Using cemented paste backfill to tackle the phosphogypsum stockpile in China:A down-to-earth technology with new vitalities in pollutant retention and CO_(2) abatement

Phosphogypsum(PG),a hard-to-dissipate by-product of the phosphorus fertilizer production industry,places strain on the biogeochemical cycles and ecosystem functions of storage sites.This pervasive problem is already widespread worldwide and requires careful stewardship.In this study,we review the presence of potentially toxic elements(PTEs)in PG and describe their associations with soil properties,anthropogenic activities,and surrounding organisms.Then,we review different ex-/in-situ solutions for promoting the sustainable management of PG,with an emphasis on in-situ cemented paste backfill,which offers a cost-effective and highly scalable opportunity to advance the value-added recovery of PG.However,concerns related to the PTEs'retention capacity and long-term effectiveness limit the implementation of this strategy.Furthermore,given that the large-scale demand for ordinary Portland cement from this conventional option has resulted in significant CO_(2) emissions,the technology has recently undergone additional scrutiny to meet the climate mitigation ambition of the Paris Agreement and China's Carbon Neutrality Economy.Therefore,we discuss the ways by which we can integrate innovative strategies,including supplementary cementitious materials,alternative binder solutions,CO_(2) mineralization,CO_(2) curing,and optimization of the supply chain for the profitability and sustainability of PG remediation.However,to maximize the co-benefits in environmental,social,and economic,future research must bridge the gap between the feasibility of expanding these advanced pathways and the multidisciplinary needs.

Wetting-drying effect on the strength and microstructure of cementphosphogypsum stabilized soils

Phosphogypsum has often been used as an effective and environmentally friendly binder for partial replacement of cement,improving the engineering properties of slurries with high water content.However,the influence of phosphogypsum on the physicomechnical properties of stabilized soil subjected to wettingedrying cycles is not well understood to date.In this study,the effect of phosphogypsum on the durability of stabilized soil was studied by conducting a series of laboratory experiments,illustrating the changes in mass loss,pH value and unconfined compressive strength(qu)with wettingdrying cycles.The test results showed that the presence of phosphogypsum significantly restrained the mass loss in the early stage(lower than the 4th cycle),which in turn led to a higher qu of stabilized soil than that without phosphogypsum.After the 4th cycle,a sudden increase in mass loss was observed for stabilized soil with phosphogypsum,resulting in a significant drop in qu to a value lower than those without phosphogypsum at the 6th cycle.In addition,the qu of stabilized soils correlated well with the measured soil pH irrespective of phosphogypsum content for all wettingedrying tests.According to the microstructure observation via scanning electron microscope(SEM)and X-ray diffraction(XRD)tests,the mechanisms relating the sudden loss of qu for the stabilized soils with phosphogypsum after the 4th wetting-drying cycle are summarized as follows:(i)the disappearance of ettringite weakening the cementation bonding effect,(ii)the generation of a larger extent of microcrack,and(iii)a lower pH value,in comparison with the stabilized soil without phosphogypsum.

Study on synergistic leaching of potassium and phosphorus from potassium feldspar and solid waste phosphogypsum via coupling reactions

To achieve the resource utilization of solid waste phosphogypsum(PG)and tackle the problem of utilizing potassium feldspar(PF),a coupled synergistic process between PG and PF is proposed in this paper.The study investigates the features of P and F in PG,and explores the decomposition of PF using hydrofluoric acid(HF)in the sulfuric acid system for K leaching and leaching of P and F in PG.The impact factors such as sulfuric acid concentration,reaction temperature,reaction time,material ratio(PG/PF),liquid–solid ratio,PF particle size,and PF calcination temperature on the leaching of P and K is systematically investigated in this paper.The results show that under optimal conditions,the leaching rate of K and P reach more than 93%and 96%,respectively.Kinetics study using shrinking core model(SCM)indicates two significant stages with internal diffusion predominantly controlling the leaching of K.The apparent activation energies of these two stages are 11.92 kJ·mol^(-1)and 11.55 kJ·mol^(-1),respectively.

Copper slag assisted coke reduction of phosphogypsum for sulphur dioxide preparation

The reduction of phosphogypsum(PG)to lime slag and SO_(2)using coke can effectively alleviate the environmental problems caused by PG.However,the PG decomposition temperature remains high and the product yield remains poor.By adding additives,the decomposition temperature can be further reduced and PG decomposition rate and product yield can be improved.However,the use of current additives such as Fe_(2)O_(3)and SiO_(2)brings the problem of increasing economic cost.Therefore,it is proposed to use solid waste copper slag(CS)as a new additive to reduce PG to prepare SO2,which can reduce the cost and meet the environmental benefits at the same time.The effects of proportion,temperature and thermostatic time on PG decomposition are investigated by experimental and kinetic analysis combined with FactSage thermodynamic calculations to optimize the roasting conditions.Finally,the reaction mechanism is proposed.It is found that adding CS to the coke and PG system can increase the rate of PG decomposition and SO_(2)yield while lowering the PG decomposition temperature.For example,when the CS/PG mass ratio increases from 0 to 1,PG decomposition rate increases from 83.38%to 99.35%,SO_(2)yield increases from 78.62%to 96.81%,and PG decomposition temperature decreases from 992.4℃to 949.6℃.The optimal reaction parameters are CS/PG mass ratio of 1,Coke/PG mass ratio of 0.06 at 1100℃for 20 min with 99.35%PG decomposition rate and 96.81%SO_(2) yield.The process proceeds according to the following reactions:2CaSO_(4)+ 0.7C + 0.8Fe_(2)SiO_(4)→0.8Ca_(2)SiO_(4)+ 0.2Ca_(2)Fe_(2)O_(5)+ 0.4Fe_(3)O_(4)+2SO_(2)+ 0.7CO_(2)Finally,a process for decomposing PG with coke and CS is proposed.

Upcycling of phosphogypsum waste for efficient zinc-ion batteries

Zinc metal is a promising anode material for next-generation aqueous batteries,but its practical application is limited by the formation of zinc dendrite.To prevent zinc dendrite growth,various Zn^(2+)-conducting but water-isolating solid-electrolyte interphase(SEI)films have been developed,however,the required high-purity chemical materials are extremely expensive.In this work,phosphogypsum(PG),an industrial byproduct produced from the phosphoric acid industry,is employed as a multifunctional protective layer to navigate uniform zinc deposition.Theoretical and experimental results demonstrate that PG-derived CaSO_(4)2H_(2)O can act as an artificial SEI layer to provide fast channels for Zn^(2+)transport.Moreover,CaSO_(4)2H_(2)O could release calcium ions(Ca^(2+))due to its relatively high Kspvalue,which have a higher binding energy than that of Zn^(2+)on the Zn surface,thus preferentially adsorbing to the tips of the protuberances to force zinc ions to nucleate at inert region.As a result,the Zn@PG anode achieves a high Coulombic efficiency of 99.5%during 500 cycles and long-time stability over 1000 hours at 1 m A cm^(-2).Our findings will not only construct a low-cost artificial SEI film for practical metal batteries,but also achieve a high-value utilization of phosphogypsum waste.

Study on the Recycling of P in Phosphogypsum Leachate

After washing and curing, P is transported from the phosphogypsum to the leachate during the phosphogypsum detoxification process, providing two ideas for phosphorus recovery from phosphogypsum leachate: 1) preparation of calcium hydrogen phosphate for feed;2) preparation of calcium phosphate. A ready-to-use calcium oxide slurry was used to recover P from phosphogypsum leachate at a slurry concentration of 20% and a quantitative link between calcium to phosphorus ratio and fixation rate was fitted by mixed use batch experiments, reaction kinetics and thermodynamics, and theoretical calculations were used to demonstrate that phosphorus cannot be completely reused in the preparation of calcium hydrogen phosphate. The findings demonstrated that: a) the residual phosphorus concentration was in the range of 1300 - 1500 mg/L for the preparation of type I feed grade calcium hydrogen phosphate from phosphogypsum leachate;b) the P removal effect could reach 99.99% for the preparation of calcium phosphate from phosphogypsum using the theoretical equation: fixation rate = 87.91 - 10.96(Ca/P) + 3.22(Ca/P)2 (R2 = 0.9954);c) The procedure follows the suggested secondary kinetics, and according to the Freundlich isothermal model, the reaction process is under the control of the chemical reaction, with a reaction index of 0.7605. This study can be used as a theoretical guide for the recovery of P from phosphogypsum leachate, the preparation of products to bring about economic by-products, and the purification of wastewater for reuse.

磷石膏配料碳热熔融还原硫逸出及熔渣物相分析

基于配料计算在磷石膏中添加硅、铝、镁等,使其渣系满足矿渣棉生产对酸度系数、氢离子指数、黏度系数的要求。通过热重分析、熔融特性的测定及高温还原焙烧/熔融实验,探究了磷石膏配料在高温还原过程中硫逸出及熔渣的物相结构。结果表明:碳的加入可以促进磷石膏分解,加入量以n(C)/n(S)=0.5为宜;还原剂(石墨、无烟煤、焦炭)及配料的加入均可以降低磷石膏体系的熔融特征温度,CaO-MgO-SiO_(2)-Al2O_(3)四元相图计算表明配料体系在1255.73℃时形成最低共熔点。磷石膏及其配料在高温焙烧过程中的物相演变规律表明,CaS为CaSO_(4)还原过程的中间产物,配料中加入的SiO_(2)可结合更多的CaO促进CaS和CaSO_(4)反应的进行。还原熔融实验表明,n(C)/n(S)对熔渣硫含量及体系脱硫率影响较大。以焦炭为还原剂,磷石膏配料的酸度系数Mk=1.4、pH=4.85、n(C)/n(S)为0.5时,采用刚玉坩埚在1450℃下高温熔融20min后,脱硫率可达99.05%,硫高效逸出的同时形成的熔渣呈非晶态,具有良好的玻璃相结构。

石膏基复合相变储能材料的研究进展

建筑能耗、工业能耗和交通能耗是能源消耗的主要方式。其中,建筑能耗约占能源消耗的40%,建筑能耗的持续上升会增加碳排放和加速化石能源的消耗,因此,如何提升建筑材料的保温节能性能逐渐成为建筑材料领域的研究热点。储热技术不仅可以降低建筑能耗,还可以减少环境污染。相变储能材料具有优异的储放热能力,是实现热能储存以及温度控制的重要技术手段,在建筑节能领域具有广阔的应用前景。该文主要综述了石膏基相变储能材料的研究进展;根据石膏基相变材料的不同,分析归纳了石膏基有机相变材料和石膏基复合相变材料;介绍了浸渍法、多孔材料吸附法、微胶囊法等制备石膏基复合相变储能材料的方法和机理及影响石膏基相变储能材料的因素;展望了石膏基相变储能材料的研究方向。

CaCl_(2)和MgCl_(2)及其复合溶液制备α-半水石膏

为提高磷石膏的利用率和附加值,采用常压水热合成法以磷石膏为主要原材料制备α-半水石膏材料,主要研究不同质量分数的CaCl_(2)、MgCl_(2)及其复合溶液对磷石膏常压水热制备α-半水石膏脱水速率、物相组成和微晶形貌的影响。研究发现,磷石膏在95℃的CaCl_(2)溶液、MgCl_(2)溶液及CaCl_(2)-MgCl_(2)复合溶液中均可脱水转晶生成α-半水石膏。在CaCl_(2)溶液和MgCl_(2)溶液中,随着盐溶液浓度的增加,α-半水石膏的生成速率加快,其中经质量分数为35%的CaCl_(2)溶液反应4 h后或质量分数为25%的MgCl_(2)溶液反应1 h后,磷石膏可完全反应成α-半水石膏。在CaCl_(2)-MgCl_(2)复合溶液中,随着MgCl_(2)溶液浓度的增加,磷石膏的脱水转化速率逐渐加快,当CaCl_(2)质量分数≤19%和MgCl_(2)质量分数≥11%时,磷石膏水热反应1 h即可形成颗粒分布较为完整的α-半水石膏。

NaCl溶液浓度对磷石膏制备α-半水石膏转晶行为的影响

为提高湿法磷酸工艺排放的副产品磷石膏的利用率和附加值,采用常压水热合成法在NaCl溶液中制备α-半水石膏材料,研究了NaCl溶液浓度对α-半水石膏的结晶水含量、转晶行为、矿相组成和显微形貌的影响。研究结果表明,在温度为95℃质量分数为10.0%~20.0%的NaCl溶液中,磷石膏的结晶水含量均随着反应时间的延长逐渐降低,且降至约6%后将逐渐趋于平缓。结合XRD和SEM分析认为磷石膏在95℃质量分数为10.0%~20.0%的NaCl溶液中可脱水转晶形成稳定的六方柱状α-半水石膏。同时,磷石膏的脱水转晶速率呈现先缓慢上升而后快速升高,最后逐渐趋于平缓的变化趋势,属于典型的生长-成核动力学过程。随着NaCl溶液浓度的升高,α-半水石膏的诱导成核时间和晶体生长时间逐渐加快,总转晶时间逐渐缩短。其中,磷石膏在质量分数为20.0%的NaCl溶液中水热反应0.5 h后即可完全转变为α-半水石膏,与质量分数为15.0%的NaCl溶液相比缩短了1.38 h。因此认为,NaCl溶液浓度的提高有助于加快磷石膏的脱水转晶效率,这可为实际规模化生产α-半水石膏提供指导。

磷石膏动模量及阻尼比试验研究

近年来,磷石膏废渣的生产和堆积迅速增长,给库区安全以及环境带来不小的隐患。该文利用英国GDS公司的GDS-DYNTTS型微机控制振动三轴试验系统,对杨家箐磷石膏堆场库区不同取土深度下的磷石膏废渣进行动力特性试验,主要针对其在围压较大、偏压固结条件下的动弹性模量E_(d)、阻尼比λ进行较详细的研究。试验结果表明:密度相同条件下,动弹性模量随着固结比和围压的增加而变大,且在动应变ε_(d)增长初期曲线变化率不大,ε_(d)超过0.01%后动弹性模量会迅速减小,再逐渐趋于平缓;利用Kondner模型发现最大动弹性模量倒数和动应变的曲线呈较好的线性关系;对动模量比(E_(d)/E_(d0))曲线进行归一化分析,可以得出动模量与动应变的变化趋势,并且根据Darendeli模型对磷石膏动模量比的衰变阶段进行划分;利用最小二乘法对阻尼比与动弹性模量比λ-Ed/Ed0分布进行拟合,得到归一性较好的经验模型曲线。

磷建筑石膏矿渣水泥的水化过程与耐水性能

通过凝结时间、流动度、孔溶液pH值、抗折强度、抗压强度、吸水率、软化系数、水化热和水化产物分析测试,探究了磷建筑石膏(CPG)掺量对石膏矿渣水泥水化过程与耐水性能的影响.结果表明:随着CPG掺量的增加,石膏矿渣水泥的凝结时间缩短,流动度减小,吸水率与3 d水化累计放热量均增大;水泥净浆孔溶液的pH值在水化早期快速下降,56 d时保持不变;当CPG掺量从40%增加到70%时,56 d水泥净浆孔溶液的pH值从11.02减小到10.62,水泥胶砂的软化系数从0.98减小到0.91,主要水化产物均为二水石膏和钙矾石,并且钙矾石的含量随着CPG掺量的增加而减少.

聚丙烯纤维磷石膏胶结体早期力学强度特性及增韧机理研究

在传统水泥基复合材料的研究领域,纤维增强了材料的强度、韧性、延展性和抗裂性。为了提高磷石膏胶结体的早期强度,掺入聚丙烯纤维作为增强剂,开展了掺纤维磷石膏胶结体制备试验以及单轴抗压强度试验,分析了纤维对磷石膏胶结体破坏规律的影响,并通过SEM探究了纤维对磷石膏胶结体的增韧机理。研究结果表明:随纤维掺量增加磷石膏胶结体单轴抗压强度呈先增加后降低的趋势,且纤维最优掺量为1%;掺入纤维的磷石膏胶结体能延缓峰值抗压强度达到时间且破坏时的峰值应力更大,未掺入纤维的磷石膏胶结体在荷载超过应力峰值后快速失稳,掺入聚丙烯纤维的磷石膏胶结体则呈缓慢降低趋势;随着纤维的掺入,磷石膏胶结体的裂纹数量逐渐减少,且裂而不断,磷石膏胶结体的延性变形明显;微观下聚丙烯纤维表面附着有絮团状水化产物,且在磷石膏胶结体固结过程中相互缠结形成稳定的网状结构。研究成果可为磷石膏基复合材料在固废胶结充填现场的应用提供一定参考。

磷石膏改良滨海盐土效果及对小麦生长的影响

江苏滨海盐土(盐碱土)约66.22万公顷,大多未开发利用,主要因为含盐量很高,迫切需要进行改良。本试验采用田间试验方法,利用磷肥厂副产物磷石膏进行盐(碱)土改良试验。试验设置不施肥、不施用磷石膏、单施复合肥、施用复合肥+磷石膏不同用量等8个处理进行。结果表明,施用磷石膏可以降低盐碱土土壤pH,与不施用磷石膏的对照相比,施用磷石膏后表层0~20 cm土壤pH下降0.07~0.40个单位,碳酸氢根离子下降15.81%~43.53%;土壤钠离子浓度下降17.25%~89.83%,土壤钾离子含量增加8.17%~384.90%,土壤钙离子含量增加59.51%~1977.72%,土壤有机质增加4.51%~19.50%。施用磷石膏处理小区小麦叶片全氮含量较不施磷石膏处理增加7.85%~26.21%,叶片全磷含量增加5.02%~35.97%;小麦增产11.41%~45.26%。滨海盐土及盐碱土可以采用磷石膏进行改良,有较好的改良效果。综合考虑,以处理为30%复合肥1050 kg·hm^(-2)+磷石膏1125 kg·hm^(-2)和30%复合肥1050 kg·hm^(-2)+磷石膏2250 kg·hm^(-2)处理效果最好。

高掺量磷石膏道路基层材料配比设计及性能研究

按传统矿质混合料设计掺磷石膏道路基层材料难以大规模消纳磷石膏,为实现磷石膏在道路基层材料中大规模利用,通过骨料替代法进行高掺量磷石膏道路基层材料配比设计,确定适宜的碎石比(5~10 mm粒级与10~25 mm粒级质量比39∶61)后以不同掺量替代磷石膏基胶凝材料体系,再击实然后得出最佳含水率及最大干密度。通过对设计好的配比进行性能试验筛选,得出适宜配比为P85S60,养护28 d的试件抗压强度最大达5.39 MPa,体积变化率较低,且养护7 d后试件的体积增长稳定,体积变化率最终维持在0.5%左右,有利于现场道路施工应用。所有配比浸出氟、磷均满足《污水综合排放标准》(GB 8978—1996)一级限值,相较于常规水泥稳定碎石材料,该道路基层材料浸出液的酸碱性不会额外增加不利影响。通过XRD和SEM分析可知,胶凝材料水化产生的钙矾石和水化硅酸钙包裹在未反应的二水石膏周围,另外针棒状钙矾石和水化硅酸钙填充微小孔隙,使得试件整体结构密实、强度增加、体积稳定性增强。

改性磷石膏作水泥缓凝剂的研究

为将磷石膏应用于水泥缓凝剂,采用水洗等方式对磷石膏进行预处理。确定水洗磷石膏的最优用水量和水洗时间。对比研究天然石膏、原状磷石膏和改性磷石膏对硅酸盐水泥凝结时间和强度的影响。通过水化热、XRD和SEM分析改性磷石膏对硅酸盐水泥水化特性的影响机理。结果表明,磷石膏在液固比为4和水洗时间为25 min条件下水洗效果最佳;生石灰单掺以及生石灰和膨润土复掺对磷石膏中可溶性磷和可溶性氟表现出较好的固化效果;水洗改性后磷石膏可有效缩短水泥的凝结时间,提高早期强度,其中生石灰与膨润土按2∶1复掺水洗改性后磷石膏用于硅酸盐水泥,水泥初、终凝时间比使用原状磷石膏时缩短了50%和31%;改性磷石膏制备的水泥早期水化速率正常,水泥固结体结构致密,缺陷较少,早期强度高。

含硫酸盐废水对磷石膏胶结充填体材料性能的影响

鉴于矿山废水处理工艺具有一定的局限性,且磷石膏充填工艺需要消耗大量的水资源,将矿山含硫酸盐废水作为磷石膏充填用水并探讨其可行性。结果表明:废水中的硫酸盐能够促进磷石膏充填体的早期水化反应,进而提升充填体早期强度。当SO_(4)^(2-)浓度从0增加至30 000 mg/L时,充填体7 d强度由0.46 MPa升高至0.63 MPa,提高了37%;14 d强度由0.64 MPa升高至1.03 MPa,提高了61%。这主要跟水化产物钙矾石(AFt)和水化硅酸钙(C-S-H)的形成有关;但随着养护时间的增长,充填体28,60,90 d强度均在硫酸盐浓度为15 000 mg/L时达到最高。过量的SO_(4)^(2-)会干扰水化硬化过程,充填体后期强度因受到钙矾石的膨胀特性以及Na2SO4重结晶等影响而出现下降。研究结果可为矿山废水治理和磷石膏充填工艺优化提供新思路。

赤泥对磷石膏生物胶结的充填性能影响研究

为了解决充填骨料磷石膏强酸性劣化生物胶结充填体材料性能的问题,提出引入碱性固废赤泥的方法,探究添加不同质量分数的赤泥对磷石膏生物胶结充填料浆和充填体力学性能的影响。结果显示:在微生物诱导碳酸盐沉淀(Microbially Induced Calcite Precipitation, MICP)作用下,充填骨料中赤泥质量分数从0提高至80%时,充填料浆的泌水率由17%增至44%,表观黏度由585 mPa·s降至121 mPa·s,初、终凝时间分别增加了139%和135%。赤泥质量分数影响磷石膏生物胶结充填体的单轴抗压强度(Uniaxial Compressive Strength, UCS)。当赤泥占骨料总质量的20%时,充填体强度最高,为2 070 kPa,而过高的赤泥添加质量分数会导致UCS降低。强度的变化与赤泥的高碱性和干缩性有关。研究为碱性固废赤泥在磷石膏生物胶结充填中的应用提供理论基础和技术支撑,实现了固废资源化利用。

脱硫石膏和磷石膏作调凝剂对水泥性能影响的对比研究

使用工业副产脱硫石膏和磷石膏替代天然石膏作水泥调凝剂,是大量消纳这些固废的有效途径之一。有鉴于此,本文在对硫石膏和磷石膏理化性质研究的基础上,系统对比研究了两类石膏作调凝剂对水泥性能的影响,结果表明:脱硫石膏呈中性,但磷石膏来源不同,可呈强酸性、中性和强碱性。试验所用四种石膏的F、P、重金属浸出特性和反射性均满足一类建材的要求。脱硫石膏所配水泥的性能稳定性较好,掺量波动对水泥性能影响也较小,但磷石膏杂质成分复杂,所配水泥的凝结时间较长,一般为脱硫石膏所配水泥凝结时间的二倍以上。磷石膏产地和掺量变化对所配水泥的凝结时间和强度影响较大,使用过程中需严格控制掺量,否则会导致水泥不合格。

磷石膏综合利用现状及展望

磷石膏长期堆存带来的环境问题日益突出,磷石膏的无害化处理及综合利用迫在眉睫。总结了磷石膏在制备工业石膏及建材、水泥缓凝剂、制备硫酸联产水泥、路基材料、填充材料、土壤改良剂等领域的研究进展,介绍了磷石膏主要的研究方向,分析了磷石膏综合利用科研与工业化的关系,指出磷石膏科研与工业化的核心矛盾在于石膏本身价格较低,而磷石膏工业化处理成本较高,无法得到推广,并针对以上问题提出了多种解决思路。指出磷石膏未来的发展需要政府政策的支持,以及维持磷石膏市场需求和新增装置之间的平衡。磷石膏利用方面,无害化处置是基础,路基材料是磷石膏消纳的主要途径,土壤化和生态修复是磷石膏利用的新方向。