煤基灰/渣的大宗固废资源化利用现状及发展趋势

近年来,煤炭工业快速发展,为国民经济运行提供了重要能源保障和原料支撑,与此同时,燃煤电厂、工业和民用锅炉等设备在煤燃烧和气化工艺过程中,产生大量的煤基灰/渣(粉煤灰、燃煤炉渣、气化渣)等工业固体废弃物,对生态环境造成了较大影响。以粉煤灰和气化渣为代表的煤基灰/渣为例,我国每年排放约8亿t粉煤灰和3500万t气化渣,但是受限于国家能源结构、产业政策等因素的影响,以及煤基灰/渣的资源分布、产地性质的制约,目前,煤基灰/渣的高效资源化利用率还有待提升,其中,粉煤灰的综合利用率为70%、气化渣的综合利用率仅为30%,未来我国大宗固废仍存在产量大、资源利用不充分、综合利用产品附加值低等困境。因此,进一步提升大宗固废综合利用水平,全面提高资源利用效率,积极落实国家“碳达峰”和“碳中和”相关政策,完成煤炭工业“十四五”发展规划中相关工作,是当前煤炭开发利用需面对的重要问题。基于此,针对煤基灰/渣的性质,开展了大量的探索,如分级、分选、提质等技术研究,开发了具有针对性的工艺技术及装备,部分实现了煤基灰/渣的大宗固废资源化利用和高附加值利用。鉴于煤基灰/渣具有比表面积大、孔隙结构发达、含碳量偏高、铝硅含量丰富等特性,目前已经作为原料广泛应用于建工建材、环保、生态、化工等领域。文章分别从大宗固废资源化利用和深加工高附加值利用两个方面对煤基灰/渣进行了阐述。①建工建材等应用领域仍是提升煤基灰/渣大宗固废资源化利用的重要方向,但由于煤基灰/渣资源化利用存在脱碳与炭−灰分离技术装备有待完善、脱水与干燥困难、重金属可能存在沉淀等问题,后续有待深入研究;②提取有用组分并用于功能性碳材料制备、环境污染治理等领域可实现煤基灰/渣深加工高附加值利用,但需对生产工艺环节中产生的酸碱性或重金属废液进行有效处理,从而减少对环境的污染。针对煤基灰/渣在大宗固废资源化利用中所存在的问题,探讨了其未来发展趋势,以期为煤基灰/渣的大宗固废资源化利用以及煤化工行业高端化、低碳化、绿色化发展提供借鉴与参考。

垃圾焚烧典型工段灰/渣理化特性及环境风险性

研究了垃圾焚烧典型工段5种灰/渣样品(余热锅炉灰/渣S1、半干法脱酸灰S2、布袋除尘灰S3、飞灰原灰S4和螯合剂稳定化飞灰S5)的表观特征、化学特性和浸出特性,并评估了灰/渣样品赋存重金属的环境风险。结果表明:S1呈现与其他灰样显著的表观特征差异,其表观颜色泛黄,颗粒大小不均,Si、Al含量较高,可资源化利用潜力较大;S3可溶性氯盐、高毒性重金属(Pb、Cd)含量较高,可进行单独脱氯、解毒处理;S5粒径级配在7~20μm和40~120μm存在两处波峰,其稳定化效果存在一定缺陷。S1赋存Cr(4.45%)和S3赋存Pb(3.04%)、Cd(4.28%)的可交换态和碳酸盐结合态占比相对较高,表明其潜在浸出环境风险较高,在其无害化处理和资源化利用过程中需重点关注,尤其是酸性(如酸雨或渗滤液浸沥)处置或应用场景。S1赋存重金属的潜在环境风险远低于其他4种灰样;模拟渗滤液浸提环境下,5种灰/渣浸出液重金属的综合性环境风险水平均高于模拟酸雨浸提环境,且S1、S3、S4和S5中Cd的浸出环境风险水平表现为“极强”等级。研究结果可为垃圾焚烧典型工段灰/渣的分类利用、精细化管理以及科学的环境风险评估提供理论依据。

Corrosion behavior of co-gasification slag of furfural residue and coal on alumina-silica refractories

Gasification of furfural residue with coal can realize its efficient and clean utilization.But the high alkali metal content in furfural slag is easy to cause the corrosion of gasifier refractory.Two gasification coals with different silica alumina ratio and a furfural residue were selected in the study.The effects of furfural residue additions on corrosion of silica brick,corundum brick,high alumina brick and mullite brick were investigated by using XRD,SEM-EDS and Factsage Software,and the corrosion mechanism was analyzed.With increasing furfural residue addition,the permeability of the slags to high-aluminium-bearing refractories first decreases and then increases,while the permeability on silica brick shows a slight decrease trend.Leucite(KAlSi_(2)O_(6))with high-melting temperature is generated from the reaction of K_(2)O and SiO_(2)in slag with Al_(2)O_(3)in refractories after furfural residue is added,which hinders the infiltration of slag in refractories.Kaliophilite(KAlSiO_(4))of low-melting point is formed when K_(2)O content increases,and this contributes to the infiltration of slag in refractories.The acid-base reaction between slag and silica brick is distinctly occurred,more slag reacts with SiO_(2)in the silicon brick,resulting in a decrease in the amount of slag infiltrating into the silicon brick as furfural residue is added.The corrosion of silica brick is mainly caused by the acid-base reaction,while the corrosion of three alumina based refractory bricks of corundum,mullite and high alumina brick is determined by slag infiltration.A linear correlation between the percolation rate and slag viscosity is established,the slag permeability increases with decreasing viscosity,resulting in stronger permeability for the high Si/Al ratio slag with lower viscosity.

Air-void parameters measurement of fresh concrete and hardened concrete

Air content, spacing factor and specific surface of fresh concrete and hardened concrete with different air contents, slumps and mineral admixtures (fly ash, slag, fly ash + slag, fly ash + slag + silica fume composite) were studied by the air-void analyzer (AVA) method and the microscopical method. The correlations between the test results obtained from different methods were analyzed. The results show that, there is a close correlation of air content and spacing factor between the fresh concrete and the hardened concrete, but the specific surface correlation is weak. The air content of concrete measured by the AVA method is smaller than that of the pressure method and the microscopical method, because AVA device captures only the air voids with the size smaller than 3 mm. Spacing factor of the fresh concrete measured by the AVA method is greater than that of the hardened concrete measured by the microscopical method, while the specific surface is smaller. When the criterion of 4%-7% air content measured by the pressure method and microscopical method is acceptable for concrete freezing-thawing (F-T) durability in cold weather, the air content measured by the AVA method should be 2.4%-4.6%. For the concrete F-T durability, when the criterion of the spacing factor measured by the microscopical method is 300 μm, the spacing factor measured by the AVA method should be 360 μm.

Physicochemical properties of arsenic-bearing lime-ferrate sludge and its leaching behaviors

Physicochemical properties and leaching behaviors of two typical arsenic-bearing lime?ferrate sludges(ABLFS),waste acid residue(WAR)and calcium arsenate residue(CAR),are comprehensively described.The chemical composition,morphological features,phase composition and arsenic occurrence state of WAR and CAR are analyzed by ICP?AES,SEM?EDS,XRD,XPS and chemical phase analysis.The toxicity leaching test and three-stage BCR sequential extraction procedure are utilized to investigate arsenic leaching behaviors.The results show that the contents of arsenic in WAR and CAR are2.5%and21.2%and mainly present in the phases of arsenate and arsenic oxides dispersed uniformly or agglomerated in amorphous particles.The leaching concentrations of arsenic excess119and1063times of TCLP standard regulatory level with leaching rates of47.66%and50.15%for WAR and CAR,respectively.About90%of extracted arsenic is in the form of acid soluble and reducible,which is the reason of high arsenic leaching toxicity and environmental activity of ABLFS.This research provides comprehensive information on harmless disposal of ABLFS from industrial wastewater treatment of lime?ferrate process.

Effect of activator on rheological properties of alkali-activated slag-fly ash pastes

The time-dependent rheological behaviors of alkali-activated cement(AAC)are expected to be precisely controlled,in order to meet the requirements of modern engineering practices.In this paper,the effects of activator,including the Na_(2)O concentration and SiO_(2)/Na_(2)O(S/N)molar ratio,on the rheological behavior of alkali-activated slag fly ash pastes were investigated.The small amplitude oscillatory shear(SAOS)and shear test were used to evaluate the structural build-up and flowability of pastes.Besides,zeta potential measurement,calorimetric test and thermogravimetric analysis(TGA)were carried out to reveal the physico-chemical mechanisms behind the rheological evolution of fresh pastes.It was found that high Na_(2)O concentration and low S/N molar ratio improved the flowability and structural build-up rate of paste.Moreover,the structural build-up of alkali-activated slag-fly ash pastes consists of two stages,which is controlled by the dissolution of solid reactants and formation of C-(A)-S-H gels,respectively.

Durability of Seawater Mixed Concrete with Different Replacement Ratio of BFS （Blast Furnace Slag） and FA （Fly Ash）

Using seawater in concrete can be considered as one of the sustainable approaches in construction industry not only to save the freshwater resource but also to promote the use of abandoned seawater resource, especially in the construction at the uninhabited area close to the sea where the procurement of fresh water is difficult. In this study, durability against chloride attack of seawater mixed concrete with different replacement ratio of BFS （blast furnace slag） and FA （fly ash） is discussed and the life time until the occurrence of corrosion crack is evaluated. The results show that： （1） Chloride penetration rate of seawater mixed specimens with BFS and FA is lower than that of freshwater mixed OPC （ordinary Portland cement） specimens; （2） Oxygen permeability of seawater mixed specimens with BFS and FA is almost the same or lower than that of freshwater mixed OPC specimens; （3） Total life time （corrosion incubation period and propagation period） of seawater mixed specimens with BFS and FA is almost the same or only slightly shorter than that of freshwater mixed OPC specimens. From the results, it was confirmed that the usage of seawater in concrete mixing is feasible in concrete with the appropriate BFS and FA replacement ratio.

Slagging characteristics of molten coal ash on silicon-aluminum combustion liners of boiler

In order to study the slagging characteristics of boiler combustion liners during pulverized coal stream combustion, the slag samples on the surface of combustion liner were investigated by X-ray diffractometry, scan electron microscopy and energy dispersive X-ray analysis, and the transformation characteristics of the compositions and crystal phases were studied. The results show that the size of slag granules decreases as the slagging temperature increases; the crystallinity of coal ash I reduces to about 48.6% when the temperature is increased up to 1 350 ℃, and that of the coal ash II reduces to about 65% when the temperature is increased up to 1 500 ℃; the encroachment of molten coal ash to the combustion liner is strengthened. At the same time, the diffusion and the segregation of the compositions in combustion liners have selectivity, which is in favor of enhancing the content of crystal phases, weakening the conglutination among molten slag compositions and combustion liner, and avoiding yielding big clinkers. But the diffusion of the compositions in combustion liners increases the porosity and decreases the mechanical intensity of combustion liner, and makes the slag encroachment to the liner become more serious.

Effects of Characteristics of Fly Ash on the Properties of Geopolymer

The properties of two types of fly ash geopolymers made from class F fly ashes produced in wet bottom and dry bottom boilers were investigated in the present study. The source material used in the geopolymer concrete was activated with sodium hydroxide and sodium silicate solution. The results revealed that the geopolymer produced with wet bottom boiler fly ash(CZ-FA)hardened quickly, and had higher early-age strength and lower shrinkage than the geopolymer produced with dry bottom boiler fly ash(SX-FA). The compressive strength of the two geopolymers made from CZ-FA and SX-FA was 45 MPa and 15 MPa respectively when cured at 60 ℃ and delayed for 14 d. However, after 90 days' delay, the compressive strength of both the samples is almost the same, up to 80 MPa. Nearly 20% volume shrinkage of the samples made from SX-FA was much higher than that made from CZ-FA, which was almost zero. XRD, SEM/EDS and FT-IR were used to analyze the main reason of the differences.

Ash-and-Slag Wastes of Energy Sector as Raw Material for Production of Rare-Earth Metals and Alumina

The results to develop a complex technology of co-extraction of germanium and gallium from the ash-and-slag wastes of coal combustion in Ukraine were presented. Based on the study of phase changes occurring in initial raw materials as a result of its processing, it was proposed to carry out a preliminary enrichment of the raw materials in order to produce secondary sublimates. Their further processing involves a combination of leaching soluble material with distillation of germanium in the form of tetrachloride. The resulting acidic solutions are trended to the gallium extraction. Optimum conditions of carrying out of processes are recommended.The chemical and phase composition of the resulting dump products and solutions have been defined. On the basis of it ways of their processing for the purpose of reception of alumina and building materials are recommended.

Effects of Nucleating Agents on Crystallization of Arc-Molten Slag from Incinerator Fly Ash

Glass-ceramics obtained from the electric arc furnace molten slag of incinerator fly ash was produced by applying nucleation and crystallization through heat treatment process. The effects of nucleating agent （TiO2 and Cr2O3） on the crystallization kinetics and heat treatment schedule of the slag were investigated. The results show that the nucleating agents changed the crystallization phase and morphology of the obtained glass-ceramics. The optimum heat treatment schedule of the glass with TiO2 was determined as nucleation at 952 K for 1.5 h and crystal growth at 1 258 K for 1.5 h, while those values with Cr203 were estimated at 971 K for 2 h and at 1 238 K for 2 h. TiO2 acting as nucleating agent could decrease the activation energy of the slag and shorten the total thermal treatment time in comparison with Cr2O3. The glass-ceramics obtained under the optimum heat treatment condition was environmentfriendly and had remarkable physical/mechanical properties and chemical durability.

Volumetric Variation and Rheology of Cement Based Mineral Additions （Blast Furnace Slag and Silica Fume）

The partial substitution of clinker by mineral additions offers very significant, both economical and environmental benefits. This adds value to industrial waste, and contributes also in the preservation of natural resources, like clay and limestone, as well as the reduction of greenhouse gas emissions （CO2）. This study is interested in the simultaneous effect of BFS （blast furnace slag） and SF （silica fume） on setting time and water requirement of cement paste. The volumetric variations are tested in mortars, prepared in the same mixture of pastes, and the tests indicate that the addition of slag increase the fluidity, reduce the water demand, shrinkage and expansion, compared to the mortar, containing ten percent （10%） of Silica Fume only. The images of pastes obtained by SEM （scanning electron microscopy）, are indicated an improvement of the microstructure of the paste with a large amount of slag, which leads to improve durability.

Comparative Study on Debris Flow Initiation in Limestone and Sandstone Spoil

Large spoil tips from reconstruction works as a result of the Wenchuan Earthquake in China are new debris flow hazards to the human society.However,there is a lack of detailed comparative study on debris flow initiation in different spoil materials.This paper describes a series of tests and analyses on debris flow characteristics(initiation,scale and mechanism) at six sites with limestone and sandstone materials near the Dujiangyan area.Research shows the limestone spoil contains debris flow prone clay content with high concentration of montmorillonite(highly expandable).In addition,limestone spoil is of such a low permeability that water mainly concentrates in the upper surface layer.Those factors make it easy for the increase of pore water pressure,decline of internal friction and conhesion force,leading to the occurence of large debris flows.In contrast,the sandstone spoil is less problematic and causes no major debris flow threats.Based on our research on the mechanism,the"stereometric drainage"method is sucessfully applied to control limestone spoil debris flows.

Use of Alkaline Slag and Crop Residue Biochars to Promote Base Saturation and Reduce Acidity of an Acidic Ultisol

This investigation was conducted by using alkaline slag and crop straw biochars to reduce acidity of an acidic Ultisol through incubation and pot experiments with lime as a comparison. The soil was amended with different liming materials: lime(1 g kg-1),alkaline slag(2 and 4 g kg-1), peanut straw biochar(10 and 20 g kg-1), canola straw biochar(10 and 20 g kg-1) and combinations of alkaline slag(2 g kg-1) and biochars(10 g kg-1) in the incubation study. A pot experiment was also conducted to observe the soybean growth responses to the above treatments. The results showed that all the liming materials increased soil p H and decreased soil exchangeable acidity. The higher the rates of alkaline slag, biochars, and alkaline slag combined with biochars, the greater the increase in soil p H and the reduction in soil exchangeable acidity. All the amendments increased the levels of one or more soil exchangeable base cations. The lime treatment increased soil exchangeable Ca2+, the alkaline slag treatment increased exchangeable Ca2+and Mg2+levels, and the biochars and combined applications of alkaline slag with biochars increased soil exchangeable Ca2+, Mg2+and K+and soil available P. The amendments enhanced the uptake of one or more nutrients of N, P, K, Ca and Mg by soybean in the pot experiment. Of the different amendments, the combined application of alkaline slag with crop straw biochars was the best choice for increasing base saturation and reducing soil acidity of the acidic Ultisol. The combined application of alkaline slag with biochars led to the greatest reduction in soil acidity, increased soil Ca, Mg, K and P levels, and enhanced the uptake of Ca, Mg, K and P by soybean plants.

Research on the slagging characteristics of blended coals in a pilot-scale furnace

This paper applies digital image techniques to observe the slagging characteristics of blended coals in a pilot-scale furnace. Collected deposit samples were analyzed by scanning electron microscopy linked with energy-dispersive X-ray analysis （SEM-EDX）, X-ray diffraction （XRD）, and X-ray Fluorescence （XRF） to acquire the microstructure, chemical composition, and mineralogy. The deposit thickness of three blends was analyzed between their parent coal A （Datong） and coal B （Shan）, and we noted that the time to reach a stable stage decreased with the ratio of coal B. The addition of coal A into coal B could remarkably restrained the growth and thickness of ash deposits. The results of XRD analysis indicated the initial layer was predominantly comprised of the crystalline minerals quartz, anorthite, or albite except for coal B. All of the blends and coals contained quartz and Ca- to Al-silicates （Ca0.68Na0.32）（All.68Si0.32）Si2O8 in the slag layer where iron-bearing minerals （e.g., ilvaite） were altered into an amorphous phase. The result of SEM-EDX suggested that there was an elemental disparity between the coal ash and deposit.

Attenuation of Metal Bioavailability in Acidic Multi-Metal Contaminated Soil Treated with Fly Ash and Steel Slag

A pot experiment was conducted with multi-metal （Pb, Cd, Cu, and Zn） contaminated acidic soil to investigate changes in available metal burden resulting from the application of industrial wastes （fly ash and steel slag）. The efficiency of amendments- induced metal stabilization was evaluated by diffusive gradients in thin films （DGT）, sequential extraction, and plant uptake. The stability of remediation was assessed by an acidification test and by chemical equilibrium modeling. Addition of fly ash （20 g kg-1） and steel slag （3 g kg-1） resulted in similar increase in soil pH. Both amendments significantly decreased the concentrations of metals measured with DGT （CDGT） and the metal uptake by Oryza sativa L. Significant correlations were found between CDGT and the concentration of a combination of metal fractions （exchangeable, bound to carbonates, and bound to Fe/Mn oxides）, unraveling the labile species that participate in the flux of metal resupply. The capability of metal resupply, as reflected by the R （ratio of CDGT to pore water metal concentration） values, significantly decreased in the amended soils. The CDGT correlated well with the plant uptake, suggesting that DGT is a good indicator for bioavailability. Acidification raised the extractable metal concentration in amended soil but the concentration did not return to the pre-amendment level. Equilibrium modeling indicated that the soil amendments induced the precipitation of several Fe, A1 and Ca minerals, which may play a positive role in metal stabilization. Chemical stabilization with alkaline amendments could be an effective and stable soil remediation strategy for attenuating metal bioavailability and reducing plant metal uptake.