JP5813417B2 - Method and apparatus for managing pickling solution - Google Patents

Description

  The present invention relates to a pickling solution management method and apparatus, and in particular, even in the case where a plurality of pickling tanks for continuously treating a metal strip are provided in the direction of the steel strip, the pickling solution The acid concentration and dissolved metal ion concentration can be measured quickly and optically on the surface of the steel plate after pickling without causing clogging of the sampling pipe due to the pickling solution. The present invention relates to a pickling solution management method and apparatus capable of producing a stainless steel plate having no scale residue.

  In order to remove oxides present on the surface of a stainless steel strip or the like, conventionally, pickling is generally performed continuously using a pickling solution containing sulfuric acid, nitric acid, hydrofluoric acid and the like. In this pickling method, the pickling ability depends on the acid concentration and temperature constituting the pickling solution.

  Further, when the stainless steel strip is continuously pickled with the pickling solution, metal ions such as Fe ions and Cr ions are eluted from the surface of the stainless steel strip as it is pickled. Accordingly, the acid concentration in the pickling solution decreases with the elution of these metal ions, so that the pickling ability of the pickling solution decreases.

  For this reason, it is necessary to periodically measure the acid concentration in the pickling solution and replenish the pickling solution with acid to prevent a drop in the pickling performance of the pickling solution and to ensure a certain level of pickling performance. There is.

  Conventionally, the following analytical methods are known as methods for periodically measuring the acid concentration in the pickling solution. For example, in order to obtain the nitric acid concentration in a mixed acid of nitric acid and hydrofluoric acid, first, the total acid concentration of the pickling solution is obtained by neutralization titration, and then the method is obtained by subtracting the hydrofluoric acid concentration from the total acid concentration. , Known as the main method. As the latter analysis method of hydrofluoric acid concentration, for example, Patent Document 1 describes an iron acetylacetone complex fading absorbance method, and Patent Document 2 describes an analysis method by an ion electrode method.

  Moreover, although not used for the management of the pickling solution of the metal steel strip, Patent Documents 3 to 5 propose a technique for managing the liquid by combining the near-infrared spectroscopic analysis with multivariate analysis.

Japanese Patent Application Laid-Open No. 07-294509 Japanese Patent Laid-Open No. 05-263279 JP 2000-187031 A JP 2000-105231 A JP-A-11-194124

  However, in the prior art described in Patent Documents 1 and 2, when the consumption of nitric acid or hydrofluoric acid is large, such as when a large amount of stainless steel strip is pickled continuously, the concentration of nitric acid and hydrofluoric acid The measurement takes time, so that the pickling solution cannot be adjusted quickly and appropriately, and there is a problem in that each acid concentration falls outside the lower limit of the control range and causes pickling failure.

  Moreover, since an acid may be added excessively so that the pickling ability does not fall below the lower limit of the control range, an excessive pickling may occur, resulting in high costs.

  Furthermore, in the process analysis in the steel production field, an accurate value of the acid concentration may not always be necessary, and it is sufficient if a certain correlation between the analysis value and the acid concentration is clear. In the ion electrode method, the correlation is likely to be shifted depending on the amount of metal contained in the mixed acid.

  Further, in the technique described in Patent Document 2, the analysis of hydrofluoric acid concentration is rapid because the ion electrode method is used, but the neutralization titration method is used for the analysis of nitric acid concentration. In addition, it takes time to obtain both values of hydrofluoric acid concentration, and there is a problem that it is inferior in rapidity.

  Furthermore, the ion electrode method is superior in speediness compared to the neutralization titration method and the iron acetylacetone complex fading absorbance method. There was also a problem that analysis accuracy deteriorated due to the influence of metal ions.

  In addition, the pickling tank is usually provided with three tanks of sulfuric acid, sulfuric acid, and mixed acid, for example, along the plate passing direction of the steel strip. The length of one tank is about 20 m, and the entire three tanks are 70 to 80 m. Due to the length, even if the analysis chamber is provided, for example, near the central second tank, it is at a position several tens of meters away from the first tank and the third tank on both sides. Therefore, it is necessary to transport the analysis solution to the analysis chamber away from the pickling tank by sampling piping, so that clogging of the piping occurs due to the formation of precipitates due to a decrease in the liquid temperature, and the metal strip is processed continuously. In many cases, line stoppages occurred.

  On the other hand, measuring the spectrum in the near infrared region of the absorbance described in Patent Documents 3 to 5 and performing multivariate analysis on the spectrum has not been performed for pickling solutions in the steel field. . This is because the liquid itself contains a solid suspended matter, which has a large influence on the absorbance, and the influence of the presence of various coexisting elements was unknown.

The present invention, wherein those so has been made to solve the conventional problems, rapidly analyzed on-line by both optical means of various acid concentrations and dissolved metal ion concentration in the pickling solution to continuously process the metal strip It is an object of the present invention to make it possible to constantly control both the acid concentration and the dissolved metal ion concentration within the optimum concentration range quickly according to the analysis result.

  In order to solve such a problem, the inventors have made it difficult to significantly reduce the analysis time in the conventional analysis of acid concentration using a wet analysis method or an ion electrode method. As a result of extensive research, the present invention has been achieved.

In the present invention, the pickling solution is sampled from the pickling tank that continuously treats the metal strip, is passed continuously or in a predetermined cycle through a filter for removing suspended solids in the solution, and the sampled solution is Measure the absorbance of the absorbance in the near-infrared region, or the absorbance at a plurality of predetermined wavenumbers or wavelengths, create a calibration curve by performing multivariate analysis on the obtained absorbance, and use the calibration curve. A method for managing a pickling solution, wherein both the acid concentration and the dissolved metal ion concentration in the sampled solution are calculated, and both the acid concentration and the dissolved metal ion concentration are constantly controlled within a predetermined concentration range according to the calculation result. Thus, the problem is solved. Here, the wave number means the reciprocal of the wavelength.

The present invention also includes a sampling means for sampling the pickling solution from the pickling tank that continuously treats the metal strip , passing through a filter for removing suspended solids in the solution continuously or in a predetermined cycle, For the sampled solution, a continuous spectrum of absorbance in the near-infrared region, or an absorbance measuring means for measuring absorbance at a plurality of predetermined wave numbers or wavelengths, and performing a multivariate analysis on the obtained absorbance to obtain a calibration curve analyzing means for creating, by using a calibration curve, both a predetermined concentration of the acid concentration and the dissolved metal ion concentration in accordance with the concentration calculation means for calculating sampled the acid concentration and the dissolved metal ion concentration in the liquid together, the calculation result The present invention provides a pickling solution management device comprising a control means for always controlling the range.

Here, the pore diameter of the filter can be 20 μm or more and 30 μm or less.

  Further, the sampled pickling solution can pass through the filter only at the time of measuring the absorbance.

  Further, a plurality of the pickling tanks can be provided in the passing direction of the metal strip.

  According to the present invention, a pickling solution for continuously treating a metal band by measuring a continuous spectrum of absorbance in the near-infrared region or measuring absorbance at a plurality of predetermined wave numbers or wavelengths and performing multivariate analysis. It is now possible to quickly analyze the acid concentration and metal ion concentration online, so that the pickling solution can be adjusted quickly and appropriately, and pickling failure due to out of control range of the acid concentration Is greatly reduced, and stable scale removal becomes possible. Therefore, it is possible to produce a stainless steel plate having no scale residue on the steel plate surface after pickling.

The block diagram which shows the principal part of 1st Embodiment of the manufacturing process of the stainless steel plate by which this invention is implemented. The figure which shows the filter of 1st Embodiment. Figure showing the same analysis cell The figure which also shows a near-infrared analyzer Trend graph of total acid concentration in examples of the present invention Similarly, trend graph of Fe concentration Trend graph of total acid concentration by conventional method using wet analysis method Similarly, trend graph of Fe concentration The block diagram which shows the principal part of 2nd Embodiment of the manufacturing process of the stainless steel plate by which this invention is implemented. The figure which shows the analysis cell of 2nd Embodiment

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

  In FIG. 1, the manufacturing process of the stainless steel plate by which 1st Embodiment of this invention was employ | adopted is shown.

  In the figure, the hot-rolled sheet is passed through the first tank 11, the second tank 12, and the third tank 13, which are pickling tanks. Under the 1st tank 11, the 2nd tank 12, and the 3rd tank 13, the circulation tanks 21, 22, and 23 of the volume of each tank are each provided, and the circulation piping 31, 32, 33, pump (P) 41, 42, 43, heat exchangers 51, 52, 53, the pickling solution is at a predetermined temperature (for example, the first tank 11 and the second tank 12 is 80 ° C., the third tank 13 is 60 ° C. (Centigrade) while maintaining circulation. Then, when an abnormality occurs in each of the tanks 11, 12, and 13, the pickling liquid in each of the tanks 11, 12, and 13 is naturally circulated by gravity by stopping the operation of the pumps 41, 42, and 43. , 22 and 23 are accommodated.

  The circulation tanks 21, 22, and 23 are provided with sampling pipes 61, 62, and 63, respectively. In addition, for example, quartz analysis cells (also referred to as quartz cells) 71, 72, and 73 are connected to each other.

  Filters 81, 82, and 83 are provided on the inlet sides of the analysis cells 71, 72, and 73 of the sampling pipes 61, 62, and 63, respectively.

  The pickling tanks 11, 12, and 13 include, for example, sulfuric acid tanks 11 and 12 and a mixed acid tank (nitric acid + hydrofluoric acid) 13. The total acid is sulfuric acid concentration in the sulfuric acid tanks 11 and 12, and nitric acid concentration in the mixed acid tank 13. And the sum of hydrofluoric acid concentrations.

  As the filters 81, 82, 83, for example, as shown in FIG. 2, a filter having a configuration in which a liquid is injected from the periphery of a cylindrical filter element 81a and a filtrate is taken out from the center can be used. In the figure, 81b is a filter case.

  The filter element 81a can be made of, for example, polypropylene.

  Here, bypass pipes 65, 66, and 67 are provided in the middle of the sampling pipes 61, 62, and 63 so that the pickling solution is allowed to flow through the filters 81, 82, and 83 only during the analysis. , 82 and 83 can be made hard to occur.

  Further, as the analysis cells 71, 72, 73, for example, as shown in FIG. 3, light is applied to the side surface of the sample (pickling solution) introduced into the cylindrical measurement cell 71a from below and discharged from above. Things can be used.

  The measurement cell 71a is made of, for example, a fluororesin, and PFA (tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer), sapphire, Kalrez, or the like can be used as the liquid contact material.

  Further, as the near-infrared analyzer 70, as shown in FIG. 4 for example, only one system including the analysis cell 71, a near-infrared light source 74, an interferometer 76, and light detection capable of measuring light in the near-infrared region. A device provided with a vessel 78 can be used. The light emitted from the light source 74 is guided to the analysis cell 71, irradiates the pickling solution in the analysis cell 71, and the light transmitted therethrough is guided to the photodetector 78. At this time, in the absorbance spectrum measurement, it is general to measure the absorbance corresponding to the wave number, but it is also possible to measure and apply the absorbance corresponding to the wavelength. What is necessary is just to select suitably according to measurement conditions.

In the near-infrared analyzer 70, for example, using a method similar to that described in Patent Documents 3 to 5, a continuous spectrum of absorbance in the near-infrared region or a plurality (for example, 2 to 10 points) of predetermined spectra. Multivariate analysis is performed using absorbance at wave number or wavelength, and at the same time, acid concentration and metal ion concentration are analyzed. This near-infrared spectrum measurement and multivariate analysis can be completed in a few minutes, so the analysis time can be greatly shortened.As a result, the acid concentration can be adjusted quickly, and the acid concentration The pickling failure due to out-of-control is greatly reduced, and stable scale removal becomes possible.

  Table 1 shows the results of experiments using near-infrared rays on the pore sizes of the filters 81, 82, and 83.

The pickling solution of the sulfuric acid tank that is actually operating is sampled, and the spectrum in the wave number region of 4800 to 11500 cm ^-1 is obtained under the measurement conditions where the liquid temperature is 80 ° C. and the near-infrared transmission distance in the analysis cell is 1 mm Measurements were conducted and the optimum filter diameter was examined. At this time, if the absorbance at a wave number of 11000 cm ⁻¹ not used in the variable analysis is 0.50 or less, the solid suspended matter in the liquid has no effect on the absorbance in the wave number region used for the multivariate analysis. It was judged that it was possible. Further, filter clogging was visually confirmed. If the liquid did not flow due to clogging, the mark was x. If there was clogging but liquid was flowing, the mark was o.

  As is apparent from Table 1, it was found that the absorbance can be analyzed without causing filter clogging when the filter pore diameter is 20 μm or more and 30 μm or less.

  In a stainless steel plate manufacturing facility having a configuration as shown in FIG. 1, the pickling solution of the stainless steel plate was analyzed, and trends were evaluated by the method of the present invention and the conventional method. At this time, the control range of all acids is 5 to 8 [au], and Fe is 6 [au] or less. Further, the filters 81, 82, and 83 have a pore diameter of 20 to 30 μm based on the experimental results, and the solid suspended matter in the sampling solution is removed. The spectrum measurement in the near infrared region was performed for about 1 minute.

Trend graphs of total acid concentration and Fe concentration by the method of the present invention are shown in FIGS. 5 and 6, respectively. In the examples according to the method of the present invention, the analysis interval was measured at 10 minutes. As a result, the acid concentration and the Fe concentration can be quickly adjusted, and both the total acid concentration and the Fe concentration can be constantly controlled within the control range.

On the other hand, trend graphs of total acid concentration and Fe concentration by a conventional method using a wet analysis method are shown in FIGS. 7 and 8, respectively. Since the conventional method requires at least one hour of analysis time, the analysis interval in the comparative example is one hour. As a result, it is difficult to adjust both of the acid concentration and the Fe concentration, and the total acid concentration and the Fe concentration are out of the management range.

As described above, according to the present invention, it is possible to speed up the analysis when continuously pickling a metal strip, the acid concentration and the Fe concentration can be easily maintained in the control range, and the control concentration of the pickling solution It was possible to prevent the pickling failure of the steel strip due to detachment.

  In the first embodiment, the sampling pipes 61, 62, 63 are connected to the circulation tanks 21, 22, 23, but can be directly connected to the pickling tanks 11, 12, 13.

  Next, a second embodiment of the present invention will be described with reference to FIG.

  In the present embodiment, the filters 81, 82, 83 and the analysis cells 71, 72, 73 are provided in the vicinity of the pickling tanks 11, 12, 13, respectively, and the analysis cells 71, 72 using the optical fibers 91, 92, 93 are used. , 73 are guided to a near-infrared analyzer 70 provided in the analysis chamber 100.

  The analysis cell of this embodiment is shown in FIG. The light emitted from the light source 74 as illustrated in FIG. 4 is guided to the analysis cell 71 by one of the pair of optical fibers 91a, irradiates the pickling solution in the analysis cell 71, and the light transmitted therethrough is The other end 91b of the optical fiber leads to the photodetector 78.

  In the present embodiment, an analysis sample is sampled by filtering the pickling solution through the filters 81, 82, 83 in the vicinity of the pickling tanks 11, 12, 13. In the analysis cells 71, 72, 73 installed in the vicinity, the passing light is detected. The detection light at this time is guided by optical fibers 91, 92, 93 to a near-infrared analyzer 70 placed in the analysis chamber 100, for example, several meters to several hundred meters away from the pickling tanks 11, 12, 13. Then, a continuous spectrum of absorbance in the near infrared region, or absorbance at a plurality of predetermined wave numbers or wavelengths (for example, 2 to 10 points) is measured.

  Since other points are the same as those in the first embodiment, description thereof will be omitted.

  According to the present embodiment, analysis can be quickly performed with a small number of near-infrared analyzers 70. It is also possible to provide a near-infrared analyzer for each analysis cell.

  Further, the number of predetermined wave numbers or wavelengths is not limited to 2 to 10 points.

  In the said embodiment, although this invention was applied to the manufacturing process of a stainless steel plate, the application object of this invention is not limited to this.

DESCRIPTION OF SYMBOLS 11, 12, 13 ... Pickling tank 61, 62, 63 ... Sampling piping 65, 66, 67 ... Bypass piping 70 ... Near-infrared analyzer 71, 72, 73 ... Analysis cell 74 ... Light source for near-infrared generation 76 ... Interferometer 78 ... Photodetector 81, 82, 83 ... Filter

Claims (8)

Sampling of the pickling solution from the pickling tank that continuously treats the metal strip is performed continuously or at a predetermined cycle by passing through a filter for removing suspended solids in the solution ,
For the sampled liquid, measure the continuous spectrum of absorbance in the near infrared region, or the absorbance at a plurality of predetermined wave numbers or wavelengths,
Perform a multivariate analysis on the obtained absorbance to create a calibration curve,
Using the calibration curve, calculate both the acid concentration and the dissolved metal ion concentration in the sampled solution,
A pickling solution management method, wherein both the acid concentration and the dissolved metal ion concentration are constantly controlled within a predetermined concentration range according to the calculation result. 2. The pickling solution management method according to claim 1 , wherein a pore diameter of the filter is 20 μm or more and 30 μm or less. The sampled pickling solution, how to manage pickling solution according to claim 1 or 2, characterized in that it has to pass through the filter only when absorbance measurement. Management of pickling solution according to any one of claims 1 to 3, characterized in that the pickling tanks is provided with a plurality in the passing direction of the metal strip. Sampling means for sampling the pickling solution from the pickling tank for continuously treating the metal strip, passing through a filter for removing suspended solids in the solution continuously or at a predetermined cycle,
Absorbance measurement means for measuring the absorbance at a plurality of predetermined wave numbers or wavelengths for the sampled liquid, or a continuous spectrum of absorbance in the near-infrared region,
An analysis means for performing a multivariate analysis on the obtained absorbance to create a calibration curve;
Concentration calculation means for calculating both the acid concentration and the dissolved metal ion concentration in the sampled liquid using the calibration curve;
A control means for constantly controlling both the acid concentration and the dissolved metal ion concentration within a predetermined concentration range according to the calculation result;
An apparatus for managing pickling solution. 6. The pickling solution management device according to claim 5 , wherein a pore diameter of the filter is 20 μm or more and 30 μm or less. The pickling solution management device according to claim 5 or 6 , wherein the sampled pickling solution passes through the filter only at the time of measuring absorbance. The pickling solution management device according to any one of claims 5 to 7 , wherein a plurality of the pickling tanks are provided in a direction in which the metal strip passes.

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