基于石油焦的浆体燃料制备及特性研究
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摘要
利用石油焦制备水焦浆,能够拓宽代油和气化燃料的原料范围,应对烟煤供应紧张的难题。水焦浆具有成浆浓度高、热值高、灰分低等特点,可以代油、代气、代煤燃烧,亦可作为气化原料,为大规模高效清洁煤气化技术提供原料基础。我国燃料型石油焦的产量逐年递增,水焦浆技术可以实现石油焦的清洁高效利用,但其较差的稳定性制约了水焦浆的发展和应用,改善水焦浆的稳定性是一个亟待解决的关键问题。
本文以提高水焦浆的品质为目的,研究了水焦浆的特性及其影响因素,提出了改善水焦浆稳定性的几种方法,主要进行了以下工作：
采用多种石油焦、多种添加剂制备水焦浆,深入研究了水焦浆的成浆性、流变性和稳定性。结果表明,石油焦的成浆性良好,定粘浓度普遍在70%左右;随着粒径分布范围的变宽和平均粒径的变大,石油焦的成浆性变好；水焦浆的定粘浓度与石油焦的内水分和灰分均成反比,且内水分对定粘浓度的反作用效果较大；随着比表面积和总孔容的减小,成浆性提高；石油焦的强疏水性表面特性,有利于成浆浓度的提高,但易使水焦浆呈现“剪切变稠”的胀流性特征,且具有较差的稳定性。
研究了各种灰分对水焦浆稳定性的影响。结果表明,加入少量CaO能有效提高水焦浆的稳定性,当CaO的添加质量为石油焦干基质量的0.3%时,可以制得定粘浓度为68.0%、定粘流动特征指数为0.78、定粘析水率为3.4%的高品质水焦浆。
选用褐煤和污泥分别与石油焦共成浆,研究了煤焦比(或污泥含量)对浆体表面特性及浆体品质的影响。结果表明,随着煤焦比(或污泥含量)的增加,一方面浆体表面张力变大,成浆性变差,另一方面Zeta电位绝对值增加,稳定性变好,假塑性增强；褐煤焦浆(或污泥焦浆)的稳定性与假塑性正相关,与成浆性负相关；当煤焦比为1：4时,可以制得定粘浓度大于65%、定粘流动特征指数约0.9、定粘析水率约4%的褐煤焦浆；当污泥含量为6%时,可以制得定粘浓度约64%、定粘流动特征指数小于0.8、定粘析水率约5%的污泥焦浆,是浓度较高、稳定性较好、假塑性特征较强的高品质浆体燃料。
研制气泡水焦浆以期改善水焦浆的稳定性,分别采用单一因素分析法和多因素多水平的正交试验法研究了浆体制备过程中各因素对稳定性的影响。结果表明,吹气时间、起泡剂用量和浆体浓度对气泡水焦浆稳定性的影响十分显著,而起泡剂种类和布风板孔径大小的影响较弱；获得最佳稳定性的操作条件是：吹气时间为30min,成浆浓度为65%,起泡剂用量为0.030%,布风板孔径为2～5μm,起泡剂种类为AOS。在此最优条件下,气泡水焦浆的倒出率可达96%以上,比同等条件下的纯水焦浆(无气泡)提高了约80个百分点,稳定性大大改善,且浆体的流动特征指数在0.8左右,假塑性特征明显。
在实验研究基础上,分析了气泡水焦浆形成的微观作用机理。结果发现,气泡的生成主要依赖起泡剂的加入,起泡剂存在一个最佳用量；气泡在浆体中最稳定的状态就是以气固联合体的形式存在,气固联合体的形成存在碰撞、黏附和脱附三个微观过程；气泡直径越小,浆体微湍流强度越大,颗粒与气泡间的碰撞概率越高；颗粒表面疏水性越强,接触角越大,越易黏附在气泡上
Preparation of petroleum-coke-water-slurry (PCWS) can broaden scope of raw materials of fuel of oil substitute and gasification, and settle problem of tension supply of bituminous coal. PCWS, which has high solid concentration, high heat value and low ash content, can burn instead of oil, gas and coal, also can provide raw materials of large-scale efficient clean coal gasification technology. The production of fuel type petroleum coke increases year by year in China. The technology of PCWS can achieve high efficient and clean utilization of petroleum coke, but the bad stability restricts development and application of PCWS. It's important to improve stability of PCWS.
In order to improve the quality of PCWS, this paper studies properties of PCWS and its influencing factors, and puts forward methods of improving the stability. The main work is carried out as follows:
Many types of petroleum cokes and additives are used for PCWS whose slurryability, rheological characteristics and stability are investigated. Results show that petroleum cokes have good slurryability with solid concentration being about70%generally. The slurryability is enhanced with increasing particle size distribution range and average particle size, and with decreasing specific surface area and pore volume. The solid concentration is inversely proportional to inherent moisture content and ash content of the petroleum coke, and the inherent moisture content is more adverse. Surface characteristic of petroleum coke is strong hydrophobicity, which is in favor of enhancing the concentration and makes PCWS be dilatant and unstable fluid easily.
The effect of various kinds of ash on the stability of PCWS is researched. Results show that the stability can be improved effectively by adding a small amount of CaO. When the adding quality of CaO is0.3%of dry basis petroleum coke, PCWS has high performance, whose concentration is68.0%, flow characteristic index is0.78, and drainage rate is3.4%at fixed viscosity.
The influence of ratio of coal and coke (or sludge content) on surface characteristic of slurries prepared with petroleum coke and lignite or sludge is studied. Results show that surface tension and Zeta potential absolute value increase, and stability and pseudoplasticity enhance, but slurryability goes worse, with increasing ratio of coal and coke (or sludge content). The stability is positively related to the pseudoplasticity and negatively related to the slurryability. When the ratio of coal and coke is1:4, lignite coke slurry has high performance, whose concentration is above65%, flow characteristic index is about0.9, and drainage rate is about4%at fixed viscosity. When the sludge content is6%, sludge coke slurry also has high performance, whose concentration is about64%, flow characteristic index is less than0.8, and drainage rate is about5%at fixed viscosity.
Bubble-petroleum-coke-water-slurry (BPCWS) is prepared to improve stability of PCWS. The influence of various factors in the preparation process on the stability is studied by single factor analysis and multiple factors orthogonal method respectively. Results show that the effects of blowing time, foaming agent dosage and solid concentration on the stability are very significant, while the effects of foaming agent type and ventilation panel aperture size are slight. The operating conditions of obtaining the best stability are blowing for30min, concentration being65%, foaming agent dosage being0.030%,2～5μm aperture size and AOS. Under the optimal conditions, pouring rate of BPCWS is more than96%, which increases by about80percentage points compared with pure PCWS (no bubbles). The BPCWS has good stability and obvious pseudoplasticity with flow characteristic index being about0.8.
On the basis of experimental research, the microscopic mechanism of BPCWS is analysed. Results show that bubble formation depends mainly on the foaming agent which has an optimum dosage. The most stable form of bubbles in slurry is gas-solid-union forming through collision, adhesion and desorption. The collision probability between particles and bubbles is enhanced with decreasing bubble diameter, and with increasing microturbulence intensity. The stronger the hydrophobicity of particle surface, the larger the contact angle, the more easily the particles adhere to the bubbles.
本文以提高水焦浆的品质为目的,研究了水焦浆的特性及其影响因素,提出了改善水焦浆稳定性的几种方法,主要进行了以下工作：
采用多种石油焦、多种添加剂制备水焦浆,深入研究了水焦浆的成浆性、流变性和稳定性。结果表明,石油焦的成浆性良好,定粘浓度普遍在70%左右;随着粒径分布范围的变宽和平均粒径的变大,石油焦的成浆性变好；水焦浆的定粘浓度与石油焦的内水分和灰分均成反比,且内水分对定粘浓度的反作用效果较大；随着比表面积和总孔容的减小,成浆性提高；石油焦的强疏水性表面特性,有利于成浆浓度的提高,但易使水焦浆呈现“剪切变稠”的胀流性特征,且具有较差的稳定性。
研究了各种灰分对水焦浆稳定性的影响。结果表明,加入少量CaO能有效提高水焦浆的稳定性,当CaO的添加质量为石油焦干基质量的0.3%时,可以制得定粘浓度为68.0%、定粘流动特征指数为0.78、定粘析水率为3.4%的高品质水焦浆。
选用褐煤和污泥分别与石油焦共成浆,研究了煤焦比(或污泥含量)对浆体表面特性及浆体品质的影响。结果表明,随着煤焦比(或污泥含量)的增加,一方面浆体表面张力变大,成浆性变差,另一方面Zeta电位绝对值增加,稳定性变好,假塑性增强；褐煤焦浆(或污泥焦浆)的稳定性与假塑性正相关,与成浆性负相关；当煤焦比为1：4时,可以制得定粘浓度大于65%、定粘流动特征指数约0.9、定粘析水率约4%的褐煤焦浆；当污泥含量为6%时,可以制得定粘浓度约64%、定粘流动特征指数小于0.8、定粘析水率约5%的污泥焦浆,是浓度较高、稳定性较好、假塑性特征较强的高品质浆体燃料。
研制气泡水焦浆以期改善水焦浆的稳定性,分别采用单一因素分析法和多因素多水平的正交试验法研究了浆体制备过程中各因素对稳定性的影响。结果表明,吹气时间、起泡剂用量和浆体浓度对气泡水焦浆稳定性的影响十分显著,而起泡剂种类和布风板孔径大小的影响较弱；获得最佳稳定性的操作条件是：吹气时间为30min,成浆浓度为65%,起泡剂用量为0.030%,布风板孔径为2～5μm,起泡剂种类为AOS。在此最优条件下,气泡水焦浆的倒出率可达96%以上,比同等条件下的纯水焦浆(无气泡)提高了约80个百分点,稳定性大大改善,且浆体的流动特征指数在0.8左右,假塑性特征明显。
在实验研究基础上,分析了气泡水焦浆形成的微观作用机理。结果发现,气泡的生成主要依赖起泡剂的加入,起泡剂存在一个最佳用量；气泡在浆体中最稳定的状态就是以气固联合体的形式存在,气固联合体的形成存在碰撞、黏附和脱附三个微观过程；气泡直径越小,浆体微湍流强度越大,颗粒与气泡间的碰撞概率越高；颗粒表面疏水性越强,接触角越大,越易黏附在气泡上
Preparation of petroleum-coke-water-slurry (PCWS) can broaden scope of raw materials of fuel of oil substitute and gasification, and settle problem of tension supply of bituminous coal. PCWS, which has high solid concentration, high heat value and low ash content, can burn instead of oil, gas and coal, also can provide raw materials of large-scale efficient clean coal gasification technology. The production of fuel type petroleum coke increases year by year in China. The technology of PCWS can achieve high efficient and clean utilization of petroleum coke, but the bad stability restricts development and application of PCWS. It's important to improve stability of PCWS.
In order to improve the quality of PCWS, this paper studies properties of PCWS and its influencing factors, and puts forward methods of improving the stability. The main work is carried out as follows:
Many types of petroleum cokes and additives are used for PCWS whose slurryability, rheological characteristics and stability are investigated. Results show that petroleum cokes have good slurryability with solid concentration being about70%generally. The slurryability is enhanced with increasing particle size distribution range and average particle size, and with decreasing specific surface area and pore volume. The solid concentration is inversely proportional to inherent moisture content and ash content of the petroleum coke, and the inherent moisture content is more adverse. Surface characteristic of petroleum coke is strong hydrophobicity, which is in favor of enhancing the concentration and makes PCWS be dilatant and unstable fluid easily.
The effect of various kinds of ash on the stability of PCWS is researched. Results show that the stability can be improved effectively by adding a small amount of CaO. When the adding quality of CaO is0.3%of dry basis petroleum coke, PCWS has high performance, whose concentration is68.0%, flow characteristic index is0.78, and drainage rate is3.4%at fixed viscosity.
The influence of ratio of coal and coke (or sludge content) on surface characteristic of slurries prepared with petroleum coke and lignite or sludge is studied. Results show that surface tension and Zeta potential absolute value increase, and stability and pseudoplasticity enhance, but slurryability goes worse, with increasing ratio of coal and coke (or sludge content). The stability is positively related to the pseudoplasticity and negatively related to the slurryability. When the ratio of coal and coke is1:4, lignite coke slurry has high performance, whose concentration is above65%, flow characteristic index is about0.9, and drainage rate is about4%at fixed viscosity. When the sludge content is6%, sludge coke slurry also has high performance, whose concentration is about64%, flow characteristic index is less than0.8, and drainage rate is about5%at fixed viscosity.
Bubble-petroleum-coke-water-slurry (BPCWS) is prepared to improve stability of PCWS. The influence of various factors in the preparation process on the stability is studied by single factor analysis and multiple factors orthogonal method respectively. Results show that the effects of blowing time, foaming agent dosage and solid concentration on the stability are very significant, while the effects of foaming agent type and ventilation panel aperture size are slight. The operating conditions of obtaining the best stability are blowing for30min, concentration being65%, foaming agent dosage being0.030%,2～5μm aperture size and AOS. Under the optimal conditions, pouring rate of BPCWS is more than96%, which increases by about80percentage points compared with pure PCWS (no bubbles). The BPCWS has good stability and obvious pseudoplasticity with flow characteristic index being about0.8.
On the basis of experimental research, the microscopic mechanism of BPCWS is analysed. Results show that bubble formation depends mainly on the foaming agent which has an optimum dosage. The most stable form of bubbles in slurry is gas-solid-union forming through collision, adhesion and desorption. The collision probability between particles and bubbles is enhanced with decreasing bubble diameter, and with increasing microturbulence intensity. The stronger the hydrophobicity of particle surface, the larger the contact angle, the more easily the particles adhere to the bubbles.
引文
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