模拟原油废水用于煤气化渣浮选分离研究

Study of simulated crude oil wastewater for flotation separation of coal gasification slag

  • 摘要: 煤气化渣是一种典型的煤基固废,煤气化渣中残炭和灰组分的分离是实现其资源化和高值化利用的重要保障。泡沫浮选是实现煤气化渣炭灰分离最有效的方式,但存在捕收剂成本高、消耗量大的问题。原油废水含有长链烷烃、环烷烃、芳香族化合物及酚、酮、酸、酯类等物质,与煤气化渣常用捕收剂成分相似,具有应用于煤气化渣浮选分离的潜力。研究了煤气化渣的物化特性和原油的物质组成,并将模拟原油废水用于煤气化渣浮选分离,结果表明:煤气化渣中主要的物质为莫来石、硅铝酸盐、金属氧化物和不定形炭,煤气化渣中未燃炭的质量分数为25.37%;煤气化渣表面除了甲基和亚甲基外,还有丰富的含氧官能团如C—O/C=O/O—C=O等,导致煤气化渣的亲水性较强。原油中含有较多结构复杂的多环烷烃、长链烷烃和部分极性物质。多环烷烃及芳香烃对未燃炭的捕收能力强于一般正构烷烃,且极性组分的存在也有利于煤气化渣的浮选分离,因此原油具有较强的捕收能力;浮选结果表明:当搅拌速率1 800 r/min,矿浆质量浓度60 g/L,模拟原油废水质量浓度40 mg/L,起泡剂用量30 mg/L时,未燃炭回收率达84.62%,烧失量为76.82%;尾灰烧失量为4.31%,达到国家一级烧失标准( < 5%);同时模拟原油废水的除油率达到41.50%,化学需氧量由219.70 mg/L降至82.77 mg/L,达到国家石油化工工业中的二级排放标准。FTIR分析结果显示:模拟原油废水作用后,煤气化渣表明的—CH3和—OH伸缩振动峰发生了偏移,可分别判断原油分子与煤气化渣表面发生了疏水作用及氢键作用。Zeta电位结果显示:模拟原油废水作用后煤气化渣表面的电负性增强,结合XPS结果进一步表明原油中极性含氧组分与煤表面含氧官能团之间发生氢键桥连,形成了大的三维空间结构荷电体,增强煤气化渣的表面电负性。通过煤气化渣与模拟原油废水的协同处置,实现了未燃炭产品回收与原油废水治理,具有较强的工业应用价值。

     

    Abstract: Coal gasification slag is a typical coal-based solid waste, and the separation of residual unburned carbon and ash components in coal gasification slag is an important guarantee for its resourceful and high-value utilization. Flotation is the most effective way to separate unburned carbon and tailing from coal gasification slag, but facing the problem of high cost and consumption of collector. Crude oil wastewater contains substances such as long-chain alkanes, cyclic hydrocarbons, aromatic compounds, phenols, ketones, acids, and esters, which are similar to the components of commonly used collectors for coal gasification slag, has the potential to be applied to the flotation separation of coal gasification slag. In this paper, the physical and chemical properties of coal gasification slag and the material composition of crude oil were studied, and simulated crude oil wastewater was employed as a collector to investigate the flotation behavior on coal gasification slag. Results show that, the main substances in coal gasification slag are mullite, fused silica-aluminate, metal oxide and amorphous carbon. The relative content of unburned carbon in coal gasification slag is 25.37%, in addition to methyl and methylene, the surface of coal gasification slag also contains abundant oxygen-containing functional groups such as C—O/C=O/O—C=O, which makes coal gasification slag hydrophilic. Crude oil contains a large amount of structurally complex polycyclic alkanes, long-chain alkanes, and some polar substances. Polycyclic alkanes and aromatic hydrocarbons have a stronger ability to capture unburned carbon than general n-alkanes, and the presence of polar components is also conducive to the flotation separation of coal gasification slag. Therefore, crude oil has a strong collection ability; The flotation results show that, with the stirring rate of 1 800 r/min, slurry concentration of 60 g/L, crude oil wastewater concentration of 40 mg/L, and frother concentration of 30 mg/L, the recovery of unburned carbon reaches 84.62%, and the loss-on ignition of 76.82%; the tailings with loss-on ignition of 4.31%, which achieves the national level of the standard of loss-on ignition ( < 5%); Meanwhile, the oil removal rate of simulated crude oil wastewater is 41.50%, and the chemical oxygen demand is reduced from 219.70 mg/L to 82.77 mg/L, which meets the secondary discharge standard in the national petrochemical industry. The results of FTIR analysis showed that the —CH3 and —OH stretching vibration peaks indicated by the coal gasification slag were shifted after interacting with the simulated crude oil wastewater, and it could be judged that the crude oil molecules had hydrophobic interactions and hydrogen bonding interactions with the surface of the coal gasification slag, respectively. Zeta potential results shows that the electronegativity of the coal gasification slag surface is enhanced after the action of simulated crude oil wastewater. Combined with the XPS results, it further indicates that hydrogen bonding bridging occurs between the polar oxygenated compounds in the crude oil and the oxygenated functional groups on the coal surface, forming a large three-dimensional spatial structure of the charge body, which makes the surface potential of the coal gasification slag more negative. This paper realizes the recovery of carbon products and the treatment of simulated crude oil wastewater through the co-disposal of coal gasification slag and crude oil wastewater, which has strong industrial application value.

     

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