磷石膏预分解的热分析研究

采用热分析的方法对磷石膏在不同掺碳量、不同气氛条件下的热反应过程进行了研究，针对近年来提出的利用水泥新型干法技术实现磷石膏预分解制硫酸联产水泥的设想，研究了磷石膏的热分解过程对预热分解炉的适应性。结果表明，在碳与磷石膏的混合体系中，碳仅能在一定程度上促进磷石膏分解，其完全分解温度接近1 300℃。而在较强还原气氛中，磷石膏+碳系统生成硫化钙，在约1 260℃时才完全分解。因此新型干法水泥工艺分解磷石膏制酸联产水泥新工艺在实际过程中将受限于硫酸盐及硫化物熔点较低与硫酸钙分解温度较高这对矛盾而不宜直接采用。     

磷石膏窑外分解中试研究

以无烟煤为还原剂、添加3.5%矿化剂,在有效容积为0.25 m3的竖罐反应装置中对磷石膏进行了窑外分解中试研究。结果表明:随着反应温度的升高,磷石膏分解率逐渐增大;适宜的还原氛围有利于磷石膏的热分解进程;混合物料的碳硫比为0.75时,在950℃条件下磷石膏分解率最高可达90.6%,窑气中SO_2体积分数约为8%。HSC热力学计算表明:生成中间产物Ca S是硫酸钙热分解过程的必经阶段,鼓入适量空气是保证磷石膏热分解中间产物Ca S较为彻底地转化为Ca O与SO_2的必要条件。     

磷石膏中杂质及预处理对α半水石膏性能的影响

磷石膏在建筑材料上的应用受到限制源于其中的杂质对产品质量和生产经济产生了不利影响。磷石膏中可溶性磷和氟化物的存在对α半水石膏的强度和凝结时间有负面影响。采用XRD、SEM和FTIR分析,结合宏观性能实验,对磷石膏中杂质及预处理对α半水石膏的性能的影响进行了研究。研究结果表明,由于杂质的存在,原状磷石膏制备出的α半水石膏强度很低,不易凝结,不能应用于实际生产。经过石灰中和后的磷石膏作为原料,强度较好。杂质可溶磷中的磷酸对α半水石膏的性能影响最大,强度显著降低,凝结时间延长,可溶氟含量大于1%时对其性能影响较大,有促凝作用。石灰处理磷石膏时,中性和弱碱性环境最利于α半水石膏形成和生长,性能最好。     

磷石膏再生利用途径的综合评价

依据层次分析法原理,用经济、环境和资源化3个影响因素建立磷石膏资源化途径优选的递阶层次结构模型。以山东某化工厂生产磷酸产生的磷石膏为研究案例,从磷石膏组成成分与含量分析的角度出发,结合磷石膏各资源化途径的独特要求,探讨磷石膏资源化特性与资源化途径的密切关系,拟合出磷石膏的各种资源化特性,作为结构模型中的资源化因子。然后分别对模型中的3个影响因素进行定性和半定量化处理,最终实现磷石膏资源化途径优选的决策评价,为政府部门和环境管理者提供决策参考。     

初始含水率及固结特性对湿法磷石膏堆场渗滤液产量的影响

目前我国的大部分磷石膏采用堆存处置,但对磷石膏等工业固废堆场渗滤液产量的研究较少。从磷石膏的水分存在形式及变化分析出发,通过固结实验确定孔隙水的沉降挤出性能,建立磷石膏堆场水量平衡分析模型,对影响渗滤液的各因素进行分析,按照水量平衡分析法提出渗滤液计算公式,演算了某含水率条件下各阶段的渗滤液产量、不同含水率条件下和不同计算方法的总渗滤液产量,并进行了分析。分析表明,磷石膏堆场运行初期需要补充新鲜水量才能保证堆场正常运行,随时间的增加渗滤液产量逐渐增加,但各阶段的渗漏液产量与整个运行周期内的平均产量计算结果相差较大,整个周期内总渗滤液产量随磷石膏的饱和初始含水率增大而减少。经过对各计算公式的比较,仅考虑降雨蒸发量的堆场盈亏水量计算结果偏大,未考虑沉降挤出水量的计算结果偏小,采用本文推荐的计算公式可得出较为科学合理的渗滤液产量。     

糠醛渣和磷石膏对菱镁矿粉尘污染土壤的改良效果研究

采用盆栽试验,研究糠醛渣、磷石膏及两者混合物施入菱镁矿粉尘污染土壤后,土壤理化性质以及玉米幼苗生长状况、生物量、叶绿素含量、超氧化物歧化酶(SOD)、过氧化氢酶(CAT)、过氧化物酶(POD)活性的变化,旨在了解糠醛渣和磷石膏对菱镁矿粉尘污染土壤的改良作用与效果。结果表明:糠醛渣和磷石膏均能显著增加土壤中微生物生物量碳和氮,糠醛渣能有效降低土壤p H,增加有机质含量;磷石膏能有效调节土壤水溶性Mg2+/Ca2+。糠醛渣和磷石膏混合施用时,玉米幼苗最大根长、株高、生物量、叶绿素含量及SOD、CAT、POD活性均优于其他处理组。可见,糠醛渣与磷石膏可有效改善菱镁矿粉尘污染土壤理化性质,促进植物生长,且两者混合施用效果优于单施。     

Plackett-Burman设计和响应曲面法优化除磷陶粒的制备

为制备得到除磷效果较强的功能型陶粒,采用Plackett-Burman和响应曲面法对陶粒原料配比进行优化研究。采用Plackett-Burman实验设计筛选出具有显著除磷效应的4种原料——粉煤灰、水泥、石膏和氢氧化钠。以Box-Behnken Design响应面法建立数学回归模型,确定了最佳原料配比为:粉煤灰60.0 g、水泥15.0 g、氨基材料2.0 g、生石灰15.0 g、石膏3.0 g、氢氧化钠15.0 g,制得的陶粒磷去除率可达93.04%,颗粒强度为118.3 N。通过显著性检验和响应曲面等高线图分析,粉煤灰和氢氧化钠是显著影响陶粒磷去除率的主要原料,且粉煤灰与石膏、粉煤灰与氢氧化钠对陶粒的磷去除率有显著的交互影响,显著性p值分别为0.010 8和0.029 5。     

中国磷石膏资源化管理分析

磷石膏是湿法生产磷酸工艺过程中的伴生物,产生量巨大,对环境造成了很大的影响.磷石膏的资源化利用正在国内悄悄兴起,对磷石膏的规范管理也势在必行.阐述了美国磷石膏的产生以及管理的现状,对比中国现有磷石膏的资源化利用及管理的现状,为中国磷石膏的资源化管理政策提出建议.     

磷石膏的改性及其在水泥生产中的应用

研究了磷石膏的改性方法及改性磷石膏在水泥生产中的应用，结果表明，通过改性，可将磷石膏中对水泥有害的杂质转化为难溶性，并能改善磷石膏中硫酸钙的溶解性能，改性磷石膏可以替代天然石膏用于水泥生产。     

磷石膏基胶结材固结磷尾矿性能及浸出特征

以磷石膏基材料代替水泥作为磷尾矿充填胶结材,研究了磷尾矿固结浆体和硬化体性能、浸出液污染特性和固结机理。结果表明,在同样条件下,磷石膏基材料固结磷尾矿浆体比水泥泌水量要小、浆体流动性能更优;磷石膏基材料胶结磷尾矿硬化体除3 d抗压强度略低外,其他龄期的强度是水泥的1.21~1.95倍。3 d之后,磷石膏基材料和水泥胶结尾矿硬化体浸出液总磷含量基本相近,但pH明显远低于水泥,总磷也低于污水综合排放标准限值,对环境危害低。硬化体SEM和XRD分析发现,磷石膏基材料水化生成的水化硅酸钙凝胶、针状钙矾石晶体和磷尾矿中白云石、含磷矿物生成的透钙磷石等,是整个磷尾矿固结硬化体具有较高强度、较低总磷含量和pH值主要原因。该研究表明,磷石膏基材料固化磷尾矿比水泥更有应用前景。     

Urban energy mining from sewage sludge

This work showed that sewage sludge could be a strong candidate for biodiesel production. High lipid content (18–20%) with C_16?18-carbon range was experimentally identified and measured. These lipids from sewage sludge were converted into biodiesel via the transesterification reaction with MgO–CaO/Al₂O₃ derived from magnesium slag, and biodiesel conversion was ～98%. The experimental work enabled explaining that temperature is the main driving force for the transesterification reaction, which can be enhanced in the presence of CO₂. This also enables combination of esterification of free fatty acids and transesterification of triglycerides into a single process within 1 min in the temperature range of 350–500 °C. Sewage sludge residue after extracting lipids was also a good feedstock for recovering energy via thermo-chemical processes. The impact of CO₂ co-feed on the pyrolysis/gasification process of SS residue was also investigated in this work. The CO₂ injected into the thermo-chemical process remarkably increased the generation of CO by a factor of 2. Moreover, the introduction of CO₂ into the pyrolysis/gasification process enabled reducing condensable hydrocarbons (tar) by expediting cracking; thus, utilizing CO₂ as chemical feedstock for the gasification process not only leads to higher thermal efficiency but also has environmental benefits.     

烧结烟气脱硫剂性能的研究

为了提高脱硫效率和合理利用烧结过程中产生的机头灰,在半干法烟气脱硫剂生石灰中,加入一定量的烧结机头灰作为脱硫催化剂。在测定机头灰与生石灰化学成分、粒度和比表面积的基础上,研究和分析了机头灰与生石灰的质量配比对于脱硫效率的影响。结果表明,脱硫剂与机头灰在粒径分布和比表面积上都较接近,但经过消化活化后的混合脱硫剂的比表面积明显增大。当机头灰添加量为脱硫剂质量的2%～5%时,脱硫效率提高了2%～3%。机头灰与生石灰的胶凝反应以及机头灰中Fe2O3的催化作用是主要的作用机理。     

新型微生物菌剂对垃圾渗滤液的除臭效果

利用从食材中筛选纯化的特定微生物制成新型复合菌剂,以不同浓度梯度处理垃圾渗滤液,测定其在自然条件下的嗅阈值,监测NH3和H2S即时挥发浓度的变化,评价菌剂的综合除臭效果,设计三因素三水平实验并采用响应面优化法对反应适宜的实验参数进行了优化。研究结果表明,新型复合菌剂的投加会使垃圾渗滤液嗅阈值明显下降;响应面优化模型分析表明,反应时间2.5 d时和0.5%的菌剂投加对抑制NH3的挥发效果最好,而反应时间2.5 d和0.2%的投入量对抑制H2S的挥发效果最好,氧气的供应情况对两者的挥发抑制效果影响不显著。     

改性玉米秸秆吸附Cu2+的动力学和热力学

本研究用ZnCl2作为活化剂,使用功率640 W的微波照射4 min的方法制备改性玉米秸秆。考察投加量、pH、吸附时间对吸附性能的影响,并对等温吸附特征、吸附动力学和热力学进行了系统研究。结果表明:投加量为0.2 g,pH为6,改性玉米秸秆对Cu2+具有很好的吸附效果,吸附在8 h后达到平衡。该吸附过程符合Langmuir及Freundlich等温吸附模型和准二级动力学方程,其反应的吉布斯自由能△G<0,为自发反应过程。     

CS-Fe和CS-Fe/Ni的制备及其用于去除钴离子

以氯化铁为铁源，硼氢化钠为还原剂，壳聚糖为稳定剂，采用液相还原法制备壳聚糖稳定纳米铁（CS-Fe）；并以氯化铁为铁源，硫酸镍为镍源，硼氢化钠为还原剂，壳聚糖为稳定剂，采用液相还原共沉淀法制备壳聚糖稳定纳米铁镍（CS-Fe/Ni）。通过SEM、EDS、XRD、FT-IR等表征手段，对所制备的CS-Fe和CS-Fe/Ni的形貌及微观结构进行表征，并以Co²⁺为目标去除物评价CS-Fe和CS-Fe/Ni的反应活性。初步研究表明，制成的CS-Fe含有单质纳米铁，颗粒多数以30~90 nm球形颗粒为主；而CS-Fe/Ni材料中含有纳米铁镍，颗粒多数以30~60 nm球形颗粒为主；在相同的实验条件下，反应60 min，CS-Fe/Ni对Co²⁺的去除率高达100%，但是CS-Fe仅为88%，即CS-Fe/Ni对Co²⁺的去除率比CS-Fe高。     

How does biased technological progress affect haze pollution? Evidence from APEC economies

Biased technological progress is the act of energy conservation and emission reduction by changing the marginal rate of substitution. In this study, we introduced renewable energy into a production function, and proposed a method of identifying biased characteristics of technological progress, based on marginal productivity theory. A panel dataset for the Asia–Pacific Economic Cooperation (APEC) economies from 2000 to 2017 was analyzed to explore the effect of biased technological progress in reducing particulate matter (PM_2.5). We found that input biased technological progress tended to use more non-renewable energy. Input biased technological progress aggravated haze pollution; however, this effect decreased as the PM_2.5 concentration increased. Output biased technological progress significantly reduced haze pollution in high-income economies, but increased it in low-income economies. The effect of neutral technological progress on haze pollution was the opposite of the effect from output biased technological progress. We also found that increasing renewable energy consumption and reducing energy intensity were separate effective paths for input and output biased technological progress, respectively, to mitigate haze pollution. For neutral technological progress, improving total factor productivity was an important way to mitigate haze pollution. Finally, several policy recommendations are proposed to mitigate haze pollution in APEC economies.

     

低温等离子体氧化氨气影响因素及动力学研究

采用电晕放电低温等离子体处理模拟氨气恶臭气体,考察了输入功率、初始浓度、气体湿度、停留时间等因素对降解效果和能量效率的影响,同时对反应过程进行了动力学研究。研究表明,输入功率以及停留时间对氨气降解的影响是积极的,但能量效率随着两者的增加先增大后减小。氨气的降解率随着初始浓度的增加而降低,而能量效率随着输入功率的增加而增加。氨气降解率和能量效率均随着气体湿度的增加而增加,当气体湿度为45%时达到最大值,然而随着气体湿度的进一步增加,其降解率和能量效率反而降低。反应尾气中臭氧浓度随着输入功率的增加而不断升高,而氨气的存在却使臭氧浓度有不同程度的降低。对电晕放电低温等离子体处理NH3的反应动力学进行了分析,得到NH3的反应速率常数为kNH3=0.0707 m3/(W·h)。     

Dechlorination of PCBs in the simulative transformer oil by microwave-hydrothermal reaction with zero-valent iron involved

The conventional hydrothermal reaction with iron powder, NaOH and H₂O as reactants was reported to occur at temperature above 423 K, and iron oxides (Fe₃O₄ and NaFeO₂) and hydrogen were produced. In this study, microwave heating was adopted to take the place of conventional heating to induce the hydrothermal reaction. Under microwave irradiation, NaOH and H₂O absorbed microwave energy by space charge polarization and dipolar polarization and instantly converted it into thermal energy, which initiated the hydrothermal reaction that involved with zero-valent iron. X-ray diffraction (XRD) analysis found Fe₃O₄/NaFeO₂ and confirmed the occurrence of microwave-induced hydrothermal reaction. The developed microwave-hydrothermal reaction was employed for the dechlorination of PCBs. Hexadecane containing 100 mg L⁻¹ of Aroclor1254 was used as simulative transformer oil, and the dechlorination of PCBs was evaluated by GC/ECD, GC/MS and ion chromatography. For PCBs in 10 mL simulative transformer oil, almost complete dechlorination was achieved by 750 W microwave irradiation for 10 min, with 0.3 g iron powder, 0.3 g NaOH and 0.6 mL H₂O added. The effects of important factors including microwave power and the amounts of reactants added, on the dechlorination degree were investigated, moreover, the dechlorination mechanism was suggested. Microwave irradiation combined with the common and cheap materials, iron powder, NaOH and H₂O, might provide a fast and cost-effective method for the treatment of PCBs-containing wastes.     

A review on ex situ mineral carbonation

The increased CO₂ quantities in the environment have led to many harmful effects. Therefore, it is very important to decrease the CO₂ levels in the environment. CO₂ capture along with safe and permanent storage using mineral CO₂ sequestration method can play an important role to reduce carbon emissions into the environment. Mineral sequestration is a stable storage method that provides long-term storage and an appropriate substitute for the more popular geological storage method. The process is most suited for places where there is a lack of underground cavities for underground geological storage. Minerals rich in Ca and Mg are used predominantly in carbonation reactions. In addition, those alkaline wastes that are rich in Mg and Ca such as cement waste, steel slag and many process ashes can also be employed in CO₂ sequestration. Mineral carbonation could be used for the sequestration of billions of tonnes of CO₂ every year. However, various drawbacks related to mineral carbonation still need to be addressed, such as resolving the slow rate of reactions, necessity of large amounts of feedstock, decreasing the high overall cost of CO₂ sequestration and reducing the huge energy requirements to accelerate the carbonation reaction. This study explores a number of carbonation methods, parameters that control the process and future potential applications of carbonated products.

     

Nitrate reduction by green rusts modified with trace metals

A kinetic study of nitrate reduction by green rust (GR), a group of layered Fe(II)-Fe(III) hydroxide solids, was performed using a batch reactor system. The reduction rate of nitrate by GRs was affected by the anion content in the interlayer of GRs. GR containing F^- (GR-F) showed the fastest reduction rate while GR-SO₄ showed 9 times slower reaction rate than GR-F. The addition of 1 mM Pt or Cu to GR that contained 85 mM Fe(II) improved the reduction kinetics of nitrate by up to 200 times. Pt was an effective activating agent for all GRs. The sequential step reaction model that we proposed appropriately simulated the experimental data. The fastest nitrate reduction by GR-F with Pt was achieved at pH 9 among 7.5 to 11. At that condition, 1 mM nitrate transformed completely into ammonium within 23 min.