Goethite, a typical iron-containing monomineral in red mud, was synthesized under the simulated Bayer digestion condition during the alumina production. The effects of dissolved organic compounds including sodium formate, sodium acetate, sodium oxalate, sodium salicylate and disodium phthalate on the settling performance of goethite slurries were studied. The settling performance of the slurries was also investigated with the addition of self-made hydroxamated polyacrylamide flocculant （HCPAM）. The adsorption mechanism of dissolved organic compounds on the goethite surfaces was studied by FT-IR and XPS, respectively. The results show that the addition of organic compounds lowers the settling performance of the slurries and a deterioration in settling performance is observed in the order of sodium oxalate 〉 sodium salicylate （~ disodium phthalate） 〉 sodium formate 〉 sodium acetate. Moreover, HCPAM can efficiently eliminate the negative effects of sodium formate, sodium acetate and sodium oxalate on the settling performance of the goethite slurries, but it can only partially improve the settling performance of the goethite slurries containing sodium salicylate or disodium phthalate. FT-IR and XPS results show that these organic compounds are chemically adsorbed on the goethite surface.
Hydration grossular and hematite monominerals were synthesized. The effects of dissolved organic compounds(including sodium formate, sodium acetate, sodium oxalate, sodium salicylate or disodium phthalate) on the settling performance of hydration grossular or hematite slurries were studied. The settling of the slurries was also investigated with the addition of sodium polyacrylate(PAAS) or hydroxamated polyacrylamide flocculant(HCPAM). The adsorption mechanism of organic compounds on monominerals surfaces was studied by FT-IR and XPS, respectively. A deterioration in settling is observed in order of disodium phthalate>sodium salicylate>sodium oxalate>sodium formate(or sodium acetate). Moreover, PAAS can efficiently eliminate the negative effects of organic compounds on the settling performance of the hydration grossular slurry. HCPAM can efficiently eliminate the negative effects of sodium formate, sodium acetate and sodium oxalate on the settling performance of the hematite slurry, but it only partially improves the settling performance of hematite slurry containing sodium salicylate or disodium phthalate. FT-IR and XPS results show that organic compounds are physically adsorbed on hydration grossular surface, and chemisorptions of organic compounds occur on hematite surface with a bidentate chelating complex.
Suitable amounts of Al(OH)3, Na OH and synthetic hematite or goethite were taken to be digested under the simulated condition of the Bayer process and subsequently diluted with simulative Bayer red mud lotion, then the synthetic hematite or goethite suspension was obtained. The flocculation effect of self-made modified poly(acrylic acids) flocculants containing hydroxamic acid groups(abbreviated as HPAA) on the synthetic hematite or goethite suspension was studied. The experimental results show that with the increase of the dosages of added flocculants, the average settling rate of the synthetic hematite or goethite suspension in the first 1min speeds up, the supernatant solids decrease. It could also be found that there is generally a decrease in the average settling rate of the synthetic hematite or goethite suspension in the first 1 min with increasing solid content of the suspension. When the solid content of hematite or goethite of the suspension is 50 g/L with 240 g/t dosage of HPAA, HPAA has a better flocculation effect on the synthetic goethite suspension than on the synthetic hematite suspension. The adsorption mechanism of HPAA on the surface of hematite or goethite was investigated by Fourier transform infrared spectroscopy(FT-IR) and X-ray photoelectron spectroscopy(XPS).All the results suggest that HPAA is adsorbed on the hematite or goethite surface by a chemisorption, and it has a stronger adsorption on the goethite surface than on the hematite surface.
Hydroxamated polyacrylamide（HPAM） was synthesized from polyacrylamide（PAM） with high relative molecular mass under the optimum reaction conditions（p H 12 and a molar ratio of hydroxylamine to amide groups of 1.5 at 50 ℃for 12 h）. The hydroxamate groups of HPAM were verified by Fourier transform infrared spectrum（FT-IR）. 46%（molar fration） hydroxamate groups and 23%（molar fraction） carbonyl groups on HPAM were determined by conductometric titration combined with Kjeldahl＇s microanalysis method. The settling performance achieved at different flocculant dosages was investigated with high goethite-containing red mud slurry of simulated Bayer process synthesized in laboratory. It turns out that the settling performance of high goethite-containing red mud was better with HPAM. The average settling rate of red mud in the first 5 min and the turbidity of supernatant after settling for 30 min are 2.36 m/h and 507 NTU, respectively, at a flocculant dosage of 120 g/t, which is similar to that achieved with Hx-600.
采用傅里叶变换红外(FT-IR)光谱、X射线光电子能谱(XPS)以及基于周期平面波的密度泛函理论(DFT)分别研究了水杨酸钠在针铁矿或赤铁矿表面上的吸附结构,并将计算得到的光电子能谱移动(CLS)和电荷转移与实验得到的XPS结果进行对比。FT-IR结果表明,水杨酸钠可能以双齿双核(V)和双齿单核(IV)的形式分别吸附于针铁矿或赤铁矿表面。由DFT计算结果可知,水杨酸钠在针铁矿(101)晶面上形成双齿双核化合物(V)的吸附能为-5.46 e V。而水杨酸钠在针铁矿(101)晶面上形成双齿单核化合物(IV)的吸附能为3.80 e V,因此水杨酸钠在针铁矿上基本不以双齿单核化合物(IV)构型存在。水杨酸钠在赤铁矿(001)晶面上形成双齿单核化合物(IV)时吸附能为-4.07 e V,说明水杨酸钠在赤铁矿(001)晶面上形成了双齿单核化合物(IV)。另外,理论计算的针铁矿(101)晶面上吸附位点铁原子的Fe 2p的CLS值(-0.68 e V)与实验观察到的Fe 2p的CLS值(-0.5 e V)吻合。理论计算的赤铁矿(001)晶面上吸附位点铁原子的Fe 2p的CLS值(-0.80 e V)与实验观察到的Fe 2p的CLS值(-0.8 e V)吻合。因此,水杨酸钠吸附在针铁矿表面时能够通过羧酸基团上一个氧原子和酚羟基上的氧原子与针铁矿(101)表面上的两个铁原子形成双齿双核(V)结构,而在赤铁矿(001)表面上,水杨酸钠中羧酸基团上一个氧原子和酚羟基上的氧原子与赤铁矿(001)表面上的一个铁原子形成了双齿单核(IV)结构。
