随着全球能源需求的增长，煤炭的高效清洁利用变得至关重要。煤气化技术通过将煤炭转化为合成气来生产电力、化工原料和燃料油，但同时产生大量含硅、铝、铁、钙的固体废弃物——煤气化渣。若不加以处理，这些渣料会占用土地并对环境造成潜在危害。通过改性和加工，煤气化渣可作为胶凝材料或骨料，用于制备充填材料和混凝土等功能材料加以利用，降低传统材料生产成本。因此，研究煤气化渣的资源化利用具有科学价值和战略意义。

本文针对陕北榆林地区煤气化渣的资源化利用需求，利用改性镁渣和脱硫石膏激发煤气化细渣的反应活性，开发了一种绿色低碳的改性煤气化渣基胶凝材料(MCC)。同时，以煤气化粗渣为骨料，研制了一种高性低价的改性煤气化渣基充填材料(MCB)。通过室内试验、理论分析和现场试验，明确了煤气化渣的水化活性来源及其改性原理，揭示了MCC的水化硬化机制，研究了MCB中骨料与硬化浆体的相互作用和协同承载特性，成功制备出适用于矿山充填和场地硬化的高性能材料。主要开展了以下工作：

(1) 通过BET、FT-IR和XRD等表征手段，对比分析了煤气化细渣和粗渣的粒度分布、化学成分、物相组成、孔隙特征、化学基团和元素化学状态等物化特性。研究了细渣和粗渣中残炭和硅铝酸盐的化学形态和占比，并分析了其在氢氟酸中的Ca、Si和Al的溶出特性差异，量化了其火山灰反应活性。结果表明，煤气化渣的水化活性主要来自低聚合度的硅铝酸盐，粗渣的聚合度高于细渣，且其粒径大比表面积小，不利于火山灰反应，导致其活性指数远低于细渣(约低20%)，且二者均未达到活性指数不低于60%的标准要求，无法直接作为胶凝材料使用。

(2) 针对煤气化细渣活性低的问题，利用当地改性镁渣和脱硫石膏，开展盐碱复合激发的活化改性研究。通过模拟改性镁渣中CaO和MgO形成的碱性环境，与脱硫石膏配置不同组分溶液，研究煤气化细渣中Si和Al的溶出规律，建立了溶出动力学模型，揭示了其在盐-碱激发剂作用下的溶解聚合机制。结果表明，改性镁渣中的CaO和MgO与脱硫石膏中的CaSO₄ꞏ2H₂O与煤气化渣的硅铝酸盐具有化学成分互补优势。改性镁渣和脱硫石膏的单一激发效果弱于二者的复合激发，复合激发的活性指数提升了38%。

(3) 通过热力学分析，明确了MCC水化反应是一个放热过程，并利用放热特性划分了水化阶段，揭示了固废种类和掺量对各反应阶段的影响。基于水化动力学，研究了MCC的水化机理，量化了晶体几何生长指数(n)和反应动力学常数(K)。采用XRD、SEM和MIP等表征了MCC硬化体的水化产物种类和生成量，揭示了其孔隙结构的演化规律。利用单纯形质心法研究了MCC凝结时间和强度的演变，揭示了MCC从矿物相溶解到水化反应再到浆体硬化的水化硬化机制。结果表明，改性镁渣、脱硫石膏和煤气化细渣中的β-C₂S，CaO，MgO、CaSO₄ꞏ2H₂O和硅铝酸盐溶解并发生水化反应，生成C-S(A)-H和AFt等水化产物，优化了孔隙分布，提高了MCC基质密实度和强度。

(4) 研究了固废种类和掺量对MCB强度的影响，建立了固废掺量与强度的多项式函数关系。揭示了MCB中骨料、界面过渡区(ITZ)和硬化浆体的微力学差异，量化了各相的显微硬度和压痕模量，明确了固废种类和掺量对ITZ微观结构、化学元素组成和形貌的影响。研究了MCB的孔隙分布特征，建立了微观孔隙、显微硬度和强度的关联关系，揭示了骨料与浆体间的作用机制。结果表明，28天MCB的抗压强度高达22.00 MPa，骨料、硬化浆体和ITZ的显微硬度分别为7.58∼9.61 GPa、0.29∼0.62 GPa 和0.07∼0.33 GPa，ITZ范围为15∼35 μm。MCB中骨料与硬化浆体存在无互动、弱互动、强互动和聚合四种作用关系，通过机械咬合、摩擦力和化学作用增强了其粘结作用。

(5) 通过单轴压缩试验，结合声发射和数值散斑技术，系统研究了不同固废种类和掺量对MCB 力学参数、应力-应变曲线、裂纹萌生与扩展规律及破坏模式的影响。结果表明，MCB 的弹性模量受固废种类和掺量影响，变化范围为88.2∼1408.2 MPa，与固废掺量呈三次函数关系。随脱硫石膏掺量增加，裂纹扩展数量先增后减，破坏形态由“X型”转为“Y 型”，再转为“II型”。随改性镁渣和煤气化细渣掺量增加，裂纹扩展数量增多，破坏形态由“X型”转为“II型”，再转为“Y型”。MCB的破坏模式主要包括拉伸、剪切及拉剪组合破坏，其中拉伸信号占主导地位，比例为52.1%∼68.4%。

(6) 采用响应面法(RSM)分析了不同材料组分对MCB抗压强度和流动性的影响及其显著性，揭示了各因素的相互作用。以流动性、强度和浸出毒性为约束条件，最小成本和最大强度为多目标函数，利用鲸鱼优化算法(WOA)进行多目标配比优化设计。将优化后的MCB应用于场地硬化工程，并进行工程示范，验证其强度和环境性能。结果表明：利用RSM-WOA多目标优化技术，提升了MCB性能，有效降低了生产成本，其设计的MCB在强度、流动性和浸出毒性方面均满足矿山充填和场地硬化的需求。

With the growth of global energy demand, the efficient and clean utilization of coal has become crucial. Coal gasification technology converts coal into synthetic gas to produce electricity, chemical raw materials, and fuel oil, but at the same time generates a large amount of solid waste (CGS) containing silicon, aluminum, iron, and calcium. If left untreated, these slags occupy land and are potentially harmful to the environment. Through modification and processing, gasification slag can be used as cementitious materials or aggregates for the preparation of backfill materials and functional materials such as concrete, reducing the production cost of traditional materials. Therefore, studying the resource utilization of coal gasification slag has scientific value and strategic significance.

In this paper, for the demand of resource utilization of coal gasification slag in Yulin area of northern Shaanxi, a green and low-carbon modified coal gasification slag-based cementitious material (MCC) was developed by using modified magnesium slag and desulfurization gypsum to stimulate the reactivity of coal gasification fine slag. Meanwhile, a cost-effective modified coal gasification slag-based backfill material (MCB) was prepared using coal gasification coarse slag as aggregate. Through indoor tests, theoretical analyses and field tests, the source of hydration activity of coal gasification slag and its modification principle were clarified, and the hydration-hardening mechanism of MCC and the interaction and synergistic load-bearing characteristics of aggregate and hardened slurry in MCB were explored, so that high-performance materials suitable for mine backfill and site hardening have been successfully prepared. The following work was mainly carried out:

(1) The physical and chemical properties such as particle size distribution, chemical composition, physical phase composition, pore characteristics, chemical groups and elemental chemical states of coal gasification fine slag and coarse slag were comparatively analyzed by means of BET, FT-IR and XRD characterization. The study reveals the chemical morphology and proportion of residual carbon and silica-aluminate in the fine and coarse slags, and analyzes the differences in the dissolution characteristics of Ca, Si and Al in HF, and quantifies their pozzolanic reactivity. The results show that the hydration activity of coal gasification slag mainly comes from silica-aluminate with low polymerization degree, and the polymerization degree of coarse slag is higher than that of fine slag, but coarse slag has a large particle size and small specific surface area, which is not conducive to the pozzolanic reaction, resulting in an activity index much lower than that of fine slag (about 20% lower), and both of them do not reach the 60% activity index required by the standard, and therefore cannot be used for cementitious materials directly.

(2) Aiming at the problem of low activity of coal gasification slag, the activation and modification research of saline and alkaline composite excitation was carried out by using local modified magnesium slag and desulfurization gypsum solid waste. By simulating the alkaline environment formed by CaO and MgO in the modified magnesium slag and configuring different component solutions with desulfurization gypsum, the dissolution law of Si and Al in the coal gasification fine slag was studied, and a dissolution kinetic model was established to reveal its dissolution and polymerization mechanism under the action of salt-alkali exciters. The results show that CaO and MgO in modified magnesium slag and sulfate (CaSO₄ꞏ2H₂O) in desulfurization gypsum have complementary advantages with silica-aluminate in coal gasification slag. The single excitation of modified magnesium slag and desulfurization gypsum was weaker than the composite excitation of the two, and the activity index of the composite excitation was enhanced by 38%.

(3) Through thermodynamic analysis, it was clarified that the hydration reaction of MCC was an exothermic process, and the exothermic properties were used to divide the hydration stages, revealing the effects of solid waste types and dosage on each reaction stage. Based on the hydration kinetic model, the hydration mechanism of MCC was investigated, and the crystal geometric growth index (n) and reaction kinetic constant (K) were quantified. XRD, SEM and MIP were used to characterize the hydration product types and production of MCC hardeners, revealing the evolution of their pore structure. The evolution of MCC condensation time and strength was investigated using the simplex centroid method, revealing the hydration-hardening mechanism of MCC from mineral phase dissolution to hydration reaction to slurry hardening. The results showed that β-C₂S, CaO, MgO, CaSO₄ꞏ2H₂O and silica-aluminate in modified magnesium slag, desulfurization gypsum and coal gasification fine slag were dissolved and underwent hydration reactions to produce hydration products such as C-S(A)-H and AFt, which optimized the pore distribution and improved the MCC matrix compactness and strength.

(4) The effects of solid waste types and dosage on the strength of MCB were investigated, and a polynomial functional relationship between solid waste dosage and strength was established. The micromechanical differences of aggregate, interfacial transition zone (ITZ) and slurry in MCB were revealed, the microhardness and indentation modulus of each phase were quantified, and the effects of solid waste types and dosing on the microstructure, chemical element composition and morphology of ITZ were clarified. The pore distribution characteristics of MCB were investigated, and the correlation relationship between microscopic pores, micro-hardness and strength was established, revealing the mechanism of interaction between aggregate and slurry. The results show that the compressive strength of MCB reaches 22.00 MPa, and the micro-hardnesses of aggregate, hardened slurry and ITZ are 7.58∼9.61 GPa, 0.20∼0.53 GPa, and 0.07∼0.33 GPa, with the ITZ ranging from 15∼35 μm. There are four kinds of interaction relationships between aggregate and hardened slurry in MCB, namely no interaction, weak interaction, strong interaction and polymerization, which enhances their bonding through mechanical occlusion, friction and chemical action.

(5) In this study, the effects of different solid waste types and dosages on the mechanical parameters, stress-strain curves, crack initiation and extension patterns, and damage modes of MCB were systematically investigated by means of uniaxial compression tests, combined with acoustic emission and numerical scattering techniques. The results showed that the modulus of elasticity of MCB was affected by the type and dosage of solid waste, with the variation range from 88.2 to 1408.2 MPa, and the relationship with the dosage of solid waste was a cubic function. With the increase of desulfurization gypsum dosage, the number of crack extension increases and then decreases, and the damage pattern changes from“X-type”to“Y-type”and then to “II-type”. With the increase of modified magnesium slag and coal gasification slag, the number of crack extension increases, and the damage pattern changes from “X-type”to “II-type”and then to “Y-type”.Damage modes of MCB The damage modes of MCB mainly include tensile, shear and combined tensile-shear damage, in which the tensile signal dominates, with a proportion of 52.1%∼68.4%.

(6) Response surface methodology (RSM) was used to analyze the effects of different material components on the compressive strength and flowability of MCB and their significance, revealing the interaction of the factors. With fluidity, strength and leaching toxicity as constraints, and minimum cost and maximum strength as multi-objective functions, a multi-objective proportioning optimization design was carried out using the Whale Optimization Algorithm (WOA). The optimized MCB was applied to the flooring project and engineering demonstration was conducted to verify its strength and environmental performance. The results show that the use of RSM-WOA multi-objective optimization technology improves the performance of MCB and effectively reduces the production cost, and its designed MCB meets the needs of mine backfill and site hardening in terms of strength, fluidity and leaching toxicity.

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