodiment, above-mentioned second segment is without in nitric acid acidwashing step S103, and described second without nitric acid acidwashing
In liquid, H2SO4Concentration is 15~20g/L, Fe3+Concentration is 0~10g/L, Fe2+Concentration is 10~30g/L, H2O2Concentration be 3~
5g/L；Described second temperature without nitric acid acidwashing liquid is 28~33 DEG C, and pickling time is 35~42.5s.Control above-mentioned parameter model
The Passivation Treatment enclosed for belt steel surface is better, and passivating film is more uniform.
Optimize the above method, due in hot rolling 409L ferritic stainless steel strip steel acid cleaning process, to avoid that overpickling occurs
Situation, each sour concentration is relatively lower in pickle, easily produces the uneven situation of pickling, causes belt steel surface brightness
It is uneven, strip surface quality is influenceed, therefore, in the present invention, through second segment without the strip after nitric acid acidwashing step S103 processing
Cleaning step S104 processing is carried out, i.e. strip cleans into cleaning section, and cleansing medium is hydrogen peroxide.Wherein, in cleansing medium,
H2O2Concentration is 2~5g/L, and the temperature of cleansing medium is 25~35 DEG C；Further preferably, in above-mentioned cleansing medium, H2O2Concentration
For 2~4g/L, temperature is 28~33 DEG C.
, usually, can be by the concentrated sulfuric acid, work for above-mentioned first without nitric acid acidwashing liquid and the second preparation without nitric acid acidwashing liquid
Industry water and hydrogen peroxide be proportionally added into complex acid tank be made into needed for after pickle, then supplied to descaling bath by acid solution supply line
It is interior；But during complex acid, amount of heat can be produced when the concentrated sulfuric acid mixes with water, the decomposition of hydrogen peroxide can be aggravated, and then is led
Hydrogen peroxide failure is caused, therefore, in the present embodiment, using following preferred embodiment：The concentrated sulfuric acid and water are added into complex acid tank to prepare
Prefabricated mixed acid liquid is obtained, the prefabricated mixed acid liquid mixes in pickle supply line with the hydrogen peroxide added by branch line
Obtain no nitric acid acidwashing liquid.For the manner of formulation of above-mentioned pickle, it is exemplified below a specific embodiment and illustrates.
Embodiment two
Such as Fig. 2, the embodiment of the present invention provides a kind of acid washing liquid for stainless steel organization of supply, for stainless steel strip pickling section
Interior nozzle 102 supplies pickle, and it includes acid solution supply line 112, and the acid solution supply line 112 is connected with pickle and matched somebody with somebody
Structure processed, the pickle, which prepares structure, includes concentrated sulfuric acid dispensing pipe 108, sparge pipe 110 and hydrogen peroxide dispensing pipeline 114；On
State concentrated sulfuric acid dispensing pipe 108 to be used to supply the concentrated sulfuric acid, sparge pipe 110 is used to supply industry water, and hydrogen peroxide dispensing pipeline 114 is used for
Supply hydrogen peroxide.The arrival end of acid solution supply line 112 is connected with complex acid tank 111, the concentrated sulfuric acid dispensing pipe 108, described
Sparge pipe 110 is connected with the arrival end of complex acid tank 111, and the branch of hydrogen peroxide dispensing pipeline 114 is connected to the acid solution
On supply line 112.During due to hydrogen peroxide by the dispensing of branch line 114 to acid solution supply line 112, the concentrated sulfuric acid and water with
It is sufficiently mixed in sour tank 111, amount of heat will not be produced again, thus the thermal decomposition of hydrogen peroxide can be prevented, ensures the acid of pickle
Wash effect.Wherein, the one end of hydrogen peroxide dispensing pipeline 114 is connected with the acid solution supply line 112, and the other end is connected with hydrogen peroxide
Dispensing tank 116 is connected, and hydrogen peroxide dispensing pump 115 is provided with the hydrogen peroxide dispensing pipeline 114；In acid solution supply line 112
Acid cycle pump 113 is provided with, the acid cycle pump 113 is located at the complex acid tank 111 and the hydrogen peroxide dispensing pipeline 114
Between branch's tie point, certainly, above-mentioned acid cycle pump 113 may be alternatively provided at the branch's tie point of hydrogen peroxide dispensing pipeline 114 and acid
Between the port of export of liquid supply line 112.
Further, the heating arrangements 117 for being used for heating pickle are provided with above-mentioned acid solution supply line 112, it is described
Heating arrangements 117 are between the branch's tie point of hydrogen peroxide dispensing pipeline 114 and the acid solution supply pipe port of export.Dioxygen
Water heats with after being mixed by the mixed acid that complex acid tank 111 exports on acid solution supply line 112 into above-mentioned heating arrangements 117,
Each nozzle 102 is delivered to again, that is, is improved the temperature of pickle, can be improved pickling effect.Preferably, the heating arrangements 117 include
Heat exchanger 117, the heat exchanger 117 can be water-water heat exchanger or the shell-and-tube heat exchanger using flue gas heat exchange etc..
The embodiment of the present invention further relates to a kind of stainless steel strip acid dip pickle, including descaling bath 101, the descaling bath 101
Interior to be provided with the spraying and blowing organ 102 for being used for spraying pickle, the spraying and blowing organ 102 is connected with above-mentioned pickle organization of supply.
Such as Fig. 2, the descaling bath 101 is interior to be provided with overflow launder 103, and the bottom of overflow launder 103 is connected with acid solution return duct
105, the bottom of descaling bath 101 is connected with acid solution evacuated tube 107, and the acid solution evacuated tube 107 is provided with exhaust-valve 106；Institute
State acid solution return duct 105 and the acid solution evacuated tube 107 is connected with the complex acid tank 111.By said structure, pickling is formed
The circulation-supplied system of liquid, reduce pickle consumption.Wherein, above-mentioned overflow launder 103 typically is provided at both ends with descaling bath 101,
When descaling bath 101 is longer, overflow launder 103 also is provided with the middle, each bottom of overflow launder 103 is provided with refluxing opening, on connecting
State acid solution return duct 105；Between adjacent two overflow launder 103, the bottom of descaling bath 101 can be easy to the pickling of spray into V-structure
Iron scale under liquid and pickling etc. collects, and above-mentioned acid solution evacuated tube 7 may connect to the bottom or a little higher than of above-mentioned V-structure
The bottom of the V-structure.During normal production, the exhaust-valve 106 in above-mentioned acid solution evacuated tube 107 is to close, when stopping pickling
During work, above-mentioned exhaust-valve 106 can be opened, the pickle in descaling bath 101 is emitted into complex acid tank 111 and recycled.Its
In, if through above-mentioned acid solution evacuated tube 107 discharge pickle it is dirtier, i.e., containing impurity such as more iron scales when, can pass through
Arranged outside outer comb, i.e., outer comb is also associated with the bottom of above-mentioned V-structure, outer comb is provided with discharging valve；Or it is above-mentioned compared with
Dirty pickle can the recycling after separation of solid and liquid, i.e., above-mentioned acid solution evacuated tube 107 is connected with equipment for separating liquid from solid, solid-liquid
The liquid outlet of separator is connected with complex acid tank 111.In addition, the top of descaling bath 101 is provided with acid mist emission pipe 118, on
Stating acid mist emission pipe 118 can be respectively provided with the both ends of descaling bath 101.
The first paragraph that the stainless steel strip acid dip pickle that the present embodiment provides can be used in above-described embodiment one is without nitric acid acid
Wash step S102 and second segment and handled without no nitric acid acidwashing is carried out in nitric acid acidwashing step S103 to strip 1.
Embodiment three
Such as Fig. 3, the embodiment of the present invention provides a kind of cleaning device of no nitric acid acidwashing strip 1, and the cleaning device is arranged on
Pickling section exports, for clearing up the strip 1 through being handled without nitric acid acidwashing.The cleaning device includes rinse bath 202, cleaning
The arrival end of groove 202 is exported close to pickling section and set, and backing roll 203 and squeeze roll 204, backing roll 203 are provided with rinse bath 202
Arrival end close to rinse bath 202 is set, and squeeze roll 204 is set close to the port of export of rinse bath 202.The cleaning device also includes
For being blown the spraying and blowing organ of cleansing medium, the spraying and blowing organ is located in rinse bath 202；Such as Fig. 3, above-mentioned spraying and blowing organ includes more
Group jet pipe group, multigroup jet pipe group are sequentially arranged along the traffic direction of strip 1 in the rinse bath 202, wherein, each jet pipe
Group includes the jet pipe 205 along at least the one of the width of strip 1 arrangement and at least once jet pipe 205, each upper jet pipe 205 are located at band
Steel 1 runs the top of passage, and for spraying cleansing medium to the upper surface of strip 1, each lower jet pipe 205 is located at strip 1 and runs passage
Lower section, for the lower surface of strip 1 spray cleansing medium.
Above-mentioned spraying and blowing organ is connected with blowing media organization of supply, and the blowing media organization of supply includes industry water supply pipe
Control valve is equipped with road and hydrogen peroxide supply line, the industry water supply line and the hydrogen peroxide supply line；Wherein,
Above-mentioned each jet pipe group connects with the industry water supply line and hydrogen peroxide supply line.Industry water supply line to injection machine
Structure supplies industry water, and austenitic stainless steel can be met without the cleaning treatment after nitric acid acidwashing；Hydrogen peroxide supply line to injection machine
Structure supply hydrogen peroxide, using the strong oxidation of hydrogen peroxide, make the surface passivation of strip 1, may be such that low chrome ferritic stainless steel without
During nitric acid acidwashing, surface brightness non-uniform phenomenon after the pickling of strip 1 is eliminated, low chrome ferritic stainless steel can be met without nitric acid acid
Cleaning treatment after washing；The break-make of respective pipeline is controlled by the control valve on two supply lines, realizes cutting for two supply lines
Change jobs, so that the pickling of different stainless steels can be used to handle needs for this cleaning device.
As one of embodiment, the industry water supply line includes supplying the clear of industry water into the rinse bath 202
Wash water service and the industrial water circulation pipeline for being connected to the bottom of rinse bath 202, the industrial water circulation pipeline and institute
Spraying and blowing organ connection is stated, and the first control valve 210 is provided with the industrial water circulation pipeline.On the industrial water circulation pipeline
Circulating pump 207 is set, increases the jetting pressure of jet pipe 205, improves cleaning performance and efficiency.
As one of embodiment, the hydrogen peroxide supply line includes dioxygen water circulating pipe, the dioxygen water-circulating pipe
Road arrival end is connected to the bottom of rinse bath 202, and the port of export is connected with the spraying and blowing organ, on the dioxygen water circulating pipe
Provided with hydrogen peroxide circulating tank 208, the pipeline of the entrance side of hydrogen peroxide circulating tank 208 is provided with the second control valve 209, outlet side
Pipeline be provided with circulating pump 207.
For above-mentioned medium organization of supply, industry water and hydrogen peroxide can be supplied by single supply line respectively, i.e., on
It is independent pipeline that industrial water circulation pipeline, which is stated, with above-mentioned dioxygen water circulating pipe；It is empty to reduce pipe arrangement cost and cloth
Between, preferably take following structure：Such as Fig. 3, the industrial water circulation pipeline shares one section with the dioxygen water circulating pipe and returned
Flow tube road is connected to the bottom of rinse bath 202, and the reflux line port of export branch forms industry water supply branch road and dioxygen
Water supply branch road, first control valve 210 is on the industrial water supply branch road, the hydrogen peroxide circulating tank 208 and institute
The second control valve 209 is stated on the dioxygen water supply branch road；Further, the industrial water supply branch road and the dioxygen
Water supply branch road shares one section of output channel and is connected to the spraying and blowing organ, and the circulating pump 207 is located on the output channel,
I.e. industry water supply line shares a set of circulating pump 207 with hydrogen peroxide supply line.
Such as Fig. 3, above-mentioned rinse water service 206 is preferably mounted on the arrival end cell wall of rinse bath 202, above-mentioned backflow
Pipeline is then set positioned at the outlet side of rinse bath 202；The bottom of rinse bath 202 is preferably to have two sections of slopes, and two sections of slopes bottom connects
Connect to form a V-type bottom, the dirt-collecting conveniently washed down, the link position of above-mentioned reflux line and rinse bath 202 is located at the V
Above the bottom of type bottom, to ensure the relative cleanliness factor of the cleansing medium of backflow.Further, it is additionally provided with the bottom of rinse bath 202
For discharging the discharge tube 211 of dirty cleansing medium, the discharge tube 211 is provided with the 3rd control valve 212, the discharge
Pipeline 211 is preferably connected to the bottom at above-mentioned V-type bottom.When cleansing medium is dirtier, can open on above-mentioned discharge tube 211
3rd control valve 212, a certain amount of cleansing medium is discharged, be supplemented new cleansing medium.
The course of work for the cleaning device that the present embodiment provides is as follows：
(1) when pickling austenitic stainless steel, cleaning liquid medium is industry water, and it is past to first pass through rinse water service 206
The inner supply industry water of rinse bath 202, rinse water is set in rinse bath 202 to reach certain liquid level, on above-mentioned dioxygen water circulating pipe
Second control valve 209 is closed, and the first control valve 210 on above-mentioned industrial water circulation pipeline is opened.During cleaning, circulating pump 207 will
Rinse water delivers to each jet pipe 205, and rinse water is sprayed onto the surface of strip 1 by each jet pipe 205, and is collected in the bottom of rinse bath 202, is passed through
Above-mentioned industrial water circulation pipeline recycles.
(2) when pickling low chrome ferritic stainless steel, cleaning liquid medium is hydrogen peroxide, on above-mentioned industrial water circulation pipeline
First control valve 210 is closed, and the second control valve 209 on above-mentioned dioxygen water circulating pipe is opened；During cleaning, hydrogen peroxide circulating tank
Hydrogen peroxide in 208 delivers to each jet pipe 205 by circulating pump 207, and hydrogen peroxide is sprayed onto the surface of strip 1 by each jet pipe 205, and is collected
In the bottom of rinse bath 202, it is back to by above-mentioned reflux line in hydrogen peroxide circulating tank 208.
When the hot rolling 409L ferritic stainless steels provided using above-described embodiment one without nitric acid acidwashing method to hot rolling 409L
Ferritic stainless steel strip steel 1 carry out pickling when, through pre- pickling+first paragraph without nitric acid acidwashing+second segment without nitric acid acidwashing after, strip
1 can enter above-mentioned cleaning device in cleaned, cleansing medium uses hydrogen peroxide.
Example IV
Such as Fig. 4, the present embodiment provides strip preheating device before a kind of pickling, available in above-described embodiment one to strip 1
Preheated.The preheating device includes preheating chamber 301, and the both ends open of preheating chamber 301 forms the band for penetrating the preheating chamber 301
Steel runs passage, and the preheating mechanism preheated to strip 1 is provided with the preheating chamber 301.The preheating chamber 301 is containment housing
Structure, opening at two is only set, to ensure pre-heat effect of the strip 1 in the preheating chamber 301；Formed via two opening limitations
Strip operation passage is preferably horizontal channel, wherein, two groups of supporting roller groups 304, one of which can be set in the preheating chamber 301
Support roller group 304 to set close to the arrival end of preheating chamber 301, another group is set close to the port of export of preheating chamber 301；Every group of supporting
Roller group 304 includes a upper roller and a lower roll, and two roller faces are set and spacing is slightly larger than the thickness of strip 1, to be supported to strip 1
And it is oriented to.
Continue the structure of above-mentioned preheating device, and above-mentioned preheating mechanism can use Electromagnetic Heating, short flame directly heat, heat
The preheating methods such as air heat-exchange；It is a kind of preferred embodiment of the present embodiment such as Fig. 4：The preheating mechanism includes at least one set of steam
Vapour nozzle sets, steam jet group described in every group include at least one steam jet 303 for blowing preheated steam, each steaming
Vapour nozzle 303 is set up in the preheating chamber 301 by injection nozzle carrier.Strip 1 is preheated by steam, on the one hand with band
The contact heat-exchanging effect on the surface of steel 1 is preferable；On the other hand, the surface of strip 1 can effectively be moistened so that strip 1 enters pre- descaling bath
When pickle contacted uniformly with the surface of strip 1, further improve pickling effect；Another further aspect, condensed water caused by steam condensation
The oxide skin chip on the surface of strip 1 can be walked by wash zone to a certain degree, lower the pickle consumption in follow-up acid cleaning process.
In above-mentioned preheating mechanism, it preferably comprises multigroup steam jet group, and each steam jet group is run along strip 1
Direction is sequentially arranged.Wherein, steam jet group described in every group includes spraying along at least one upper steam of the width of strip 1 arrangement
Mouth 303 and at least one lower steam jet 303, each upper steam jet 303 be respectively positioned on above strip operation passage and
Blowing direction down, each lower steam jet 303 be respectively positioned on below strip operation passage and blowing direction upward.Typically
Ground, every group of steam jet group include steam jet group under the upper steam jet group of a row and a row, and often arranging steam jet group includes edge
Multiple steam jets 303 of the width of strip 1 arrangement；Preferably, in every group of steam jet group, the number of upper steam jet 303
The quantity of amount is more than the quantity of lower steam jet 303, is on the one hand because under the steam and strip 1 of the injection of lower steam jet 303
The effect that liquidates on surface is preferable, and heat transfer effect is better than upper steam jet 303, and on the other hand, it is attached that the upper surface of strip 1 has condensate
, the partial coagulation water can take away the heat of part strip 1.Above-mentioned each steam jet 303 is connected with jet chimney 305, is steamed
Steam pipe road 305 is connected to steam generating system, can stablize supplying high temperature steam.
As one of embodiment, such as Fig. 4, the delivery pipe for discharging condensed water is connected with the bottom of preheating chamber 301
Road 306, the discharge tube 306 are provided with the first control valve 307.Further, the bottom of preheating chamber 301 is also associated with using
In the Backwash pipeline 309 for being passed through industry water flushing preheating chamber 301, the Backwash pipeline 309 is provided with the second control valve
308.Wherein, above-mentioned Backwash pipeline 309 can be independently arranged, i.e., be arranged at intervals with above-mentioned discharge tube 306, also can branch's connection
On the discharge tube 306, branch's tie point is between the first control valve 307 and the bottom of preheating chamber 301.
Further optimize said structure, the V-shaped structure in the bottom of preheating chamber 301, include two sections of slopes, described in two sections
Slope extends to the both ends of the preheating chamber 301 from the bottom of the V-structure respectively.Above-mentioned discharge tube 306 is preferably to connect
In the bottom of the bottom of preheating chamber 301 of the V-structure, its both discharge tube 306 as condensed water, it is broken to also serve as oxide skin
The discharge tube 306 of bits；Certainly, the position that can also connect the discharge tube 306 is arranged to a little higher than bottom of preheating chamber 301
Bottom, to improve the cleanliness factor of the condensed water of discharge, now, one need to be connected in addition in the bottom of the bottom of preheating chamber 301 and be used to arrange
Go out the chip discharge pipe of oxide skin chip.By setting slope, it is easy to collecting for condensed water and oxide skin chip.When producing one section
Between after, a certain amount of condensed water and oxide skin chip can be accumulated in the bottom of preheating chamber 301, to prevent that oxide skin chip is heavy for a long time
Product causes to be difficult to clear up in the bottom of preheating chamber 301, can be handled by above-mentioned discharge tube 306 and Backwash pipeline 309,
Specially：The first control valve 307 on discharge tube 306 is first opened, condensed water elimination is clean, it is residual now to might have part
The oxide skin chip stayed stays in the bottom of preheating chamber 301；Close above-mentioned first control valve 307, open the in Backwash pipeline 309
Two control valves 308, it is passed through industry water and rinses the bottom of preheating chamber 301 for a period of time, be then shut off above-mentioned second control valve 308, beat
The first control valve 307 is opened, the industry water being passed through is emptied, turns off above-mentioned first control valve 307；It can be imitated according to backwash
Fruit determines whether to carry out multiple backwash operation.
The condensed water of above-mentioned discharge is recyclable, after separation of solid and liquid, delivers to steam generating system and recycles.In addition, institute
State the top of preheating chamber 301 and be connected with fog discharge pipeline 302, the fog discharged through fog discharge pipeline 302 also can return to steam generating system
Recycle.
Embodiment five
The present embodiment provides a kind of hot rolling 409L ferritic stainless steels
2mm；This method comprises the following steps：
1) strip immerses pickling in sulfuric acid pickling solution, in the sulfuric acid pickling solution, H2SO4Concentration is 155g/L；The sulfuric acid washing
The temperature of liquid is 77 DEG C；The pickling processes time is 42.5s.
2) strip is after persulfuric acid pre-sour is washed, and immerses first without carrying out pickling in nitric acid acidwashing liquid.This first without nitric acid acid
In washing lotion, H2SO4Concentration is 15g/L, Fe3+Concentration is 30g/L, Fe2+Concentration is 35g/L, H2O2Concentration is 4g/L；First nothing
The temperature of nitric acid acidwashing liquid is 28 DEG C, pickling time 42.5s.
3) strip immerses second and carries out pickling without nitric acid acidwashing liquid after first without nitric acid acidwashing liquid pickling.This second
Without in nitric acid acidwashing liquid, H2SO4Concentration is 20g/L, Fe3+Concentration is 5g/L, Fe2+Concentration is 30g/L, H2O2Concentration is 3g/L；Should
Second temperature without nitric acid acidwashing liquid is 28 DEG C, pickling time 42.5s.
4) strip immerses hydrogen peroxide and cleaned after second segment is without nitric acid acidwashing.In the hydrogen peroxide, H2O2Concentration is
2g/L, temperature are 28 DEG C.
Hot rolling 409L ferritic stainless steel strip steels clean it by above-mentioned+two sections of sulfuric acid washing without nitric acid acidwashing+hydrogen peroxide
Afterwards, belt steel surface does not have remaining oxide skin, and belt steel surface finish is higher, meets No.1 class requirements.
Embodiment six
The present embodiment provides a kind of hot rolling 409L ferritic stainless steel acid washing methods, and the thickness of pending strip is 2mm；Should
Method comprises the following steps：
1) strip immerses pickling in sulfuric acid pickling solution, in the sulfuric acid pickling solution, H2SO4Concentration is 165g/L；The sulfuric acid washing
The temperature of liquid is 83 DEG C；The pickling processes time is 35s.
2) strip immerses first without carrying out pickling in nitric acid acidwashing liquid after sulfuric acid washing.This is first without nitric acid acidwashing liquid
In, H2SO4Concentration is 20g/L, Fe3+Concentration is 40g/L, Fe2+Concentration is 0g/L, H2O2Concentration is 6g/L；This first without nitric acid acid
The temperature of washing lotion is 33 DEG C, pickling time 35s.
3) strip immerses second and carries out pickling without nitric acid acidwashing liquid after first without nitric acid acidwashing liquid pickling.This second
Without in nitric acid acidwashing liquid, H2SO4Concentration is 15g/L, Fe3+Concentration is 10g/L, Fe2+Concentration is 10g/L, H2O2Concentration is 5g/L；
Second temperature without nitric acid acidwashing liquid is 33 DEG C, pickling time 35s.
4) strip immerses hydrogen peroxide and cleaned after second segment is without nitric acid acidwashing.In hydrogen peroxide, H2O2Concentration is 4g/
L, temperature are 33 DEG C.
Hot rolling 409L ferritic stainless steel strip steels clean it by above-mentioned+two sections of sulfuric acid washing without nitric acid acidwashing+hydrogen peroxide
Afterwards, belt steel surface does not have remaining oxide skin, and belt steel surface finish is higher, meets No.1 class requirements.
Embodiment seven
The present embodiment provides a kind of hot rolling 409L ferritic stainless steel strip steel acid washing methods, and the thickness of pending strip is
2mm；This method comprises the following steps：
1) strip immerses pickling in sulfuric acid pickling solution, in the sulfuric acid pickling solution, H2SO4Concentration is 160g/L；The sulfuric acid washing
The temperature of liquid is 80 DEG C；The pickling processes time is 38s.
2) strip immerses first without carrying out pickling in nitric acid acidwashing liquid after sulfuric acid washing.This is first without nitric acid acidwashing liquid
In, H2SO4Concentration is 18g/L, Fe3+Concentration is 35g/L, Fe2+Concentration is 20g/L, H2O2Concentration is 5g/L；This is first without nitric acid
The temperature of pickle is 30 DEG C, pickling time 38s.
3) strip immerses second and carries out pickling without nitric acid acidwashing liquid after first paragraph is without nitric acid acidwashing.This is second without nitre
In sour pickle, H2SO4Concentration is 18g/L, Fe3+Concentration is 8g/L, Fe2+Concentration is 20g/L, H2O2Concentration is 4g/L；This second
Temperature without nitric acid acidwashing liquid is 30 DEG C, pickling time 38s.
4) strip immerses hydrogen peroxide and cleaned after second segment is without nitric acid acidwashing.In hydrogen peroxide, H2O2Concentration is 3g/
L, temperature are 30 DEG C.
Hot rolling 409L ferritic stainless steel strip steels clean it by above-mentioned+two sections of sulfuric acid washing without nitric acid acidwashing+hydrogen peroxide
Afterwards, belt steel surface does not have remaining oxide skin, and belt steel surface finish is higher, meets No.1 class requirements.
In five~embodiment of above-described embodiment seven, it can be increased according to the different adjustment pickling times of belt steel thickness, belt steel thickness,
Accordingly increase the pickling time of each section of pickling section, belt steel thickness reduces, and accordingly reduces the pickling time of each section of pickling section.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
God any modification, equivalent substitution and improvements made etc., should be included in the scope of the protection with principle.
Claims (10)
1. a kind of hot rolling 409L ferritic stainless steels are without nitric acid acidwashing method, it is characterised in that comprise the following steps：
Pre- acid pickling step：Strip immerses pickling in pre- pickle；
First paragraph is without nitric acid acidwashing step：Strip after pre- pickling step process immerses first without in nitric acid acidwashing liquid, described
First without in nitric acid acidwashing liquid, H2SO4Concentration is 10~30g/L, Fe3+Concentration is 20~50g/L, Fe2+Concentration is 0~50g/L,
H2O2Concentration is 3~7g/L；
Second segment is without nitric acid acidwashing step：Second is immersed without nitric acid acidwashing without the strip after nitric acid acidwashing step process through first paragraph
In liquid, described second without in nitric acid acidwashing liquid, H2SO4Concentration is 10~30g/L, Fe3+Concentration is 0~20g/L, Fe2+Concentration is 0
~40g/L, H2O2Concentration is 2~5g/L.
2. hot rolling 409L ferritic stainless steels according to claim 1 are without nitric acid acidwashing method, it is characterised in that：It is described pre-
In acid pickling step, the pre- pickle is sulfuric acid pickling solution；In the sulfuric acid pickling solution, H2SO4Concentration is 150~170g/L, gold
Category ion concentration is 30~40g/L.
3. hot rolling 409L ferritic stainless steels according to claim 2 are without nitric acid acidwashing method, it is characterised in that：The sulphur
The temperature of sour pickle is 75~85 DEG C, and pre- pickling time is 25~50s.
4. hot rolling 409L ferritic stainless steels according to claim 1 are without nitric acid acidwashing method, it is characterised in that：Described
One section without nitric acid acidwashing step and second segment without in nitric acid acidwashing step, the temperature of pickle is 25~35 DEG C.
5. hot rolling 409L ferritic stainless steels according to claim 1 are without nitric acid acidwashing method, it is characterised in that：Described
One section without nitric acid acidwashing step and second segment without in nitric acid acidwashing step, pickling time is 25~50s.
6. hot rolling 409L ferritic stainless steels according to any one of claim 1 to 5 are without nitric acid acidwashing method, its feature
It is：The first paragraph is without in nitric acid acidwashing step, and described first without in nitric acid acidwashing liquid, H2SO4Concentration is 15~20g/L,
Fe3+Concentration is 30~40g/L, Fe2+Concentration is 0~35g/L, H2O2Concentration is 4~6g/L；Described first without nitric acid acidwashing liquid
Temperature is 28~33 DEG C, and pickling time is 35~42.5s.
7. hot rolling 409L ferritic stainless steels according to any one of claim 1 to 5 are without nitric acid acidwashing method, its feature
It is：The second segment is without in nitric acid acidwashing step, and described second without in nitric acid acidwashing liquid, H2SO4Concentration is 15~20g/L,
Fe3+Concentration is 0~10g/L, Fe2+Concentration is 10~30g/L, H2O2Concentration is 3~5g/L；Described second without nitric acid acidwashing liquid
Temperature is 28~33 DEG C, and pickling time is 35~42.5s.
8. hot rolling 409L ferritic stainless steels according to claim 1 are without nitric acid acidwashing method, it is characterised in that described
One prepares with the following method without nitric acid acidwashing liquid and described second without nitric acid acidwashing liquid：Into complex acid tank add the concentrated sulfuric acid and
Water is to prepare to obtain prefabricated mixed acid liquid, and the prefabricated mixed acid liquid is in pickle supply line with passing through the double of branch line addition
Oxygen water is mixed to get no nitric acid acidwashing liquid.
9. hot rolling 409L ferritic stainless steels according to claim 1 are without nitric acid acidwashing method, it is characterised in that：Through second
Section is cleaned without the strip after nitric acid acidwashing step process into cleaning section, and cleansing medium is hydrogen peroxide.
10. hot rolling 409L ferritic stainless steels according to claim 9 are without nitric acid acidwashing method, it is characterised in that：Cleaning
In medium, H2O2Concentration is 2~5g/L, and the temperature of cleansing medium is 25~35 DEG C.
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| CN107460490A (en) * | 2017-08-10 | 2017-12-12 | 武汉众登科技有限公司 | High chromium series ferritic stainless steel acid washing method in a kind of environment-friendly hot rolling |
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| CN110468442A (en) * | 2019-09-23 | 2019-11-19 | 中冶南方工程技术有限公司 | A kind of cold rolling 409L ferritic stainless steel strip steel acid cleaning process |
| CN113584493B (en) * | 2021-07-23 | 2023-02-28 | 中冶南方工程技术有限公司 | Annealing and pickling process and pickling equipment for cold-rolled stainless steel |
| CN113584498B (en) * | 2021-07-23 | 2023-02-24 | 中冶南方工程技术有限公司 | Hot-rolled stainless steel annealing and pickling process and pickling equipment |
| CN113549924B (en) * | 2021-07-23 | 2023-02-03 | 中冶南方工程技术有限公司 | Strip steel continuous pickling process and pickling equipment |
| CN113584494B (en) * | 2021-07-23 | 2023-02-03 | 中冶南方工程技术有限公司 | Low-consumption high-efficiency normalized pickling process and pickling equipment for silicon steel |
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