高碱赤泥资源化研究及其应用
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摘要
本文对赤泥的利用划分为三个方面：一是不脱碱赤泥的直接利用；二是高碱赤泥中碱的无害化处理再利用；三是钠离子的脱除后对赤泥进行利用。并针对以上三个方面的划分进行了实验研究。
本文利用多学科交叉处理赤泥的优势,研究利用拜尔法高铁赤泥磁选后含有的Fe2O3,通过掺杂烧结工艺制备出具有红外发射率在0.9以上的粉体物料。并得出了通过联合磁选工艺：弱磁后的赤泥再进入强磁选,在不磨矿的情况下可得到品位为47.29%、回收率为20.09%的铁精粉；若磨矿后可得到品位为51.32%、回收率为22.56%的铁精粉。
本文制备了赤泥橡胶复合材料,并研究了材料的有关性能,发现,1)高碱赤泥能加快硫化、缩短硫化时间,具有显著的早强性能；2)在腐蚀性实验中,赤泥橡胶复合材料的重量变化率为-0.4%,远低于国家规定-2%的耐腐蚀标准；3)在橡胶充填中,赤泥的掺加量在30份(橡胶标准)是比较合适的。赤泥作为填料的劣势为,1)赤泥比重比较大,作为填料的无机矿物以体积充填率为准,固赤泥作为充填料在比重方面的劣势比较明显；2)赤泥颜色的问题比较突出,影响赤泥橡胶复合材料的美观度。
本文制备了赤泥硅酸盐水泥无机材料,并研究了赤泥硅酸盐水泥无机材料返碱、泛霜的机理；发现材料返碱、泛霜的机理主要由两部分组成：
一是硅酸盐水泥的主要成分是硅酸钙CaSiO3,在水化条件下,熟料会生成大量的Ca(OH)2、C3S、C2S,水化生成C-S-H凝胶体系的同时大量的游离Ca2+在水中游离与赤泥中的Na+发生取代反应,生成的NaOH在硅酸盐砂浆中破坏了水泥中钙碱与骨料的反应活性,并在一定的环境中与骨料SiO2发生化学反应造成赤泥硅酸盐水泥无机材料破坏受损；反应生成胶凝体会吸收环境中的水分而发生局部膨胀；产生破坏应力,破坏赤泥硅酸盐水泥无机材料的结合度进而产生裂纹,造成硅酸盐水泥赤泥无机材料的损坏。主要反应方程式为：
CaO+H2O→Ca(OH)2
Ca(OH)2+SiO2+H2O→C-S-H
Ca(OH)2+NanC2S→C-S-H+NaOH
2NaOH+SiO2→Na2SiO3+H2O
二是赤泥中的钠碱或盐属于离子型化合物,非常容易电离,具有很强的游离性能,很难被固化住；在潮湿的环境中会电解于水分中,Na+离子电离产生的氢氧根离子与氧化物形成胶体,向外渗透,造成赤泥硅酸盐水泥复合材的表面返碱、泛霜；主要发生的反应为：
MgSiO3+2NaOH→Mg(OH)2+Na2SiO3
CaSiO3+2NaOH→Ca(OH)2+Na2SiO3
Na2CO3+Ca(OH)2→2NaOH+CaCO3
赤泥硅酸盐水泥无机材料中的Na+碱随水迁移到材料表面的动力主要是属于毛细现象,毛细迁移高度由动力学公式H=2fcosθ/(p.r)为依据；由EDS分析明确确定了,在赤泥硅酸盐水泥无机材料内部的钠盐组分明显的聚集倍增,由无机材料中钠盐的平均含量4.5%左右增加到10.28%；造成赤泥硅酸盐水泥无机材料返碱、泛霜的严重性。
依据赤泥硅酸盐水泥无机材料返碱、泛霜的机理分析,本文使用非硅酸盐类水泥作为粘结剂研究了赤泥制品的返碱、泛霜的机理；发现使用早强水泥能够把赤泥中的碱进行固化,反应方程式为：
NaOH+MgO+H2O→Mg(OH)2+NaOH
5Mg(OH)2+MgCl2+13H2O→Mg3(OH)5(H2O)m3++5Mg(OH).MgCl2.8H2O
Mg3(OH)5(H2O)m3+Na2SiO3+NaOH→Na2Mg4SiO6(OH)2
早强水泥赤泥无机材料未出现返碱现象的主要机理为：1)固化的过程主要是镁盐的羟根与钠碱发生络合反应固结；2)早强水泥由于固化时间短,能够迅速的将浆体的流动性固结下来,降低了浆体的流动性能；硬化时间短,能够迅速的把浆体中的有害物质固结住降低其流动性能。由早强水泥赤泥无机材料的EDS分析可以很明确的得出,在早强水泥的物相中钠碱的含量为4.51%,与无机材料中加入赤泥带入钠碱的平均含量基本相同,没有发生钠碱聚集倍增的现象,赤泥中的钠碱没有发生任何的游离聚集改变,也就是钠碱在早强水泥中稳定的固化下来。依据早强水泥的固碱的机理,建立了一条早强水泥赤泥板材中试生产线。
拜尔法赤泥作为建材使用,其中高含量的钠碱是最大的危害；本文对赤泥脱碱药剂的种类进行了筛选,在四种脱钠药剂的对比试验中得出：以混合盐对赤泥的脱钠效率是最高的,主要是由于混合盐既具有镁盐的阳离子取代性能,又具有铵盐类的水解电解质分解赤泥组分的性能,能够迅速的打破赤泥浆体的电位平衡,加大脱钠效率。研究发现脱钠时间不是脱钠效率的主要影响因素；加热温度、浆体PH值对脱钠效率的影响较大。并对脱钠赤泥进行了硅酸盐返碱、泛霜的检测试验,发现随着脱碱赤泥中水泥含量的增加,试样的表面发出现返碱、泛霜现象,属于轻微返碱；说明脱碱药剂对赤泥中的碱进行部分的脱除,剩余的钠碱性质趋于稳定,对硅酸盐水泥复合材的影响减小了。
In this paper, reuse of red mud was partition into three brances:First, directive reuse of high alkaline red mud. Second, high alkaline red mud of the safe disposal and reuse. Third,red mud by the removal of sodium ions from red mud to reuse.
The paper studies red mud by the interdisciplinary advantages. Red mud with high Fe2O3,by magnetic separation of red mud, through doping CuO,NiO, can be prepared with the infrared emissivity of the powder material more than 0.9 by sintering process. And through joint weak and intensity magnetic separation after the tailings into the case without grinding grade, and results obtained 47.29%, 20.09% of the recovery of fine iron powder; if after grinding, results obtained a grade of 51.32%,22.56% of the recovery of fine iron powder.
In the paper, the physical properties of red mud is studied that red mud with pH 9.0 which can reduce the curing time, and red mud has a significant early strength properity.ln the red mud-hard rubber composite materials anti-corrosion, the maximum rate of weight change is only-0.4%. the state of anti-corrosion is much smaller than the standard anti-corrosion with red mud as the filling. In the reinforced rubber filler, the mixing amount of red mud in the 30 or so is appropriate. Red mud as an additive to rubber, with excellent corrosion resistance, compared to other corrosion resistant material; So it can be carried out in the corrosion industry, replacing the addition of red mud of light calcium. However, the disadvantages of red mud as a filler is, the larger proportion of red mud, and as the inorganic mineral filler basically subject to the volume filling ratio, so the red mud as the proportion of filling material advantage in terms of obvious disadvantages; Second, the relatively poor wear resistance of red mud.The third, color of red mud is quite conspicuous for performance of products; Fourth, the expansion of moisture absorption of red mud relatively strong, as a filling material, the red mud in a wet environment the problem of expansion in the case of the more prominent wetlands; Fifth, red mud as a filler, in the mechanical extrusion, the mixing process of wear and tear on equipment is relatively high.
The paper verified red mud products alkaline back to surface,which can be divided into two parts, Firstly, alkali-aggregate reaction is silicate, portland cement main ingredient is calcium silicate CaSiO3. In the hydration conditions, the clinker will generate a large of Ca(OH)2, C3S, C2S and generated C-S-H at the same time a large number of free Ca2+in the water free and chek occurrence of red mud in the Na+ substitution reaction of NaOH alkali cement mortar and aggregate materials in the activity of SiO2 in enough oxygen and suitable temperature infiltration catalyzed chemical reaction, resulting in product damage. alkali aggregate reaction gel condensed matter, portland cement mortar cementing experience in the absorption of water and produce localized swelling stress, damage to the combination of cement, and furthermore the cracks, resulting in damage to portland cement materials. The main reaction:
CaO+H2O→Ca(OH)2
Ca(OH)2+NanC2S→C-S-H+NaOH
2NaOH+SiO2→Na2SiO3+H2O
MgSiO3+2NaOH→Mg(OH)2+Na2SiO3
CaSiO3+2NaOH→Ca(OH)2+Na2SiO3
Na2CO3+Ca(OH)2→2NaOH+CaCO3
By the EDS analysis clearly identified in the sodium silicate components increased significantly, from 4.51% of cement increased to 10.28%.
In red mud silicate Na+base material with water to migrate to the surface of the main driving force are capillarity. Kinetic formula is H=2fcosθ/(p.r). Then portland cement as a binder for non-conducted study found that use of early strength cement during the curing process and can be due to hydroxyl radicals and sodium alkali curing molecular reaction is
NaOH+MgO+H2O→Mg(OH)2+NaOH
5Mg(OH)2+MgCl2+13H20→5Mg(OH).MgCl2.8H2O. NaOH
Early strength cement with red mud is able to solidify the sodium base which is the important reasons; early strength cement curing time is short due to the rapid mobility of the slurry will be consolidated down, reducing the flow properties of the slurry; curing time is short, can quickly put the harmful substances in the consolidation of slurry reduce the flow of the main performance. EDS from the early strength of cement can be clearly seen in the physical phase of early strength cement, sodium content of 4.51% alkali, and the original red mud in the alkali content of sodium without any change in the sodium alkali early strength cement in a stable curing down.
Bayer Red Mud'alkaline is the most damaging, red mud off the alkaline of the types of agents were studied on four contrast agents sodium. sodium mixed salt removal efficiency is the highest. The complexation properties of both a magnesium salt, but also has strong electrolyte ammonium salt hydrolysis class performance, red mud can quickly break the balance, removing Na+efficiency. Removing Na+removal time is not the main factors affecting the efficiency of the heating temperature, PH value of slurry of sodium removal efficiency greatly. With the removal of red mud in cement alkali content increases, the surface of the sample that returned to base, the pan-cream phenomenon belonging to a minor, showing that alkaline sodium silicate remaining reduce the impact of cement products.
本文利用多学科交叉处理赤泥的优势,研究利用拜尔法高铁赤泥磁选后含有的Fe2O3,通过掺杂烧结工艺制备出具有红外发射率在0.9以上的粉体物料。并得出了通过联合磁选工艺：弱磁后的赤泥再进入强磁选,在不磨矿的情况下可得到品位为47.29%、回收率为20.09%的铁精粉；若磨矿后可得到品位为51.32%、回收率为22.56%的铁精粉。
本文制备了赤泥橡胶复合材料,并研究了材料的有关性能,发现,1)高碱赤泥能加快硫化、缩短硫化时间,具有显著的早强性能；2)在腐蚀性实验中,赤泥橡胶复合材料的重量变化率为-0.4%,远低于国家规定-2%的耐腐蚀标准；3)在橡胶充填中,赤泥的掺加量在30份(橡胶标准)是比较合适的。赤泥作为填料的劣势为,1)赤泥比重比较大,作为填料的无机矿物以体积充填率为准,固赤泥作为充填料在比重方面的劣势比较明显；2)赤泥颜色的问题比较突出,影响赤泥橡胶复合材料的美观度。
本文制备了赤泥硅酸盐水泥无机材料,并研究了赤泥硅酸盐水泥无机材料返碱、泛霜的机理；发现材料返碱、泛霜的机理主要由两部分组成：
一是硅酸盐水泥的主要成分是硅酸钙CaSiO3,在水化条件下,熟料会生成大量的Ca(OH)2、C3S、C2S,水化生成C-S-H凝胶体系的同时大量的游离Ca2+在水中游离与赤泥中的Na+发生取代反应,生成的NaOH在硅酸盐砂浆中破坏了水泥中钙碱与骨料的反应活性,并在一定的环境中与骨料SiO2发生化学反应造成赤泥硅酸盐水泥无机材料破坏受损；反应生成胶凝体会吸收环境中的水分而发生局部膨胀；产生破坏应力,破坏赤泥硅酸盐水泥无机材料的结合度进而产生裂纹,造成硅酸盐水泥赤泥无机材料的损坏。主要反应方程式为：
CaO+H2O→Ca(OH)2
Ca(OH)2+SiO2+H2O→C-S-H
Ca(OH)2+NanC2S→C-S-H+NaOH
2NaOH+SiO2→Na2SiO3+H2O
二是赤泥中的钠碱或盐属于离子型化合物,非常容易电离,具有很强的游离性能,很难被固化住；在潮湿的环境中会电解于水分中,Na+离子电离产生的氢氧根离子与氧化物形成胶体,向外渗透,造成赤泥硅酸盐水泥复合材的表面返碱、泛霜；主要发生的反应为：
MgSiO3+2NaOH→Mg(OH)2+Na2SiO3
CaSiO3+2NaOH→Ca(OH)2+Na2SiO3
Na2CO3+Ca(OH)2→2NaOH+CaCO3
赤泥硅酸盐水泥无机材料中的Na+碱随水迁移到材料表面的动力主要是属于毛细现象,毛细迁移高度由动力学公式H=2fcosθ/(p.r)为依据；由EDS分析明确确定了,在赤泥硅酸盐水泥无机材料内部的钠盐组分明显的聚集倍增,由无机材料中钠盐的平均含量4.5%左右增加到10.28%；造成赤泥硅酸盐水泥无机材料返碱、泛霜的严重性。
依据赤泥硅酸盐水泥无机材料返碱、泛霜的机理分析,本文使用非硅酸盐类水泥作为粘结剂研究了赤泥制品的返碱、泛霜的机理；发现使用早强水泥能够把赤泥中的碱进行固化,反应方程式为：
NaOH+MgO+H2O→Mg(OH)2+NaOH
5Mg(OH)2+MgCl2+13H2O→Mg3(OH)5(H2O)m3++5Mg(OH).MgCl2.8H2O
Mg3(OH)5(H2O)m3+Na2SiO3+NaOH→Na2Mg4SiO6(OH)2
早强水泥赤泥无机材料未出现返碱现象的主要机理为：1)固化的过程主要是镁盐的羟根与钠碱发生络合反应固结；2)早强水泥由于固化时间短,能够迅速的将浆体的流动性固结下来,降低了浆体的流动性能；硬化时间短,能够迅速的把浆体中的有害物质固结住降低其流动性能。由早强水泥赤泥无机材料的EDS分析可以很明确的得出,在早强水泥的物相中钠碱的含量为4.51%,与无机材料中加入赤泥带入钠碱的平均含量基本相同,没有发生钠碱聚集倍增的现象,赤泥中的钠碱没有发生任何的游离聚集改变,也就是钠碱在早强水泥中稳定的固化下来。依据早强水泥的固碱的机理,建立了一条早强水泥赤泥板材中试生产线。
拜尔法赤泥作为建材使用,其中高含量的钠碱是最大的危害；本文对赤泥脱碱药剂的种类进行了筛选,在四种脱钠药剂的对比试验中得出：以混合盐对赤泥的脱钠效率是最高的,主要是由于混合盐既具有镁盐的阳离子取代性能,又具有铵盐类的水解电解质分解赤泥组分的性能,能够迅速的打破赤泥浆体的电位平衡,加大脱钠效率。研究发现脱钠时间不是脱钠效率的主要影响因素；加热温度、浆体PH值对脱钠效率的影响较大。并对脱钠赤泥进行了硅酸盐返碱、泛霜的检测试验,发现随着脱碱赤泥中水泥含量的增加,试样的表面发出现返碱、泛霜现象,属于轻微返碱；说明脱碱药剂对赤泥中的碱进行部分的脱除,剩余的钠碱性质趋于稳定,对硅酸盐水泥复合材的影响减小了。
In this paper, reuse of red mud was partition into three brances:First, directive reuse of high alkaline red mud. Second, high alkaline red mud of the safe disposal and reuse. Third,red mud by the removal of sodium ions from red mud to reuse.
The paper studies red mud by the interdisciplinary advantages. Red mud with high Fe2O3,by magnetic separation of red mud, through doping CuO,NiO, can be prepared with the infrared emissivity of the powder material more than 0.9 by sintering process. And through joint weak and intensity magnetic separation after the tailings into the case without grinding grade, and results obtained 47.29%, 20.09% of the recovery of fine iron powder; if after grinding, results obtained a grade of 51.32%,22.56% of the recovery of fine iron powder.
In the paper, the physical properties of red mud is studied that red mud with pH 9.0 which can reduce the curing time, and red mud has a significant early strength properity.ln the red mud-hard rubber composite materials anti-corrosion, the maximum rate of weight change is only-0.4%. the state of anti-corrosion is much smaller than the standard anti-corrosion with red mud as the filling. In the reinforced rubber filler, the mixing amount of red mud in the 30 or so is appropriate. Red mud as an additive to rubber, with excellent corrosion resistance, compared to other corrosion resistant material; So it can be carried out in the corrosion industry, replacing the addition of red mud of light calcium. However, the disadvantages of red mud as a filler is, the larger proportion of red mud, and as the inorganic mineral filler basically subject to the volume filling ratio, so the red mud as the proportion of filling material advantage in terms of obvious disadvantages; Second, the relatively poor wear resistance of red mud.The third, color of red mud is quite conspicuous for performance of products; Fourth, the expansion of moisture absorption of red mud relatively strong, as a filling material, the red mud in a wet environment the problem of expansion in the case of the more prominent wetlands; Fifth, red mud as a filler, in the mechanical extrusion, the mixing process of wear and tear on equipment is relatively high.
The paper verified red mud products alkaline back to surface,which can be divided into two parts, Firstly, alkali-aggregate reaction is silicate, portland cement main ingredient is calcium silicate CaSiO3. In the hydration conditions, the clinker will generate a large of Ca(OH)2, C3S, C2S and generated C-S-H at the same time a large number of free Ca2+in the water free and chek occurrence of red mud in the Na+ substitution reaction of NaOH alkali cement mortar and aggregate materials in the activity of SiO2 in enough oxygen and suitable temperature infiltration catalyzed chemical reaction, resulting in product damage. alkali aggregate reaction gel condensed matter, portland cement mortar cementing experience in the absorption of water and produce localized swelling stress, damage to the combination of cement, and furthermore the cracks, resulting in damage to portland cement materials. The main reaction:
CaO+H2O→Ca(OH)2
Ca(OH)2+NanC2S→C-S-H+NaOH
2NaOH+SiO2→Na2SiO3+H2O
MgSiO3+2NaOH→Mg(OH)2+Na2SiO3
CaSiO3+2NaOH→Ca(OH)2+Na2SiO3
Na2CO3+Ca(OH)2→2NaOH+CaCO3
By the EDS analysis clearly identified in the sodium silicate components increased significantly, from 4.51% of cement increased to 10.28%.
In red mud silicate Na+base material with water to migrate to the surface of the main driving force are capillarity. Kinetic formula is H=2fcosθ/(p.r). Then portland cement as a binder for non-conducted study found that use of early strength cement during the curing process and can be due to hydroxyl radicals and sodium alkali curing molecular reaction is
NaOH+MgO+H2O→Mg(OH)2+NaOH
5Mg(OH)2+MgCl2+13H20→5Mg(OH).MgCl2.8H2O. NaOH
Early strength cement with red mud is able to solidify the sodium base which is the important reasons; early strength cement curing time is short due to the rapid mobility of the slurry will be consolidated down, reducing the flow properties of the slurry; curing time is short, can quickly put the harmful substances in the consolidation of slurry reduce the flow of the main performance. EDS from the early strength of cement can be clearly seen in the physical phase of early strength cement, sodium content of 4.51% alkali, and the original red mud in the alkali content of sodium without any change in the sodium alkali early strength cement in a stable curing down.
Bayer Red Mud'alkaline is the most damaging, red mud off the alkaline of the types of agents were studied on four contrast agents sodium. sodium mixed salt removal efficiency is the highest. The complexation properties of both a magnesium salt, but also has strong electrolyte ammonium salt hydrolysis class performance, red mud can quickly break the balance, removing Na+efficiency. Removing Na+removal time is not the main factors affecting the efficiency of the heating temperature, PH value of slurry of sodium removal efficiency greatly. With the removal of red mud in cement alkali content increases, the surface of the sample that returned to base, the pan-cream phenomenon belonging to a minor, showing that alkaline sodium silicate remaining reduce the impact of cement products.
引文
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