煤泥水化学微生物法深度处理的基础研究
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摘要
煤泥水处理是煤炭行业老大难问题，目前受管理、资金及技术等因素限制，仍然存在煤泥水外排、循环水利用率低和煤能源的浪费等问题。随着世界各国环保压力加大及节约能源的要求不断提高，急需选择高效的处理技术方法，从根本上改变目前煤泥水的处理利用现状。
论文以徐州夹河矿煤泥水、张双楼矿煤泥水、及河南永城薛湖矿煤泥水为研究对象，借助激光粒度分析仪、XRD、原子吸收光谱仪、紫外分光光度计、离子色谱仪等先进的分析仪器，对煤泥水体系的基本性质进行了测定分析。通过数学建模、回归分析、线性拟合、Design-Expert试验设计等先进的理论分析及试验方法，研究了煤泥水处理的影响因素、作用规律及相关参数。通过微生物协同处理煤泥水，研究了煤泥水中黄铁矿的脱出机理。得到以下系列研究成果：
论文创新设计了化学-微生物法协同处理煤泥水的新思路；通过氧化亚铁硫杆菌改性优育菌株选择性吸附及特性转化黄铁矿，对煤泥水中夹杂的黄铁矿进行协同深度处理，得到了相对理想的时间内（7天）较高的脱硫率79.3%；给出了煤泥水中黄铁矿脱出机理及作用过程的系列化学反应方程及生化反应方程，并具体解释了煤泥水中黄铁矿在微生物化学协同作用下的微观化学机制，反应条件，影响因素及目标产物的选择性控制及耦合过程。
设计开发了煤泥水化学-微生物法协同处理试验模型装置，微生物与可降解淀粉基聚丙烯酰胺类高分子化学絮凝剂（st-PAM）及氯化钙分步协同，既充分利用高分子药剂煤泥水处理的高效性，又避免了常规化学药剂单一使用的二次污染大的弊端，实现煤泥水环保处理。
优化实验研究，揭示出st-PAM对各矿煤泥水均有一定的絮凝沉降效果，沉降速度相对理想；单用氯化钙对煤泥水沉降速度无明显促进作用，但对上清液透光率有提升，与st-PAM连用，明显提升沉降速度和透光率；白腐菌单用情况下，煤泥水沉降速度和透光率在短时间内无明显效应，参与到st-PAM、氯化钙处理体系中，分别体现出了提高沉降速度、透光率、增强沉降速度提升的稳定性及获得理想投药量的协同处理效果。
煤泥脱水系列技术参数及基本理论数据研究结果表明，氯化钙和高分子絮凝剂联用可改善滤饼通透性，增大煤泥恒压过滤常数K，添加微生物絮凝剂，更加突出改善煤泥脱水性能，增大过滤速度；但是添加微生物絮凝剂后煤泥滤饼含水率略有升高。
论文根据最小二乘法建构二次多项预测模型方程，借助Design-Expert试验设计软件，利用多因素多水平响应曲面正交实验设计，对煤泥水进行了因素优化正交试验，进行多元回归拟合，并进行精确性及显著性等检验，得出试验条件下透光率、沉降速度、上清液pH值、压滤脱水时间、压缩层高/总高的模型方程。对处理夹河矿煤泥水上清液给出了透光率90.48%的指导优化因素实验方案，指明了上清液pH值3D表面响应规律，并对张双楼矿、薛湖矿相关评价指标响应值给出了因素交互作用规律及影响程度。
Coal slurry treatment is a difficult problem in the coal industry. Due to therestriction from management, funds, technology and other factors, there are still coalslurry efflux, low circulating water utilization rate and the waste in coal energy. Withthe increase of pressure on the world environmental protection and the improvementof energy conservation requirement, it is needed to change the current utilizationstatus of coal slurry treatment, and choose high effective methods.
Coal slurry from Xuzhou Jiahe mine, Zhangshuanglou mine and YongchengXuehu mine as the research object, with the help of advanced analytical instrumentsof laser particle size analyzer, XRD, atomic absorption spectrometer, UVspectrophotometer, ion chromatography, basic properties of coal slurry system weremeasured.The influence factors, rules and related parameters of coal slurry treatmentwere studied by mathematical modeling, regression analysis, linear fitting,Design-Expert design and other advanced theoretical analysis,test method. Throughthe combination of microbial co processing of coal slurry, the removal mechanism ofpyrite in coal slurry was researched. The series of results:
The new idea of coal slurry treatment by chemical and microbial method waspresented. With the selective adsorption to pyrite, pyrite was released from the coalslime by Thiobacillus ferrooxidans(T.f), and the high desulfurization rate79.3%wasobtained during relatively ideal time7days. The removal mechanism of pyrite wasget through the chemical reaction and biochemical reaction equations. Under theinteraction of microorganisms and chemistry, the micro chemical mechanism, reactionconditions, and influencing factors of pyrite were explained, as well as selectivecontrol and coupling process of the target product.
Chemical and microbiological method collaborative processing model test deviceto manage and clean coal slurry was designed deeply in the experimental research ofthis thesis. Microorganism, degradable modified polyacrylamide polymer flocculant(st-PAM) and calcium chloride were used by collaboration to make full use of highperformance polymer agent in coal slurry treatment, but also avoid subsequentpollution from conventional chemical ways by single use in the management of coalslurry, the implementation of environmental protection of coal slurry treatment wasfinished in the process.
Research on coal slurry by single factor and composite experimental design was optimized. The effect of st-PAM on the settlement of coal slurry had a certainflocculation effect, and the sedimentation velocity was ideal relatively.
Use calcium chloride alone has little effect on coal slurry sedimentation velocity,but a significant increase on transmittance, and both significant enhance by using withst-PAM in the sedimentation velocity and transmittance.
In the White rot fungi(W.r.f) single case, coal slurry sedimentation velocity andlight transmission rate had no obvious effect in a short time, while the increase ofsedimentation velocity, the enhancing of stability in fast sedimentation and the idealprocessing effect of dosage were reflected respectively by collaborative usingst-PAM, calcium chloride and W.r.f.
The permeability of filter cake and the constant pressure filtration coefficient Kwith calcium chloride and polymeric flocculant was improved through the study onthe technical parameters and the basic data results of coal slime dewatering. Thefiltration speed was further increased by adding microbial flocculant, but after addingmicrobial flocculant filter cake moisture content increased slightly.
With the help of Design-Expert software, the two predictive model equationaccording to the least square method, and orthogonal experimental design of multiplefactors and levels, orthogonal test factors were optimized of coal slurry treatment wascarried. The model equations under the condition of transmittance, sedimentationvelocity, pH value, filter press dewatering time, compression height/total height wereobtained through multiple regression, and accuracy and significant test. Factoroptimization experiment scheme of Jiahe coal slurry supernatant transmittance90.48%and the supernatant pH3D surface response rule were given. ForZhangshuanglou and Xuehu coal slurry, the interaction rules and influence of relatedevaluation index response value were provided.
论文以徐州夹河矿煤泥水、张双楼矿煤泥水、及河南永城薛湖矿煤泥水为研究对象，借助激光粒度分析仪、XRD、原子吸收光谱仪、紫外分光光度计、离子色谱仪等先进的分析仪器，对煤泥水体系的基本性质进行了测定分析。通过数学建模、回归分析、线性拟合、Design-Expert试验设计等先进的理论分析及试验方法，研究了煤泥水处理的影响因素、作用规律及相关参数。通过微生物协同处理煤泥水，研究了煤泥水中黄铁矿的脱出机理。得到以下系列研究成果：
论文创新设计了化学-微生物法协同处理煤泥水的新思路；通过氧化亚铁硫杆菌改性优育菌株选择性吸附及特性转化黄铁矿，对煤泥水中夹杂的黄铁矿进行协同深度处理，得到了相对理想的时间内（7天）较高的脱硫率79.3%；给出了煤泥水中黄铁矿脱出机理及作用过程的系列化学反应方程及生化反应方程，并具体解释了煤泥水中黄铁矿在微生物化学协同作用下的微观化学机制，反应条件，影响因素及目标产物的选择性控制及耦合过程。
设计开发了煤泥水化学-微生物法协同处理试验模型装置，微生物与可降解淀粉基聚丙烯酰胺类高分子化学絮凝剂（st-PAM）及氯化钙分步协同，既充分利用高分子药剂煤泥水处理的高效性，又避免了常规化学药剂单一使用的二次污染大的弊端，实现煤泥水环保处理。
优化实验研究，揭示出st-PAM对各矿煤泥水均有一定的絮凝沉降效果，沉降速度相对理想；单用氯化钙对煤泥水沉降速度无明显促进作用，但对上清液透光率有提升，与st-PAM连用，明显提升沉降速度和透光率；白腐菌单用情况下，煤泥水沉降速度和透光率在短时间内无明显效应，参与到st-PAM、氯化钙处理体系中，分别体现出了提高沉降速度、透光率、增强沉降速度提升的稳定性及获得理想投药量的协同处理效果。
煤泥脱水系列技术参数及基本理论数据研究结果表明，氯化钙和高分子絮凝剂联用可改善滤饼通透性，增大煤泥恒压过滤常数K，添加微生物絮凝剂，更加突出改善煤泥脱水性能，增大过滤速度；但是添加微生物絮凝剂后煤泥滤饼含水率略有升高。
论文根据最小二乘法建构二次多项预测模型方程，借助Design-Expert试验设计软件，利用多因素多水平响应曲面正交实验设计，对煤泥水进行了因素优化正交试验，进行多元回归拟合，并进行精确性及显著性等检验，得出试验条件下透光率、沉降速度、上清液pH值、压滤脱水时间、压缩层高/总高的模型方程。对处理夹河矿煤泥水上清液给出了透光率90.48%的指导优化因素实验方案，指明了上清液pH值3D表面响应规律，并对张双楼矿、薛湖矿相关评价指标响应值给出了因素交互作用规律及影响程度。
Coal slurry treatment is a difficult problem in the coal industry. Due to therestriction from management, funds, technology and other factors, there are still coalslurry efflux, low circulating water utilization rate and the waste in coal energy. Withthe increase of pressure on the world environmental protection and the improvementof energy conservation requirement, it is needed to change the current utilizationstatus of coal slurry treatment, and choose high effective methods.
Coal slurry from Xuzhou Jiahe mine, Zhangshuanglou mine and YongchengXuehu mine as the research object, with the help of advanced analytical instrumentsof laser particle size analyzer, XRD, atomic absorption spectrometer, UVspectrophotometer, ion chromatography, basic properties of coal slurry system weremeasured.The influence factors, rules and related parameters of coal slurry treatmentwere studied by mathematical modeling, regression analysis, linear fitting,Design-Expert design and other advanced theoretical analysis,test method. Throughthe combination of microbial co processing of coal slurry, the removal mechanism ofpyrite in coal slurry was researched. The series of results:
The new idea of coal slurry treatment by chemical and microbial method waspresented. With the selective adsorption to pyrite, pyrite was released from the coalslime by Thiobacillus ferrooxidans(T.f), and the high desulfurization rate79.3%wasobtained during relatively ideal time7days. The removal mechanism of pyrite wasget through the chemical reaction and biochemical reaction equations. Under theinteraction of microorganisms and chemistry, the micro chemical mechanism, reactionconditions, and influencing factors of pyrite were explained, as well as selectivecontrol and coupling process of the target product.
Chemical and microbiological method collaborative processing model test deviceto manage and clean coal slurry was designed deeply in the experimental research ofthis thesis. Microorganism, degradable modified polyacrylamide polymer flocculant(st-PAM) and calcium chloride were used by collaboration to make full use of highperformance polymer agent in coal slurry treatment, but also avoid subsequentpollution from conventional chemical ways by single use in the management of coalslurry, the implementation of environmental protection of coal slurry treatment wasfinished in the process.
Research on coal slurry by single factor and composite experimental design was optimized. The effect of st-PAM on the settlement of coal slurry had a certainflocculation effect, and the sedimentation velocity was ideal relatively.
Use calcium chloride alone has little effect on coal slurry sedimentation velocity,but a significant increase on transmittance, and both significant enhance by using withst-PAM in the sedimentation velocity and transmittance.
In the White rot fungi(W.r.f) single case, coal slurry sedimentation velocity andlight transmission rate had no obvious effect in a short time, while the increase ofsedimentation velocity, the enhancing of stability in fast sedimentation and the idealprocessing effect of dosage were reflected respectively by collaborative usingst-PAM, calcium chloride and W.r.f.
The permeability of filter cake and the constant pressure filtration coefficient Kwith calcium chloride and polymeric flocculant was improved through the study onthe technical parameters and the basic data results of coal slime dewatering. Thefiltration speed was further increased by adding microbial flocculant, but after addingmicrobial flocculant filter cake moisture content increased slightly.
With the help of Design-Expert software, the two predictive model equationaccording to the least square method, and orthogonal experimental design of multiplefactors and levels, orthogonal test factors were optimized of coal slurry treatment wascarried. The model equations under the condition of transmittance, sedimentationvelocity, pH value, filter press dewatering time, compression height/total height wereobtained through multiple regression, and accuracy and significant test. Factoroptimization experiment scheme of Jiahe coal slurry supernatant transmittance90.48%and the supernatant pH3D surface response rule were given. ForZhangshuanglou and Xuehu coal slurry, the interaction rules and influence of relatedevaluation index response value were provided.
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