热轧带钢紊流酸洗关键技术的研究
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摘要
酸洗是冷轧带钢生产过程中一道重要的工艺,酸洗质量的好坏很大程度上决定着带钢表面的质量。为提高带钢表面的质量,在轧制前必须将带钢表面的氧化皮通过紊流酸洗工艺加以去除。酸洗质量的优劣取决于带钢酸洗过程中的各个因素,如酸洗液的温度、浓度、带钢的运动速度、喷射梁喷射流量、喷射角度、氧化皮的剥离方式等。这其中的研究理论涉及到冲击射流理论,化学反应动力学,湍流扩散理论和对流传热理论。以往对酸洗研究的方法主要以试验为主,将试验结果拟合成经验公式,或通过大量的现场试验和酸洗槽内的流态模拟建立紊流酸洗的模型,模型以控制为主,并无明确的数学表达式,也没有考虑实际酸洗过程中气泡的剥离作用和带钢运动时带钢表面受射流冲击的传热和传质,而这些因素与酸洗效率有着直接的关系。因此,研究酸洗各因素对带钢表面的氧化皮的溶解速率、氢气泡的生成、气泡对氧化皮的剥离以及带钢表面的传热传质机理都对提高酸洗效率有至关重要的作用。
本文以带钢紊流酸洗作为研究对象,提出采用酸洗电位导数首零法来判定酸洗终点时间。采用此方法测定的酸洗终点时间与Hudson的酸洗经验公式具有很好的吻合性,验证了导数首零法判定酸洗终点时间的可靠性和可行性。精确控制酸洗终点时间可以避免过酸洗,而过酸洗会加重氢对钢材基体渗入,从而引起材料的性能发生改变,甚至使钢材发生氢脆。
对不同酸洗时间点的钢板试样进行金相分析,观测氧化皮截面随酸洗时间的变化关系,得出了酸液是从氧化皮表面薄弱的或者较易溶解的位置开始渗入内层,初始酸洗核的数量也成为酸洗效率的因素之一,为酸洗模型的建立做了铺垫。在此基础上,首次引入湍流传质系数和对流传热理论,并结合氧化皮与酸液的接触面积、酸液温度和浓度建立了带钢表面氧化皮溶解的数学模型。研究表明,对于经过破鳞的氧化皮,酸洗时间与初始氧化皮的面积以及传质系数和反应系数的倒数和成正比,而与酸液浓度和破鳞度成反比。而对于未破鳞的氧化皮,酸洗时间还与酸洗初期酸洗核的形成有关。
试验研究典型结构和成分的氧化皮在不同酸液温度、浓度和破鳞度下带钢表面氧化皮的形貌变化和氢气泡的增长规律,得到不同条件下气泡生成时间、气泡数目变化、难溶于酸的氧化皮初始剥离时间和剥离时氧化皮颗粒的尺寸。基于理想气体状态方程,假定单位时间内基体溶解的摩尔数等于氢气泡生成的摩尔数,研究气泡在基体表面的生长和脱离理论机理,建立了气泡直径与氧化皮厚度、氧化皮溶解速率、基体溶解速率、酸液温度和浓度之间的关系,并理论推导了气泡脱离和氧化皮剥离的条件。
用湍动能来表征氢离子的传质系数,计算了各酸洗参数对运动带钢表面湍动能的分布影响,并结合实际紊流酸洗槽,分析了各酸洗参数对带钢表面湍动能的影响程度。研究表明,当入射角为45°,带钢运动速度与入射速度值相同且运动方向与入射角方向相反时,能在滞止点处获得最大的湍动能。入射流量及喷射角度主要影响酸槽入口区域带钢表面流态和湍流强度分布,而其在酸槽内部的分布主要由带钢运动速度决定。
结合射流理论简化酸槽结构,采用雷诺应力模型,VOF模型和SIMPLIC算法对带钢在酸洗槽中的表面对流传热系数和引起的带钢温升进行了固气液三相耦合计算,得到了酸洗工艺参数对带钢表面努赛尔数分布和带钢温升速率的影响。
本文建立的带钢表面氧化皮溶解理论和气泡剥离理论对紊流酸洗工艺都具有一定的指导意义,对今后酸洗工艺的发展和优化提供了理论支撑和试验依据。
Steel acid pickling is an improtant technique in the process of cold-rolled strip production and the quality of the strip surface is heavily reliant upon the pickling process. In the process of steel strip production, oxide scale on the strip surface should be removed in turbulent acid pickling process so as to improve the quality of strip surface. The quality of acid pickling is determined by the parameters such as acid temperature, acid concentration, the strip speed, acid injection flow rate, the incident angle, and the peeling behaviors of the scale.
The turbulent acid pickling theory relates to jet impinging theory, chemical reaction kinetics, turbulent diffusion theory and convective heat transfer theory. However, previous studies on acid pickling were mainly aimed at testing whose results were fit to empirical formula or a acid pickling control model set up on the basis of a large number of trials and flow simulation in the acid pickling tank. Mathematical expression for turbulent acid pickling, the peeling effect of the hydrogen bubble generated by the reaction between the steel base and hydrochloric acid and the heat and mass transfer characteristic of the impingment moving strip, which play a great role in improving pickling efficiency, have not been investigated. Therefore, the investigation of each pickling parameter is essential to master the mechanism of heat and mass transfer and the bubble growth.
In this research, turbulent acid pickling for steel strip is investigated. The method of first zero potential differential value which base on electrochemistry is put forward to determin the endpoint of acid pickling. The pickling time determined by the method of first zero potential differential value is well consonant with the emprical formula done by Hudson, which verifies the reliability and feasibility of the new method. Besides, the precise control of the pickling can avoid overpickling. The overpickling of the steel will increase the penetrability of hydrogen to the steel matrix and change the material properties of the steel strip, even to cause hydrogen embrittlement.
Morphology change of the typical oxide scale with time is analysed to observe the change of the cross section of the oxide scale. It follows that the acid penetrates the inner of the scale from the position of weak or soluble surface. Besides, the number of initial pickling core is also an important factor to affect the picling efficiency. Based on this, the theory of chemical reaction dynamics and heat transfer combines with the parameters such as acid temperature, acid concentration, chemical reaction rate, concentration diffusion upon the strip and the contact area between the acid and oxide scale to build a mathematical model of the dissolution of oxide scale. The results show that for scale-breaking strip, the pickling time is proportional to initial area of the scale and reciprocal sum of the mass transfer coefficient and chemical reaction coefficient, and is inversely proportional to the acid concentration and the degree of the sacle breaking. Apart from above paremeters, for the unscale-breaking strip, the pickling time even has a relationship with the formation of the pickling nucleus.
Laws of the hydrogen bubble growing are investigated under different acid temperature, acid concentration and the degree of the scale breaking to obtain the initial time of bubble formation, changes in the number of bubbles, initial time of oxide removal and size of the detached scale for the scale which is difficult to dissolve in acid.
Assumed that the number of moles of strip base diffusion is equal to the number of moles of bydrogen bubbles generation, a theoretical bubble growing and peeling model which bases on the state equation of ideal gas is established to determine the relationship among the diameter of the bubble, thickness of the scale, dissolution rate of the scale, dissolution rate of the strip base, acid temperature and acid concentration. Based on this, the requirements of the bubble detachment and the scale removal are theoretically determined.
The turbulent kinetic energy distribution on the moving strip surface which represents the hydrogen ion diffusion coefficient is computed under different pickling parameters. Moreover, the effect of pickling parameters on the turbulent kinetic energy distribution upon the strip surface are computed to measure the degree of those parameters on the convective mass transfer of strip surface. The simulation revels that the maximal turbulent kinetic energy is obtained under the condition that the jet angle is45°when the moving direction of the strip opposites to the jet inclination. Flow rate and jet angle determine the flow state and turbulent kinetic energy in the entrance of the pickling tank, however, the speed of the moving strip determines flow state and turbulent kinetic energy in the inner of the tank.
Finally, the initial temperature of the steel strip is found to have a great effect on the acid pickling efficiency. Temperature rise of the steel strip in still acid is theoretically analyzed. The Reynolds stress turbulence model and VOF model solved sequentially by the SIMPLIC method are used to do the solid-liquid coupling calculation of the heat transfer upon the steel strip and temperature rise of the strip in the turbulent pickling tank to obtain the influence of pickling process parameters on the Nusselt number distribution and temperature rise of the strip.
The achievements of this research are beneficial to turbulent pickling process, and supply helpful theoretical and experimental guides to further process development and optimization.
本文以带钢紊流酸洗作为研究对象,提出采用酸洗电位导数首零法来判定酸洗终点时间。采用此方法测定的酸洗终点时间与Hudson的酸洗经验公式具有很好的吻合性,验证了导数首零法判定酸洗终点时间的可靠性和可行性。精确控制酸洗终点时间可以避免过酸洗,而过酸洗会加重氢对钢材基体渗入,从而引起材料的性能发生改变,甚至使钢材发生氢脆。
对不同酸洗时间点的钢板试样进行金相分析,观测氧化皮截面随酸洗时间的变化关系,得出了酸液是从氧化皮表面薄弱的或者较易溶解的位置开始渗入内层,初始酸洗核的数量也成为酸洗效率的因素之一,为酸洗模型的建立做了铺垫。在此基础上,首次引入湍流传质系数和对流传热理论,并结合氧化皮与酸液的接触面积、酸液温度和浓度建立了带钢表面氧化皮溶解的数学模型。研究表明,对于经过破鳞的氧化皮,酸洗时间与初始氧化皮的面积以及传质系数和反应系数的倒数和成正比,而与酸液浓度和破鳞度成反比。而对于未破鳞的氧化皮,酸洗时间还与酸洗初期酸洗核的形成有关。
试验研究典型结构和成分的氧化皮在不同酸液温度、浓度和破鳞度下带钢表面氧化皮的形貌变化和氢气泡的增长规律,得到不同条件下气泡生成时间、气泡数目变化、难溶于酸的氧化皮初始剥离时间和剥离时氧化皮颗粒的尺寸。基于理想气体状态方程,假定单位时间内基体溶解的摩尔数等于氢气泡生成的摩尔数,研究气泡在基体表面的生长和脱离理论机理,建立了气泡直径与氧化皮厚度、氧化皮溶解速率、基体溶解速率、酸液温度和浓度之间的关系,并理论推导了气泡脱离和氧化皮剥离的条件。
用湍动能来表征氢离子的传质系数,计算了各酸洗参数对运动带钢表面湍动能的分布影响,并结合实际紊流酸洗槽,分析了各酸洗参数对带钢表面湍动能的影响程度。研究表明,当入射角为45°,带钢运动速度与入射速度值相同且运动方向与入射角方向相反时,能在滞止点处获得最大的湍动能。入射流量及喷射角度主要影响酸槽入口区域带钢表面流态和湍流强度分布,而其在酸槽内部的分布主要由带钢运动速度决定。
结合射流理论简化酸槽结构,采用雷诺应力模型,VOF模型和SIMPLIC算法对带钢在酸洗槽中的表面对流传热系数和引起的带钢温升进行了固气液三相耦合计算,得到了酸洗工艺参数对带钢表面努赛尔数分布和带钢温升速率的影响。
本文建立的带钢表面氧化皮溶解理论和气泡剥离理论对紊流酸洗工艺都具有一定的指导意义,对今后酸洗工艺的发展和优化提供了理论支撑和试验依据。
Steel acid pickling is an improtant technique in the process of cold-rolled strip production and the quality of the strip surface is heavily reliant upon the pickling process. In the process of steel strip production, oxide scale on the strip surface should be removed in turbulent acid pickling process so as to improve the quality of strip surface. The quality of acid pickling is determined by the parameters such as acid temperature, acid concentration, the strip speed, acid injection flow rate, the incident angle, and the peeling behaviors of the scale.
The turbulent acid pickling theory relates to jet impinging theory, chemical reaction kinetics, turbulent diffusion theory and convective heat transfer theory. However, previous studies on acid pickling were mainly aimed at testing whose results were fit to empirical formula or a acid pickling control model set up on the basis of a large number of trials and flow simulation in the acid pickling tank. Mathematical expression for turbulent acid pickling, the peeling effect of the hydrogen bubble generated by the reaction between the steel base and hydrochloric acid and the heat and mass transfer characteristic of the impingment moving strip, which play a great role in improving pickling efficiency, have not been investigated. Therefore, the investigation of each pickling parameter is essential to master the mechanism of heat and mass transfer and the bubble growth.
In this research, turbulent acid pickling for steel strip is investigated. The method of first zero potential differential value which base on electrochemistry is put forward to determin the endpoint of acid pickling. The pickling time determined by the method of first zero potential differential value is well consonant with the emprical formula done by Hudson, which verifies the reliability and feasibility of the new method. Besides, the precise control of the pickling can avoid overpickling. The overpickling of the steel will increase the penetrability of hydrogen to the steel matrix and change the material properties of the steel strip, even to cause hydrogen embrittlement.
Morphology change of the typical oxide scale with time is analysed to observe the change of the cross section of the oxide scale. It follows that the acid penetrates the inner of the scale from the position of weak or soluble surface. Besides, the number of initial pickling core is also an important factor to affect the picling efficiency. Based on this, the theory of chemical reaction dynamics and heat transfer combines with the parameters such as acid temperature, acid concentration, chemical reaction rate, concentration diffusion upon the strip and the contact area between the acid and oxide scale to build a mathematical model of the dissolution of oxide scale. The results show that for scale-breaking strip, the pickling time is proportional to initial area of the scale and reciprocal sum of the mass transfer coefficient and chemical reaction coefficient, and is inversely proportional to the acid concentration and the degree of the sacle breaking. Apart from above paremeters, for the unscale-breaking strip, the pickling time even has a relationship with the formation of the pickling nucleus.
Laws of the hydrogen bubble growing are investigated under different acid temperature, acid concentration and the degree of the scale breaking to obtain the initial time of bubble formation, changes in the number of bubbles, initial time of oxide removal and size of the detached scale for the scale which is difficult to dissolve in acid.
Assumed that the number of moles of strip base diffusion is equal to the number of moles of bydrogen bubbles generation, a theoretical bubble growing and peeling model which bases on the state equation of ideal gas is established to determine the relationship among the diameter of the bubble, thickness of the scale, dissolution rate of the scale, dissolution rate of the strip base, acid temperature and acid concentration. Based on this, the requirements of the bubble detachment and the scale removal are theoretically determined.
The turbulent kinetic energy distribution on the moving strip surface which represents the hydrogen ion diffusion coefficient is computed under different pickling parameters. Moreover, the effect of pickling parameters on the turbulent kinetic energy distribution upon the strip surface are computed to measure the degree of those parameters on the convective mass transfer of strip surface. The simulation revels that the maximal turbulent kinetic energy is obtained under the condition that the jet angle is45°when the moving direction of the strip opposites to the jet inclination. Flow rate and jet angle determine the flow state and turbulent kinetic energy in the entrance of the pickling tank, however, the speed of the moving strip determines flow state and turbulent kinetic energy in the inner of the tank.
Finally, the initial temperature of the steel strip is found to have a great effect on the acid pickling efficiency. Temperature rise of the steel strip in still acid is theoretically analyzed. The Reynolds stress turbulence model and VOF model solved sequentially by the SIMPLIC method are used to do the solid-liquid coupling calculation of the heat transfer upon the steel strip and temperature rise of the strip in the turbulent pickling tank to obtain the influence of pickling process parameters on the Nusselt number distribution and temperature rise of the strip.
The achievements of this research are beneficial to turbulent pickling process, and supply helpful theoretical and experimental guides to further process development and optimization.
引文
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