磷渣-粉煤灰基地聚物材料固化含砷废渣

为了处理有色金属冶炼厂产生的含砷废渣,利用磷渣-粉煤灰基地聚物材料对其进行固化处理。在磷渣∶粉煤灰=60∶40的基础上,通过单因素实验考察了石灰的掺量、化学激发剂水玻璃的模数及掺量、含砷废渣掺量等因素对砷固化体力学性能及砷毒性浸出特性的影响。结果表明:石灰外掺掺量为10%,水玻璃的模数为M=1.2,且其掺量为4%时,砷固化体的抗压强度和As毒性浸出浓度等指标综合效果达到最佳,地聚物材料对含砷废渣的最大固化容量为34%,其固化体抗压强度可达13.6 MPa,砷毒性浸出浓度为2.4 mg·L~(-1),满足危险废弃物堆存国家标准要求。通过XRD、SEM等手段分析可以得出,固化后砷通过化学键合的方式变成难溶盐的形式被地聚物材料牢牢地包裹,结构更加密实。     

含重金属污泥制砖毒性的浸出

污泥中的重金属是影响污泥处置利用的重要因素,污泥制砖可以有效固结重金属。采用污水厂污泥与页岩按一定配比混合制备烧结砖,通过毒性浸出实验,研究烧结砖对重金属的固化程度以及重金属浸出稳定性,从而评定烧结制砖的安全性。结果表明,在浸出液为中性和酸性条件下,Cu、Cr、As和Pb的浸出浓度基本保持稳定,浸出时间的影响不大,而Zn的初始浸出浓度相对较大,最终逐渐降低;碱性条件下,Cr、Cu和Pb的浸出浓度随时间变化不大,而Zn和As的浸出浓度则在浸提时间内无明显变化规律;但不同p H浸出液下的重金属浸出浓度均远低于国家限值,污泥制砖重金属固化效果好,安全可靠。     

电镀污泥基胶凝材料的制备及性质分析

将电镀污泥作为混合材料掺到水泥中,取代部分水泥熟料制备电镀污泥基胶凝材料。测定了胶凝材料试样的标准稠度用水量、凝结时间、胶砂流动度、强度等物理性能指标,同时分析胶凝材料试样的微观水化性能与累积孔体积,测定了胶凝材料的重金属浸出浓度。结果表明,在电镀污泥掺量为0.5%(质量分数,下同)时,制备的胶凝材料试样强度达到《通用硅酸盐水泥》(GB175—2007)规定的52.5R级水泥强度标准;在掺量为1.5%、2.5%时,制备的胶凝材料试样强度达到GB 175—2007规定的42.5R级水泥强度标准,且重金属浸出浓度满足《危险废物鉴别标准浸出毒性鉴别》(GB 5085.3—2007)要求。微观测试表明,电镀污泥的掺入使得水化放热总量降低。     

3种含铁材料对重金属和砷复合污染底泥稳定化处理

选用3种含铁材料FeCl3、Fe(OH)3和FePO4,开展重金属和砷(As)复合污染底泥的稳定化处理实验,并用毒性浸出测试(TCLP)的结果和底泥交换态重金属(Pb、Cd、Cu、Zn)及As的含量来评价其稳定化效果。结果表明,(1)FeCl3和FePO4降低了底泥pH值,Fe(OH)3轻微地提高了底泥pH值。(2)FeCl3活化了底泥中Pb、Cd、Cu、Zn,使其浸出量和交换态含量增加,对As浸出量的影响不大,但使底泥中As交换态含量明显降低,且在最大添加量(8.00 g/kg)时As交换态含量未检测出;Fe(OH)3降低了Cd交换态和浸出量,稍增加了As交换态和浸出量,但对Pb、Cu、Zn交换态和浸出量影响不明显;FePO4明显降低了Pb的浸出量和交换态含量,略微降低了交换态Cd、Zn含量,对交换态Cu影响不大,但明显增加了As的浸出量和交换态含量。综上,FeCl3对As具有较好的稳定化效果,但明显活化了底泥中的4种重金属;Fe(OH)3亦对底泥中Cd有一定稳定化效果;FePO4对Pb的稳定化效果较好,但明显活化了底泥中的As。显然,3种含铁材料都不能实现底泥中重金属和As的同时稳定化。     

矿区含砷尾矿及废渣稳定化研究

通过"硫酸-硝酸法"浸出实验,以砷的浸出浓度为控制指标,选用Fe Cl2为稳定药剂,对矿区砷渣进行药剂稳定化研究。考察Fe/As摩尔比、p H值、粒度、温度及稳定时间对砷浸出浓度的影响,通过研究稳定化前后砷形态的变化,探讨重金属迁移转化规律。结果表明:砷浸出浓度随Fe Cl2投加量增加而降低,当Fe/As摩尔比为1,p H=6.5~7.5时,常温下稳定化1 h后,砷浸出浓度低于2.5 mg/L且基本达到稳定,达到《危险废物填埋污染控制标准》(GB 18598-2001)的入场要求;随反应温度升高,砷浸出浓度略有升高;矿渣稳定化处理后,砷从生物有效性高和毒性大的形态逐渐转化为毒性小、稳定性强的形态,但矿物组成和化学组成不同,砷形态的迁移转化也略有不同。     

碱激发胶凝材料及其固化Pb~(2+)的试验研究

对碱激胶凝材料(碱-偏高岭土、碱-矿渣和碱-粉煤灰)与水-水泥体系固化Pb2+进行了试验研究,其中水-水泥体系为对比样.结果表明:对于相同稠度的碱激发胶凝材料,即使Pb2+含量达到2.4%,除了碱-粉煤灰的抗压强度略低外,其他都达到30 MPa以上,满足填埋或做建筑基材的使用要求;与水泥相比,碱激发胶凝材料能显著降低重金属离子(Pb2+)浸出浓度,其规律性与其NH4+交换容量大小的规律性一致,与其固化体的抗压强度的大小没有相关性.     

硫酸钙对含电镀污泥渣料水泥基材料性能的影响

为了提高危险废物电镀污泥的高值化利用程度，研究了掺加CaSO₄对含磨细粉(由电镀污泥协同建筑渣土高温处理渣料磨细得到)水泥基材料力学性能、微观结构特征及重金属浸出的影响及机理。结果表明：CaSO₄掺量(基于其在胶凝材料的质量占比)为0.6%时，其长期力学性能较优，含磨细粉水泥基材料养护60 d后抗压强度和抗折强度比未掺加CaSO₄时分别提升20.1%和22.2%。适量的CaSO₄可以补充含磨细粉水泥基材料基体中Ca²⁺含量，促进水泥和磨细粉中具有潜在水化活性的组分充分进行水化，同时使基体中生成更多的钙矾石填充孔隙，从而增强了基体结构密实度。研究还发现多余钙矾石的形成对重金属离子的固结起到了正向作用，适量的CaSO₄掺加能明显降低含磨细粉水泥基材料基体中有害重金属离子的浸出浓度。当CaSO₄掺量为0.6%时，含磨细粉水泥基材料养护28 d后，Cu、Ni、Zn的浸出率比未掺加CaSO₄时分别降低了33.6、31.0、...     

高砷烧渣酸浸-深度还原-磁选提铁除杂

对云南某高砷烧渣进行了酸浸-深度还原-磁选实验研究,采用HSC、SEM-EDS、XRD等检测技术分析了提铁脱杂的机理。研究结果表明,原料中Fe品位为57.35%,含As高达2.78%,As主要以金属砷酸盐形式赋存,Cu和Zn的品位分别为0.52%和0.57%。在浸出温度60℃,硫酸质量分数25%的条件下,浸出作业As脱除率为86.43%。浸出渣碳热深度还原最佳实验条件为:还原温度1 050℃,还原时间120 min,煤粉质量分数30%,砷的作业挥发率78.23%。焙烧样品经磁选后,最终获得铁品位71.19%,总回收率约92%,含As 0.08%,含Cu 0.29%,含Zn 0.10%的铁精矿。基础理论分析及样品特性研究结果表明,酸浸促使难溶性金属砷酸盐中As转变为易溶性的H_3AsO_4,碳热深度还原实现了氧化铁矿物向金属铁相的转变以及As的进一步脱除。研究为类似硫酸烧渣的综合利用提供了一定的理论基础和技术支撑。     

针对含砷硫酸烧渣酸浸液的铁盐沉淀固砷

为考察含砷硫酸烧渣中酸浸脱砷效果和铁盐沉淀固砷行为,采用常温常压酸浸法脱除硫酸烧渣中的砷,并对进入浸出液中的砷以铁盐沉淀的形式脱除,进而对沉淀渣的浸出毒性进行研究。同时,研究了磨矿细度、酸浓度、固液比、浸出时间对硫酸烧渣中砷脱除效率的影响。结果表明,通过控制浸出参数可以将硫酸烧渣中砷的质量分数降低到0.2%以下,通过调节浸出液的pH和Fe/As摩尔比将其中的砷以沉淀的形式脱除。当Fe/As 2、pH=4～6时,溶液中砷浓度降到了0.5 mg·L~(-1)以下。沉淀砷渣主要是以非晶态的形式存在,提高铁砷比有利于提高砷渣稳定性,从而降低浸出毒性。在Fe/As=3、pH=6.04～6.22的条件下,得到的沉淀渣的浸出毒性为0.711 mg·L~(-1)。因此,通过酸浸脱除硫酸烧渣中的砷,进而采用铁盐沉淀的方法能够实现硫酸烧渣中砷的安全处置。     

复掺粉煤灰吸附剂碳化固碳反应及对重金属浸出特性的影响

针对复掺方法提高粉煤灰矿物固碳效率和重金属析出钝化作用,采用粉煤灰掺入不同比例的消石灰和氧化铝制备了固碳吸附剂,利用三相高压反应釜模拟碳酸化固碳反应,利用热重-差热测试分析了不同配比固化剂CO_2固定量和固定效率,对碳酸化反应前后固化剂的化学成分进行了分析,揭示了复掺粉煤灰吸附剂固碳机理,对碳酸化反应前后固化剂材料中重金属浸出毒性进行了实验模拟。结果表明,粉煤灰基固化剂复掺消石灰后,增加了固化材料中CaO量,显著提高了碳酸化体系中pH值,当粉煤灰与消石灰质量比为1∶1时,碳固定效率最高,达到6.98%。当消石灰的投加量为50%时,As、Cd、Cu、Pb、Cr受到了较强的抑制效果,Ni、Zn的浸出浓度没有变化。因此,复掺消石灰、氧化铝的粉煤灰基碳固化材料可有效改善纯粉煤灰碳酸化固定CO_2的效率,并可降低粉煤灰碳酸化后重金属的浸出毒性。     

水泥对垃圾焚烧飞灰的固化处理试验研究

对垃圾焚烧飞灰的化学成分、重金属物质的含量及浸出浓度进行测试分析.结果表明,飞灰中Pb和Cr等重金属物质浸出量超过浸出毒性标准,因而被认为是危险废物,必须进行固化处理.还考察了水泥对焚烧飞灰中重金属物质固化的效果,研究表明当飞灰掺量适当时,重金属物质的固化效果良好.重金属物质通过物理固封、替代,沉淀反应和吸附等形式可固化进水泥水化产物结构中.     

Bioleaching of metal from municipal waste incineration fly ash using a mixed culture of sulfur-oxidizing and iron-oxidizing bacteria

We investigated the behavior and characteristics of metal leaching from municipal solid waste incineration (MSWI) fly ash among pure cultures of a sulfur-oxidizing bacterium (SOB) and an iron-oxidizing bacterium (IOB) and a mixed culture. The IOB has a high metal-leaching ability, though its tolerability against the ash addition is low. The SOB might better tolerate an increase in ash addition than the IOB, though metal leaching ability of the SOB is limited. Mixed culture could compensate for these deficiencies, and high metal leachability was exhibited in the 1% ash culture, i.e., 67% and 78% of leachabilities for Cu and Zn, respectively, and 100% for Cr and Cd. Furthermore, comparably high leachabilities such as 42% and 78% for Cu and Zn were observed even in the 3% ash cultures. Characterization of metal leaching by the mixed culture revealed that the acidic and oxidizing condition had remained stable thorough the experimental period. Ferric iron remained in the mixed culture, and the metal leaching was enhanced by redox mechanisms coupling with the leaching by sulfate. An increase of ferrous iron enhanced the Cr, Cu, and As leaching. The optimum concentration of sulfur existed for As and Cr (5 gl(-1)) and Cu (2 gl(-1)). The presence of the degradable and non-degradable organic compound that must be existed in the natural environment or waste landfills made no significant change in the leachability of metals other than Zn. These results suggested that bioleaching using a mixed culture of SOB and IOB is a promising technology for recovering the valuable metals from MSWI fly ash.     

Preliminary study on removing Cs+/Sr2+ by activated porous calcium silicate—A by-product from high-alumina fly ash recycling industry

¹³⁷Cs⁺/⁹⁰Sr²⁺-containing radioactive wastewater is one of the most important problems that the world has been facing with. A by-product, activated porous calcium silicate, is generated at high levels by the pre-desiliconizing and soda-lime-sintering processes for producing Al₂O₃ from high-alumina fly ash. In order to examine if this by-product could be used as an absorbent for removal of ¹³⁷Cs⁺/⁹⁰Sr²⁺ from radioactive wastewater, various parameters, such as pH, adsorbent dose, contact time, and initial concentration, were discussed. Results indicated that the equilibrium reached in about 2 hr. Activated porous calcium silicate was highly pH sensitive and able to remove Cs⁺/Sr²⁺ in a near-neutral environment. The adsorption equilibrium was best described by Freundlich isotherm equations, and the adsorption of Cs⁺/Sr²⁺ was a physical process. The adsorption kinetic data could be better fitted by the pseudo-second-order model, and the adsorption was controlled by multidiffusion. Current study showed that activated porous calcium silicate has a good adsorption of Cs⁺/Sr²⁺ for their removal. However, other characteristics, such as selectivity because of coexisting cations, elution and regeneration, thermal stability, and acid resistance, should be discussed carefully before using it in an actual field.

Implications:Removing ¹³⁷Cs⁺/⁹⁰Sr²⁺ from radioactive wastewater is one of the tough issues that has been attracting more and more attention world widely, which is the same as fly ash. For recycling high-alumina fly ash, in which Al is extracted to produce Al₂O₃, a huge amount of activated porous calcium silicate is generated year by year. In this paper, this by-product was successfully used as an absorbent to remove ¹³⁷Cs⁺/⁹⁰Sr²⁺ from radioactive wastewater for the first time. Factors that affect the absorbability and the mechanisms were discussed in details, providing a possible choice for disposal of ¹³⁷Cs⁺/⁹⁰Sr²⁺-containing radioactive wastewater.     

Arsenic and copper stabilisation in a contaminated soil by coal fly ash and green waste compost

In situ metal stabilisation by amendments has been demonstrated as an appealing low-cost remediation strategy for contaminated soil. This study investigated the short-term leaching behaviour and long-term stability of As and Cu in soil amended with coal fly ash and/or green waste compost. Locally abundant inorganic (limestone and bentonite) and carbonaceous (lignite) resources were also studied for comparison. Column leaching experiments revealed that coal fly ash outperformed limestone and bentonite amendments for As stabilisation. It also maintained the As stability under continuous leaching of acidic solution, which was potentially attributed to high-affinity adsorption, co-precipitation, and pozzolanic reaction of coal fly ash. However, Cu leaching in the column experiments could not be mitigated by any of these inorganic amendments, suggesting the need for co-addition of carbonaceous materials that provides strong chelation with oxygen-containing functional groups for Cu stabilisation. Green waste compost suppressed the Cu leaching more effectively than lignite due to the difference in chemical composition and dissolved organic matter. After 9-month soil incubation, coal fly ash was able to minimise the concentrations of As and Cu in the soil solution without the addition of carbonaceous materials. Nevertheless, leachability tests suggested that the provision of green waste compost and lignite augmented the simultaneous reduction of As and Cu leachability in a fairly aggressive leaching environment. These results highlight the importance of assessing stability and remobilisation of sequestered metals under varying environmental conditions for ensuring a plausible and enduring soil stabilisation.     

Latent Hydraulic Reactivity of Blended Cement Incorporating Slag Made from Municipal Solid Waste Incinerator Fly Ash

Abstract

The reactivity of cement pastes made by blending Portland cement with slag from municipal solid waste incinerator (MSWI) fly ash was investigated to assess the potential of recycling MSWI fly ash slag. The slag, prepared by melting MSWI fly ash at 1400 °C for 30 min, was pulverized and ground, then blended with ordinary Portland cement (OPC), using various substitution levels to make slag-blended cement (SBC). The pozzolanic reactivity of the ecocement was then characterized by determining variations in the compressive strength, degree of hydration, microstructure, speciation, and mineralogical crystalline phases. The results suggest that the strength of the pastes at an early age decreased with increasing substitution levels, whereas the strength at a later age of the tested pastes (with substitution levels less than 10%) outperformed OPC paste because of typical SBC properties. The development of strength at a later age was also confirmed by X-ray diffraction and scanning electron microscopy techniques. This implies that active silica (Si) and alumina (Al) react with the hydration product, calcium hydroxide (Ca(OH)₂), to form calcium silicate hydrate (C-S-H), which contributed to strength development at a later age by the filling up of pores in the SBC pastes. The pozzolanic activity of the SBC pastes indicates that it is suitable for use as a substitute for OPC in blended cement.     

Remediation of metal-contaminated soils with the addition of materials - part II: leaching tests to evaluate the efficiency of materials in the remediation of contaminated soils

The effect of the addition of materials on the leaching pattern of As and metals (Cu, Zn, Ni, Pb, and Cd) in two contaminated soils was investigated. The examined materials included bentonites, silicates and industrial wastes, such as sugar foam, fly ashes and a material originated from the zeolitization of fly ash. Soil + material mixtures were prepared at 10% doses. Changes in the acid neutralization capacity, crystalline phases and contaminant leaching over a wide range of pHs were examined by using pH_stat leaching tests. Sugar foam, the zeolitic material and MX-80 bentonite produced the greatest decrease in the leaching of pollutants due to an increase in the pH and/or the sorption capacity in the resulting mixture. This finding suggests that soil remediation may be a feasible option for the reuse of non-hazardous wastes.     

Immobilization and volume reduction of heavy metals in municipal solid waste fly ash using nano-size calcium and iron-dispersed reagent

This study was conducted to examine the synthesis and application of novel nano-size calcium/iron-based composite material as an immobilizing and separation treatment of the heavy metals in fly ash from municipal solid waste incineration. After grinding with nano-Fe/Ca/CaO and with nano-Fe/Ca/CaO/[PO₄], approximately 30 wt% and 25 wt% of magnetic fraction fly ash were separated. The highest amount of entrapped heavy metals was found in the lowest weight of the magnetically separated fly ash fraction (i.e., 91% in 25% of treated fly ash). Heavy metals in the magnetic or nonmagnetic fly ash fractions were about 98% and 100% immobilized, respectively. Additionally, scanning electron microscopy combined with energy-dispersive X-ray spectrometry (SEM-EDS) observations indicate that the main fraction of enclosed/bound materials on treated fly ash includes Ca/PO₄-associated crystalline complexes. After nano-Fe/Ca/CaO/[PO₄] treatment, the heavy metal concentrations in the fly ash leachate were much lower than the Japan standard regulatory limit for hazardous waste landfills. These results appear to be extremely promising. The addition of a nano-Fe/Ca/CaO/PO₄ mixture with simple grinding technique is potentially applicable for the remediation and volume reduction of fly ash contaminated by heavy metals.

Implications: After grinding with nano-Fe/Ca/CaO and nano-Fe/Ca/CaO/[PO₄], approximately 30 wt% and 25 wt% of magnetic fraction fly ash were separated. The highest amount of entrapped heavy metals was found in the lowest weight of the magnetically separated fly ash fraction (i.e., 91% in 25% of treated fly ash), whereas heavy metals either in the magnetic or nonmagnetic fly ash fractions were about 98% and 100% immobilized. These results appear to be very promising, and the addition of nano-Fe/Ca/CaO/PO₄ mixture with simple grinding technique may be considered potentially applicable for the remediation and volume reduction of contaminated fly ash by heavy metals.     

高温堆肥与蚯蚓堆肥对城市污泥重金属形态的影响

采用高温堆肥和蚯蚓堆肥工艺,研究了城市污泥与锯末、粉煤灰或磷矿粉按不同比例混合堆肥前后重金属（Cu、Pb、Zn、Cd和As）交换态、碳酸盐结合态、铁锰氧化物结合态、有机结合态和残留态的变化。研究表明：高温堆肥和蚯蚓堆肥前后各试验污泥的重金属形态和含量呈现出不同的变化,都可以降低污泥中交换态Cu、Pb、Zn、Cd和As的含量;对于Cu和Pb,高温堆肥优于蚯蚓堆肥;对于Zn、Cd和As,蚯蚓堆肥优于高温堆肥。2种堆肥方式中,粉煤灰用量为10%的钝化效果优于20%,磷矿粉的钝化效果同粉煤灰一样。     

Development and Pilot Plant Evaluation of Silica- Enhanced Lime Sorbents for Dry Flue Gas Desulfurization

EPA’s efforts to develop low cost, retrofitable flue gas cleaning technology include the development of highly reactive sorbents. Recent work addressing lime enhancement and testing at the bench-scale followed by evaluation of the more promising sorbents in a pilot plant are discussed here.

The conversion of Ca(OH)₂ with SO₂ increased several-fold compared with Ca(OH)₂ alone when Ca(OH)₂ was slurrled with fly ash first and later exposed to SO₂ in a laboratory packed bed reactor. Ca(OH)₂ enhancement increased with the increased fly ash amount. Dlatomaceous earths were very effective reactivity promoters of lime-based sorbents. Differential scanning calorimetry of the promoted sorbents revealed the formation of a new phase (calcium silicate hydrates) after hydration, which may be the basis for the observed Improved SO₂ capture.

Fly ash/lime and diatomaceous earth/lime sorbents were tested in a 100 m³/h pilot facility incorporating a gas humidifier, a sorbent duct injection system, and a baghouse. The inlet SO₂ concentration range was 1000-2500 ppm. With once-through dry sorbent injection into the humidified flue gas [approach to saturation 10–20°C (18–36°F) in the baghouse], the total SO₂ removal ranged from 50 to 90 percent for a stoichiometric ratio of 1 to 2. Recycling the collected solids resulted in a total lime utilization exceeding 80–90 percent. Increased lime utilization was also investigated by the use of additives.     

Reaction of arsenic vapor species with fly ash compounds: kinetics and speciation of the reaction with calcium silicates

In coal combustion systems, the partitioning of arsenic between the vapor and solid phases is determined by the interaction of arsenic vapors with fly ash compounds under post-combustion conditions. This partitioning is affected by gas–solid reactions between the calcium components of the ash particles and arsenic vapors. In this study, bench scale experiments were conducted with calcium compounds typical of coal-derived fly ash to determine product formation, the extent of reaction and reaction rates when contacted by arsenic oxide vapors. Experiments conducted with arsenic trioxide (As₄O_6(g)) vapors in contact with calcium oxide, di-calcium silicate and mono-calcium silicate over the temperature range 600–1000 °C indicated that these solids were capable of reacting with arsenic vapor species in both air and nitrogen. Calcium arsenate was the observed reaction product in all the samples analyzed. Maximum capture of arsenic occurred at 1000 °C with calcium oxide being the most effective of the three solids over the range of temperatures studied. Using a shrinking core model for a first order reaction and the results from intrinsic kinetic experiments conducted in air, the reaction rate constants were found to be 1.4×10⁻³exp(−2776/T) m/s for calcium oxide particles, 7.2×10⁻³exp(−3367/T) m/s for di-calcium silicate particles and 5.5×10⁻³exp(−3607/T) m/s for mono-calcium silicate particles. These results therefore suggest that any calcium present in fly ash can react with arsenic vapor and capture the metal in water-insoluble forms of the less hazardous As(V) oxidation state.