氧化铝熟料制备的基础理论和工艺
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摘要
理论上烧结法铝硅分离彻底,氧化铝回收率可达100%,是高效处理我国中低品位铝土矿的主要方法。而熟料烧结工序是铝酸钠和硅酸钙生成、铝硅分离的关键工序,传统熟料烧结因钙比高、氧化铝含量较低,导致其能耗和生产成本高。针对我国铝土矿资源～80%属中低品位铝土矿的现状,在熟料烧结过程中,通过设计高稳定性低钙比硅酸钙,提高熟料中氧化铝含量,以降低烧结能耗和生产成本。因此,深入研究熟料烧结中组份反应机理和相互间影响规律以及开发低钙比熟料烧结工艺显得尤为重要。
本文通过热力学计算,借助于热分析技术,结合物相分析,研究了熟料烧结过程中铝、硅、铁等反应规律和相互影响规律,通过分析熟料中组份的溶出率,评价熟料烧结中各因素的影响规律,提出熟料烧结过程中生料浆配方和烧结工艺。结合工业实验和产业化,优化了熟料烧结工艺。主要研究结论如下：
1.热力学计算结果表明：无论Na2O·Al203、Na2O·Al203·2Si02,还是Na2O·Fe203和2CaO·Fe2O3在高温度下均可生成。同时铁酸钠可与硅酸钙反应生成硅酸钠钙,但铁酸钙与铝酸钠难以反应生成铁铝酸钙。在CaO-SiO2系或Al2O3-CaO-SiO2系中,钙量充足的条件下,各种硅酸钙均可生成；钙比和烧结温度影响各硅酸钙物相的生成。当[CaO]:[SiO2]=3:2时,在CaO-SiO2系最可能生成的化合物为3CaO·2Si02;在Na2O-Al203-CaO-SiO2系中可生成3CaO·2SiO2,同时3CaO·2Si02和2CaO-SiO2可与Na2O·Al2O3稳定存在。
2.在非等温条件下,Na2CO3-Al2O3、Na2C03-AlOOH、Na2CO3-Al2O3·2SiO2、Na2CO3-Al2O3·2SiO2·2H2O、Na2C03-Fe2O3、Na2O·A203-Fe2O3和Na2O·Al2O3·2SiO2-CaO系组份的反应动力学机理均符合Jander模型,反应由二维或三维扩散控制,可表示为[1-(1-x)1/3]2=Ae-Ea/RTt或1-(2/3)x-(l-x)2/3=Ae-Ea/RTt; Na2CO3与A1203在650～970℃温度段间反应活化能(268.0kJ/mol)大于Na2CO3与Fe203反应活化能(99.20kJ/mol),铝硅酸钠与氧化钙反应生成硅酸钙在780～800℃反应活化能为189.29kJ/mol, Na2O·Fe2O3与A12O3反应的活化能为246.37kJ/mol上述反应模型均获实验证明。
3.实验研究结果表明,无论是二元体系或多元体系,钙比减小,烧结温度升高,烧成时间延长,加入矿化剂等均可提高氧化钙的反应率,减少游离氧化钙量,有利于低钙比硅酸钙的生成。同时,在较低烧结温度下,Na2CO3与Fe203反应生成Na2O-Fe2O3的反应速率比Na2CO3与A12O3反应生成Na2O·Al2O3的反应速率大。在高温下,Fe2O3的存在有利于促进Na2CO3与A12O3的反应速率。同时,获得了熟料烧结的炉料配方和烧结工艺条件：碱比为1,钙比为1.5,铁铝比～0.1,烧成温度在1250～1300℃间,烧成时间30min左右。此时熟料中氧化铝溶出率大于95%,碱溶出率大于98%。该工艺条件适用中低品位铝土矿的熟料烧结。
4.工业试验结果表明,实验结果与小实验结果一致。优化后的工艺指标为：(1)生料浆制备：H2O<40%,碱比[N]/([A]+[F])1.02土0.04,钙比[C]/[S]1.5土0.05, A/S 7.5-7.8;(2)熟料烧结：A/S 7.0-7.4,[N]/([A]+[F])0.9-0.98,[C]/[S]1.3土0.05,容重0.9-1.15,ηA标>95%ηN标>97%。
5.在工业应用过程中,提出提高窑皮挂结温度、缩短挂结时间挂窑皮方案,采用偏上限温度控制的思路进行窑皮维护,以长火焰操作、控制火焰落着点、控制窑尾温度等控制窑内温度,调整喷煤管位置,始终保持火焰中心与料层距离1.5米的喷煤管调整方法,从而提出了适当增强前风、拉大后风、长火焰操作以调整系统温度制度,保证熟料窑作业稳定高产。
6.熟料烧结新技术应用后,在同等条件下,相对于传统烧结法,工艺能耗降低39.9%,单台窑产能增加70%,窑龄由100天提高到200多天；在相同产量情况下,中州分公司可节省大量的原煤和石灰石,减少赤泥和CO2排放。
As alumina can be separated from silica thoroughly in the sintering process and thus the extraction of alumina can reach 100% theoretically, the sintering process is a very important technology to deal with the medium or even low grade diasporic bauxite in China alumina industry. The sintering operation is the key to the formation of sodium aluminate and calcium silicate, The energy consumption and production cost is high by the traditional sintering process with high mole ratio of calcium oxide to silica and low alumina content. As for the-80% of Chinese diasporic bauxite with high silica, the objective of saving energy greatly and reducing production cost significantly may come into true by controlling the species of calcium silicate, strengthening the stability of calcium silicate, increasing the content of alumina in sinter, So the studies on the reaction mechanism of components and the influencing law among the components in the sintering process are of great importance to improve the sintering technology with low molar ratio of calcium oxide to silica ([C]/[S]).
By means of thermodynamic calculation, thermal analysis and XRD analysis, the reaction rule of alumina, silica and iron oxide, as well as the influencing principle of the components were systematically investigated in this work. And the influence of factors on the sintering process was assessed by the extraction of alumina, sodium oxide and silica. Then the formula for the raw material slurry and the sintering technology was proposed. Finally, the proposed sintering technology was optimized based on the results of industrial scale experiments and industrial alumina production. The main conclusions were listed as follows.
1. Thermodynamic calculation shows that Na2O-Al2O3 and Na2O·Al203-2Si02, as well as Na2O·Fe203 and 2CaO·Fe2O3, can be formed at elevated temperatures; that calcium sodium silicate can be formed by the reaction of sodium ferrite and calcium silicate, while calcium iron aluminate can not be formed by the reaction of calcium ferrite and sodium aluminate; that all kinds of calcium silicates may be formed in CaO-SiO2 system or Al2O3-CaO-SiO2 system when the lime is sufficient, and [C]/[S] and sintering temperature affect the formation of calcium silicate species; and that 3CaO·2Si02 is the most possible species in CaO-SiO2 system when [C]/[S] is 1.5. In contrast, in addition to 2CaO·Si02,3CaO·2SiO2 may be formed in Na20-Al2O3-CaO-SiO2 system with [C]/[S] of 1.5, and 2CaO·Si02 and 3CaO·2Si02 can not readily react with Na2O·Al203.
2. All the reaction kinetic equations of components in Na2CO3-Al2O3, Na2CO3-AlOOH,Na2CO3-Al2O3·2SiO2, Na2CO3-Al2O3-2SiO2·2H2O, Na2CO3-Fe2O3, Na2O-Al2O3-Fe2O3 and Na2O·Al2O3·2SiO2-CaO system correspond with the Jander model, being controlled by two-dimension or three- dimension diffusion, and can be expressed as [1-(1-x)1/3]2=Ae-Ea/RTt or 1-(2/3)x-(1-x)2/3=Ae-Ea/RTt. The apparent activation energy of the reaction of Na2CO3 and Al2O3(268.0kJ/mol) is larger than that of the reaction of Na2CO3 and Fe2O3 (99.20kJ/mol) at the temperature range from 650℃to 970℃, and the activation energy of the reaction of sodium aluminosilicate and calcium oxide, where calcium silicate can be formed, is 189.29kJ/mol at the temperature range from 780℃to 800℃. The activation energy of reaction between Na2O·Fe203 and AI2O3 is 246.37kJ/mol. The experiments prove the models above are reasonable.
3. The conclusions obtained by the experiment results can be made as following: the reaction rate of calcium oxide can be improved by reducing [C]/[S], increasing the sintering temperature and sintering duration time, and adding mineralizer in two-element systems or mutil-element systems, favoring the formation of calcium silicate with low [C]/[S]. The reaction rate of Na2CO3 with Fe2O3 is larger than that of Na2CO3 with Al2O3 at relatively low sintering temperature. The reaction rate of Na2CO3 and Al2O3 can be accelerated with the present of Fe2O3 at elevated sintering temperature. Based on the experimental research results, the favorable formula for the charge and the detailed sintering technological parameters being suitable for the sintering operations of diasporic bauxite with high silica are determined:molar ratio of Na2O to the sum of A12O3 and Fe2O3 ([N]/([A]+[F])) of 1, [C]/[S] of 1.5, molar ratio of Fe2O3 to Al2O3 ([F]/[A]) of about 0.1, sintering temperature at the range of 1250℃～1300℃, sintering duration time of approximate 30min. The leaching rate of Al2O3 and Na2O exceeds 95% and 98%, respectively, under the above sintering conditions. This technology applies to sintering process of high-silica diasporic bauxite.
4. The results of industrial experiments are consistent with those of the laboratorial experiments. The optimized technological parameters are as follows:1) the preparation of raw material slurry:[N]/([A]+[F]) 1.02±0.04, [C]/[S] 1.5±0.05, mass ratio of alumina to silica(A/S) 7.5-7.8, H2O<40%; (2) the sinter:A/S 7.0-7.4, [N]/([A]+[F]) 0.9-0.98, [C]/[S] 1.3±0.05, bulk density 0.9-1.15,ηAstandard>95%,ηN standard>97%.
5. In the industrial applications, the measures to form kiln skin are proposed by increasing the sintering temperature, decreasing the sintering duration time and maintaining the kiln skin at upper temperature limit. Maintaining stability of the sintering operation and improving productivity of the sintering rotary kiln need to control the temperature and regulate the temperature system in the kiln, by regulating the amount of the first and second wind to form long-flame operation, controlling kiln tail temperature, modifying the coal-spraying gun positon to maintain the distance from the flame center to the charge of 1.5 meter.
6. After applying the new sintering technology in Zhongzhou Branch, Chalco, comparing with the traditional sintering process, there was a reduction of 39.9% and an increase of 70% in the technological energy consumption and the production capacity of single rotary kiln, respectively. In addition, the lifespan of the liner in rotary kiln increased from 100 days to 200 days. This means that the enterprise can greatly reduce the consumption of raw materials of coal and limestones, and thus obviously reduce the emission of CO2 and the discharge of red mud to the environment with the same annual alumina yields.
本文通过热力学计算,借助于热分析技术,结合物相分析,研究了熟料烧结过程中铝、硅、铁等反应规律和相互影响规律,通过分析熟料中组份的溶出率,评价熟料烧结中各因素的影响规律,提出熟料烧结过程中生料浆配方和烧结工艺。结合工业实验和产业化,优化了熟料烧结工艺。主要研究结论如下：
1.热力学计算结果表明：无论Na2O·Al203、Na2O·Al203·2Si02,还是Na2O·Fe203和2CaO·Fe2O3在高温度下均可生成。同时铁酸钠可与硅酸钙反应生成硅酸钠钙,但铁酸钙与铝酸钠难以反应生成铁铝酸钙。在CaO-SiO2系或Al2O3-CaO-SiO2系中,钙量充足的条件下,各种硅酸钙均可生成；钙比和烧结温度影响各硅酸钙物相的生成。当[CaO]:[SiO2]=3:2时,在CaO-SiO2系最可能生成的化合物为3CaO·2Si02;在Na2O-Al203-CaO-SiO2系中可生成3CaO·2SiO2,同时3CaO·2Si02和2CaO-SiO2可与Na2O·Al2O3稳定存在。
2.在非等温条件下,Na2CO3-Al2O3、Na2C03-AlOOH、Na2CO3-Al2O3·2SiO2、Na2CO3-Al2O3·2SiO2·2H2O、Na2C03-Fe2O3、Na2O·A203-Fe2O3和Na2O·Al2O3·2SiO2-CaO系组份的反应动力学机理均符合Jander模型,反应由二维或三维扩散控制,可表示为[1-(1-x)1/3]2=Ae-Ea/RTt或1-(2/3)x-(l-x)2/3=Ae-Ea/RTt; Na2CO3与A1203在650～970℃温度段间反应活化能(268.0kJ/mol)大于Na2CO3与Fe203反应活化能(99.20kJ/mol),铝硅酸钠与氧化钙反应生成硅酸钙在780～800℃反应活化能为189.29kJ/mol, Na2O·Fe2O3与A12O3反应的活化能为246.37kJ/mol上述反应模型均获实验证明。
3.实验研究结果表明,无论是二元体系或多元体系,钙比减小,烧结温度升高,烧成时间延长,加入矿化剂等均可提高氧化钙的反应率,减少游离氧化钙量,有利于低钙比硅酸钙的生成。同时,在较低烧结温度下,Na2CO3与Fe203反应生成Na2O-Fe2O3的反应速率比Na2CO3与A12O3反应生成Na2O·Al2O3的反应速率大。在高温下,Fe2O3的存在有利于促进Na2CO3与A12O3的反应速率。同时,获得了熟料烧结的炉料配方和烧结工艺条件：碱比为1,钙比为1.5,铁铝比～0.1,烧成温度在1250～1300℃间,烧成时间30min左右。此时熟料中氧化铝溶出率大于95%,碱溶出率大于98%。该工艺条件适用中低品位铝土矿的熟料烧结。
4.工业试验结果表明,实验结果与小实验结果一致。优化后的工艺指标为：(1)生料浆制备：H2O<40%,碱比[N]/([A]+[F])1.02土0.04,钙比[C]/[S]1.5土0.05, A/S 7.5-7.8;(2)熟料烧结：A/S 7.0-7.4,[N]/([A]+[F])0.9-0.98,[C]/[S]1.3土0.05,容重0.9-1.15,ηA标>95%ηN标>97%。
5.在工业应用过程中,提出提高窑皮挂结温度、缩短挂结时间挂窑皮方案,采用偏上限温度控制的思路进行窑皮维护,以长火焰操作、控制火焰落着点、控制窑尾温度等控制窑内温度,调整喷煤管位置,始终保持火焰中心与料层距离1.5米的喷煤管调整方法,从而提出了适当增强前风、拉大后风、长火焰操作以调整系统温度制度,保证熟料窑作业稳定高产。
6.熟料烧结新技术应用后,在同等条件下,相对于传统烧结法,工艺能耗降低39.9%,单台窑产能增加70%,窑龄由100天提高到200多天；在相同产量情况下,中州分公司可节省大量的原煤和石灰石,减少赤泥和CO2排放。
As alumina can be separated from silica thoroughly in the sintering process and thus the extraction of alumina can reach 100% theoretically, the sintering process is a very important technology to deal with the medium or even low grade diasporic bauxite in China alumina industry. The sintering operation is the key to the formation of sodium aluminate and calcium silicate, The energy consumption and production cost is high by the traditional sintering process with high mole ratio of calcium oxide to silica and low alumina content. As for the-80% of Chinese diasporic bauxite with high silica, the objective of saving energy greatly and reducing production cost significantly may come into true by controlling the species of calcium silicate, strengthening the stability of calcium silicate, increasing the content of alumina in sinter, So the studies on the reaction mechanism of components and the influencing law among the components in the sintering process are of great importance to improve the sintering technology with low molar ratio of calcium oxide to silica ([C]/[S]).
By means of thermodynamic calculation, thermal analysis and XRD analysis, the reaction rule of alumina, silica and iron oxide, as well as the influencing principle of the components were systematically investigated in this work. And the influence of factors on the sintering process was assessed by the extraction of alumina, sodium oxide and silica. Then the formula for the raw material slurry and the sintering technology was proposed. Finally, the proposed sintering technology was optimized based on the results of industrial scale experiments and industrial alumina production. The main conclusions were listed as follows.
1. Thermodynamic calculation shows that Na2O-Al2O3 and Na2O·Al203-2Si02, as well as Na2O·Fe203 and 2CaO·Fe2O3, can be formed at elevated temperatures; that calcium sodium silicate can be formed by the reaction of sodium ferrite and calcium silicate, while calcium iron aluminate can not be formed by the reaction of calcium ferrite and sodium aluminate; that all kinds of calcium silicates may be formed in CaO-SiO2 system or Al2O3-CaO-SiO2 system when the lime is sufficient, and [C]/[S] and sintering temperature affect the formation of calcium silicate species; and that 3CaO·2Si02 is the most possible species in CaO-SiO2 system when [C]/[S] is 1.5. In contrast, in addition to 2CaO·Si02,3CaO·2SiO2 may be formed in Na20-Al2O3-CaO-SiO2 system with [C]/[S] of 1.5, and 2CaO·Si02 and 3CaO·2Si02 can not readily react with Na2O·Al203.
2. All the reaction kinetic equations of components in Na2CO3-Al2O3, Na2CO3-AlOOH,Na2CO3-Al2O3·2SiO2, Na2CO3-Al2O3-2SiO2·2H2O, Na2CO3-Fe2O3, Na2O-Al2O3-Fe2O3 and Na2O·Al2O3·2SiO2-CaO system correspond with the Jander model, being controlled by two-dimension or three- dimension diffusion, and can be expressed as [1-(1-x)1/3]2=Ae-Ea/RTt or 1-(2/3)x-(1-x)2/3=Ae-Ea/RTt. The apparent activation energy of the reaction of Na2CO3 and Al2O3(268.0kJ/mol) is larger than that of the reaction of Na2CO3 and Fe2O3 (99.20kJ/mol) at the temperature range from 650℃to 970℃, and the activation energy of the reaction of sodium aluminosilicate and calcium oxide, where calcium silicate can be formed, is 189.29kJ/mol at the temperature range from 780℃to 800℃. The activation energy of reaction between Na2O·Fe203 and AI2O3 is 246.37kJ/mol. The experiments prove the models above are reasonable.
3. The conclusions obtained by the experiment results can be made as following: the reaction rate of calcium oxide can be improved by reducing [C]/[S], increasing the sintering temperature and sintering duration time, and adding mineralizer in two-element systems or mutil-element systems, favoring the formation of calcium silicate with low [C]/[S]. The reaction rate of Na2CO3 with Fe2O3 is larger than that of Na2CO3 with Al2O3 at relatively low sintering temperature. The reaction rate of Na2CO3 and Al2O3 can be accelerated with the present of Fe2O3 at elevated sintering temperature. Based on the experimental research results, the favorable formula for the charge and the detailed sintering technological parameters being suitable for the sintering operations of diasporic bauxite with high silica are determined:molar ratio of Na2O to the sum of A12O3 and Fe2O3 ([N]/([A]+[F])) of 1, [C]/[S] of 1.5, molar ratio of Fe2O3 to Al2O3 ([F]/[A]) of about 0.1, sintering temperature at the range of 1250℃～1300℃, sintering duration time of approximate 30min. The leaching rate of Al2O3 and Na2O exceeds 95% and 98%, respectively, under the above sintering conditions. This technology applies to sintering process of high-silica diasporic bauxite.
4. The results of industrial experiments are consistent with those of the laboratorial experiments. The optimized technological parameters are as follows:1) the preparation of raw material slurry:[N]/([A]+[F]) 1.02±0.04, [C]/[S] 1.5±0.05, mass ratio of alumina to silica(A/S) 7.5-7.8, H2O<40%; (2) the sinter:A/S 7.0-7.4, [N]/([A]+[F]) 0.9-0.98, [C]/[S] 1.3±0.05, bulk density 0.9-1.15,ηAstandard>95%,ηN standard>97%.
5. In the industrial applications, the measures to form kiln skin are proposed by increasing the sintering temperature, decreasing the sintering duration time and maintaining the kiln skin at upper temperature limit. Maintaining stability of the sintering operation and improving productivity of the sintering rotary kiln need to control the temperature and regulate the temperature system in the kiln, by regulating the amount of the first and second wind to form long-flame operation, controlling kiln tail temperature, modifying the coal-spraying gun positon to maintain the distance from the flame center to the charge of 1.5 meter.
6. After applying the new sintering technology in Zhongzhou Branch, Chalco, comparing with the traditional sintering process, there was a reduction of 39.9% and an increase of 70% in the technological energy consumption and the production capacity of single rotary kiln, respectively. In addition, the lifespan of the liner in rotary kiln increased from 100 days to 200 days. This means that the enterprise can greatly reduce the consumption of raw materials of coal and limestones, and thus obviously reduce the emission of CO2 and the discharge of red mud to the environment with the same annual alumina yields.
引文
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