Enhanced dealkalization of bauxite residue through calcium-activated desulfurization gypsum

A novel integrated approach to remove the free alkalis and stabilize solid-phase alkalinity by controlling the release of Ca from desulfurization gypsum was developed.The combination of recycled FeCl_(3)solution and EDTA activated desulfurization gypsum lowered the bauxite residue pH to 7.20.Moreover,it also improved the residual Ca state,with its contribution to the total exchangeable cations increased(68%-92%).Notably,the slow release of exchangeable Ca introduced through modified desulfurization gypsum induced a phase transition of the alkaline minerals.This treatment stabilized the dealkalization effect of bauxite residue via reducing its overall acid neutralization capacity in abating pH rebound.Hence,this approach can provide guidance for effectively utilizing desulfurization gypsum to achieve stable regulation of alkalinity in bauxite residue.

Effect of integration of mechanical ball milling and flue gas desulfurization gypsum on dealkalization of bauxite residue

The synergistic impact of mechanical ball milling and flue gas desulfurization(FGD)gypsum on the dealkalization of bauxite residue was investigated through integrated analyses of solution chemistry,mineralogy,and microtopography.The results showed a significant decrease in Na_(2)O content(>30 wt.%)of FGD gypsum-treated bauxite residue after 30 min of mechanical ball milling.Mechanical ball milling resulted in differentiation of the elemental distribution,modification of the minerals in crystalline structure,and promotion in the dissolution of alkaline minerals,thus enhancing the acid neutralization capacity of bauxite residue.5 wt.%FGD gypsum combined with 30 min mechanical ball milling was optimal for the dealkalization of bauxite residue.

Transformation of Flue-Gas-Desulfurization Gypsum to α-Hemihydrated Gypsum in Salt Solution at Atmospheric Pressure

Direct phase transformation of flue gas desulfurization gypsum in hot salt solution at atmospheric pres-sure was investigated.The effects of temperature,salt species,salt concentration,solids content,pH and modifier were examined.The crystals obtained under different conditions and solubility of calcium sulfate in contact with solid gypsum were also determined.α-Calcium sulfate hemihydrate crystals of stubby columnar shape and regular pentahedral sides were obtained under the following conditions：salt concentration 20%-30%,operation tempera-ture 95-100 °C,solids mass content in the slurry 10%-30% and neutral pH.Thermodynamic analysis revealed that phase transformation of calcium sulfate dihydrate to α-calcium sulfate hemihydrate occurs because of the difference in solubilities between the two solid gypsum phases in this system.

Promotion of conversion activity of flue gas desulfurization gypsum into α-hemihydrate gypsum by calcination-hydration treatment

The massive accumulation of flue gas desulfurization(FGD)gypsum produced in the wet limestone-gypsum flue gas desulfurization process not only encroaches on lands but also causes serious environmental pollution.The preparation ofα-hemihydrate gypsum(α-HH)is an important way to achieve high-value utilization of FGD gypsum.Although the glycerol-water solution approach can be used to produceα-HH from FGD gypsum under mild conditions,the transition is kinetically unfavorable in the mixed solution.Here,an easy pretreatment was used to activate FGD gypsum by calcination and hydration to readily complete the transition.The pretreatment deteriorated the crystallinity of FGD gypsum and caused it to form small irregular flaky crystals,which dramatically increased the specific surface area.Additionally,most of the organics adsorbed onto FGD gypsum surfaces were removed after pretreatment.The poor crystallinity,increased specific surface area,and elimination of organics adsorbed onto crystal surfaces effectively improved the conversion activity of FGD gypsum,thereby promoting dihydrate gypsum(DH)dissolution andα-HH nucleation.Overall,the phase transition of FGD gypsum toα-HH is facilitated.

Fluoride Ion Adsorption Effect and Adsorption Mechanism of Self-Supported Adsorbent Materials Based on Desulfurization Gypsum-Aluminate Cement

The adsorption method has the advantages of low cost,high efficiency,and environmental friendliness in treating fluorinated wastewater,and the adsorbent material is the key.This study combines the inherent anion-exchange adsorption properties of layered double hydroxides(LDHs).Self-supported porous adsorbent materials loaded with AFm and AFt were prepared from a composite cementitious system consisting of calcium aluminate cement(CAC)and flue gas desulfurization gypsum(FGDG)by chemical foaming technique.The mineral composition of the adsorbent material was characterized by X-ray diffraction(XRD)and Scanning electron microscopy(SEM).Through the static adsorption experiment,the adsorption effect of the mineral composition of the adsorbent on fluoride ions was deeply analyzed,and the adsorption mechanism was revealed.XRD and SEM showed that the main hydration phases of the composite cementitious system consisting of CAC and FGDG are AFm,AFt,AH_(3),and CaSO_(4)·2H_(2)O.FGDG accelerates the hydration process of CAC and inhibits the transformation of AFt to AFm.The AFt content increased,and the AFm content decreased or even disappeared as the amount of FGDG increased.Static adsorption experiment results showed that AFm and AFt in adsorbent materials could significantly enhance the adsorption of fluoride ions.The adsorption of F^(−)in aqueous solution by PAG tends more towards monolayer adsorption with a theoretical maximum capacity of 108.70 mg/g and is similar to the measured value of 112.77 mg/g.

Deep decalcification of factory-provided freezing acidolysis solution to achieveα-high-strength gypsum

The freezing acidolysis solution of the nitric acid-phosphate fertilizer process has a high calcium content,which makes it difficult to produce fine phosphate and high water-soluble phosphate fertilizer products.Here,based on the potential crystallization principle of calcium sulfate in NH_(4)NO_(3)-H_(3)PO_(4)-H_(2)O,the deep decalcification(i.e.calcium removal)technology to achieveα-high-strength gypsum originated from freezing acidolysis-solutions has been firstly proposed and investigated.Typically,calcium can be removed from the factory-provided freezing acidolysis-solution by neutralizing it with ammonia,followed by the addition of ammonium sulfate solution.As a result,the formation of calcium sulfate in the reaction system undergoes the nucleation and growth of CaSO_(4)·2H_(2)O(DH),as well as its dissolution and crystallization into short columnarα-CaSO_(4)·0.5H_(2)O(α-HH).Remarkably,with the molar ratio of SO_(4)^(2-)/Ca^(2+)at 1.8,the degree of neutralization(NH_(3)/HNO_(3) molar ratio)at 1.7,the reaction temperature of 94℃,and the reaction time of 300 min,the decalcification rate can reach 86.89%,of which the high-strengthα-CaSO_(4)·0.5H_(2)O(α-HH)will be obtained.Noteworthy,the deep decalcification product meets the standards for the production of fine phosphates and highly water-soluble phosphate fertilizers.Consequently,the 2 h flexural strength ofα-HH is 5.3 MPa and the dry compressive strength is 36.8 MPa,which is up to the standard of commercialα-HH.

Preparation of Multifunctional β-hemihydrate Gypsum using Oyster Shell Powder as the Partial Replacement of Ag/TiO2 Particle

This work aimed to use oyster shell powder (OSP) as the partial replacement of Ag/TiO2 particle to obtain multifunctional β-hemihydrate gypsum.Thus,the β-hemihydrate gypsum was mixed with different contents of OSP and Ag/TiO2 particle.Antibacterial and MB removal experiments were conducted to assess the antibacterial characteristic and photocatalytic activity of β-hemihydrate gypsum with Ag/TiO2 particle and OSP.Besides,the formaldehyde degradation test was carried out to evaluate its formaldehyde removal ratio.Moreover,their setting times,compressive and flexural strengths at 1,3,and 28 days were comparatively analyzed.The experimental results prove that the composite use of OSP and Ag/TiO2 particle provide feasible multifunction for the β-hemihydrate gypsum.They can further improve the bactericidal rates and exhibit extra MB removal ratios compared with the gypsum plasters with single Ag/TiO2 particle.Besides,they can increase the formaldehyde degradation ratios,and this promotion is related to the introduction of Ag/TiO2 particle.However,OSP delays the initial setting time but promotes the final setting time of β-hemihydrate gypsum,and Ag/TiO2 particle hardly affects the setting times.Furthermore,OSP reduces the strengths of plasters at 1,3,and 28 days.But in general,the composite addition of OSP and Ag/TiO2 particle increase the compressive and flexural strengths of gypsum plasters at 1,3,and 28 days.These results provide theoretical guidance for the recycling of OSP and the preparation of gypsum-based products with antibacterial and formaldehyde degradation capabilities.

Calcium sulfate whisker prepared by flue gas desulfurization gypsum:A physical–chemical coupling production process

In this paper,the solid waste desulfurization gypsum produced by coal-fired power plants was used as a raw material to prepare calcium sulfate whiskers with high application prospects.Calcium sulfate whiskers with uniform morphology and high aspect ratio can be prepared by hydrothermal method in sulfuric acid solution.A new process of desulfurization gypsum activated by high-energy grinding to reduce the reaction temperature and sulfuric acid concentration was developed.Through the comparison of product morphology,the best grinding time was determined to be 3.5 h.The mechanism of desulfurization gypsum through physical–chemical coupling to reduce energy consumption was clarified.The activation of desulfurization gypsum by grinding and the acidic environment provided by the sulfuric acid solution made the calcium sulfate solution reached rapid saturation and accelerated the nucleation rate.By calculating the conversion and crystallization rate of calcium sulfate whiskers,it was found that there were obvious"autocatalytic"kinetic characteristics during the crystallization process.

Influence of Thermally Treated Flue Gas Desulfurization(FGD) Gypsum on Performance of the Slag Powder Concrete

The feasibility of flue gas desulphurization （FGD） as concrete admixture was studied. A combined concrete admixture of the thermally-treated FGD gypsum and slag powder was explored. The FGD gypsum was roasted at 200℃ for 60 min and then mixed with the slag powder to form FGD gypsum-slag powder combined admixture in which the SO3 content was 3.5wt%. Cement was partially and equivalently replaced by slag powder alone or FGD gypsum-slag powder, at concentration of 25wt%, 40wt%, and 50wt%, respectively. The setting times, hydration products, total porosity and pore size distributions of the paste were determined. The compressive strength and drying shrinkage of cement mortar and concrete were also tested. The experimental results show that, in the presence of FGD gypsum, the setting times are much slower than those of pastes in the absence of FGD gypsum. The combination of FGD gypsum and slag powder provides synergistic benefits above that of slag powder alone. The addition of FGD gypsum provides benefit by promoting ettringite formation and forms a compact microstructure, increasing the compressive strength and reduces the drying shrinkage of cement mortar and concrete.

脱硫石膏制备α-半水石膏研究进展及应用

随着中国工业的不断发展,产生了大量的脱硫石膏,目前脱硫石膏的综合利用量虽在逐年增加,但其利用率却在降低,探寻脱硫石膏的高值化利用途径迫在眉睫,其中脱硫石膏资源化利用途径之一是将其脱水转化成α-半水石膏。利用脱硫石膏来制备高性能、高附加值的α-半水石膏,不仅能减轻石膏堆积对环境的污染,减少天然石膏的开采,还能带来新的经济效益。基于此,系统地综述了国内外脱硫石膏制备α-半水石膏的研究现状及影响因素,总结了其生产工艺路径及应用,并对推进脱硫石膏的减量化、资源化利用提出了展望,旨在提高固废利用率,促进“碳中和、碳减排”。

脱硫石膏强度及耐水性改善方法研究综述

针对脱硫石膏强度及耐水性改善方法和改性机理做了系统的归纳与分析。详细阐述了水泥、各种矿物掺合料、有机硅防水剂以及其他有机乳液等对脱硫石膏及其复合胶凝材料的强度和耐水性的影响,对各种改性方法的作用机理、优点以及不足之处进行了讨论。结果表明:掺入适量的水泥和矿物掺合料时会生成水硬性产物,脱硫石膏的强度和耐水性得到一定的改善,但是掺入过量时会造成不利的影响;水泥、粉煤灰和脱硫石膏之间的比例变化会对胶凝体系的强度和耐水性产生较大的影响;有机硅防水剂可以在脱硫石膏表面形成一层疏水性薄膜,显著提升脱硫石膏的耐水性,当与矿物掺合料复合作用于脱硫石膏时可以得到更好的力学性能和耐水性能;其他类型的有机防水剂均能改善脱硫石膏的耐水性,但是大部分会改变脱硫石膏的晶体形貌,对脱硫石膏的强度和耐水性产生不利影响;目前脱硫石膏的改性材料都比较复杂,单独作用时综合性能不佳,需要进一步研究与探讨更加简单、有效的改性材料和方法。

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。

脱硫石膏基自流平砂浆的制备与性能研究

目的以脱硫石膏为主要胶凝材料,通过优化材料组成制备出主要性能满足相关标准要求的石膏基自流平砂浆。方法将脱硫石膏、水泥、细砂、减水剂和缓凝剂等组分按不同比例混合,以力学性能、30 min流动度为考查指标,设计单因素试验,探讨各组分用量对自流平砂浆性能的影响。结果随水灰比的增加,脱硫石膏净浆流动度增加,力学性能降低;减水剂掺量增加会使脱硫石膏净浆的30 min流动度提高,力学性能降低;掺入普通硅酸盐水泥能明显提高净浆30 min流动度以及抗折、抗压强度;随细砂掺量的增加,脱硫石膏基自流平砂浆的30 min流动度降低,抗折强度明显降低,抗压强度在细砂掺量为40%后明显降低。结论经优化后配制出的脱硫石膏基自流平砂浆的力学性能和30 min流动度满足《石膏基自流平砂浆》要求。

粉煤灰基地聚合物的制备及其性能研究

以低钙粉煤灰为硅铝原料制备了地聚合物胶凝材料,研究了激发剂种类和掺量对地聚合物抗压强度的影响,以及产物对Cr^(3+)和Pb^(2+)固化效果。结果表明:当水玻璃掺量为15%,脱硫石膏掺量为7%时,所制得地聚合物抗压强度最高,3 d、 7 d、28 d龄期抗压强度分别为19.8 MPa、32.5 MPa和53.5 MPa;地聚合物对重金属离子Cr^(3+)和Pb^(2+)的固化效果均较好,其在去离子水和硫酸硝酸混合酸液中的浸出量均远低于国标限值。

工业废渣固化淤泥力学特性及微观机理研究

目的针对大宗固废难以消化、疏浚淤泥处理困难、传统水泥固化淤泥不符合新发展理念等问题,采用钢渣、石灰和脱硫石膏制备环保型复合固化剂,应用在淤泥质土固化处理领域,以达到“以废治废”的目的。方法对固化淤泥土开展无侧限抗压强度、pH、扫描电镜等试验及其固化机理探究。结果复合固化剂最优配比为钢渣5%、石灰9%、脱硫石膏6%,龄期28d时固化土的强度高达1.657MPa,略低于同掺量龄期的水泥固化淤泥土,但延性有显著提高。碱性环境主要由石灰提供,pH阈值约为13,当pH值约12~13时最有利于水化反应的进行。微观特性分析表明,AFt与C-S-H为固化土提供骨架结构作用,填充颗粒孔隙,使其形成更加致密的网状结构,显著提高了淤泥固化土的宏观力学特性。结论此环保型复合固化剂可以固化淤泥土用于建筑回填和路基填土,能有效提高淤泥的资源化利用率。

脱硫石膏与粉煤灰配施对碱化土壤改良及苜蓿生长的影响

【目的】筛选适宜新垦龟裂碱化土壤改良和苜蓿生长的脱硫石膏和粉煤灰配比。【方法】采用小区试验,试验设置CK(脱硫石膏0、粉煤灰0)、T1(脱硫石膏30 t/hm^(2)、粉煤灰15 t/hm^(2))、T2(脱硫石膏30 t/hm^(2)、粉煤灰30 t/hm^(2))、T3(脱硫石膏30 t/hm^(2)、粉煤灰45 t/hm^(2))、T4(脱硫石膏45 t/hm^(2)、粉煤灰15 t/hm^(2))、T5(脱硫石膏45 t/hm^(2)、粉煤灰30 t/hm^(2))、T6(脱硫石膏45 t/hm^(2)、粉煤灰45 t/hm^(2))共7个处理,研究脱硫石膏和粉煤灰配施对土壤pH值、碱化度和可溶性盐量及苜蓿生长影响。【结果】脱硫石膏和粉煤灰配施显著改善龟裂碱化土壤物理性质,与CK相比,T3处理土壤体积质量降低7.69%,土壤孔隙度和田间持水率分别提高9.69%和18.70%;脱硫石膏和粉煤灰配施对0~40 cm土层土壤化学性质改良效果较好,T4处理0~10、10~20 cm土层土壤pH值分别降低10.51%、11.66%,碱化度分别降低56.76%和50.27%;T4处理0~10、10~20、20~40 cm土层土壤可溶性盐量分别下降32.33%、52.55%、3.04%;T4、T1处理苜蓿增产效果较好,与CK相比,苜蓿鲜质量分别提高61.76%、43.21%,干物质量分别提高48.80%、30.72%;但脱硫石膏和粉煤灰配施量过大则会造成减产,T6处理苜蓿鲜质量和干物质量分别较CK降低19.69%、10.24%。【结论】脱硫石膏和粉煤灰配合施用能有效降低龟裂碱化土壤的体积质量、pH值、碱化度和可溶性盐量,提高土壤孔隙度、田间持水率,从而有利于苜蓿的生长和发育,其中45 t/hm^(2)脱硫石膏与15 t/hm^(2)粉煤灰为最优配比组合。

脱硫石膏在碱土改良中的无机固碳作用

脱硫石膏溶解产生的Ca^(2+)会和土壤中含碳的阴离子(CO_(3)^(2–)、HCO_(3)^(–))发生反应,最终将CO_(2)吸收并固定为土壤无机碳。脱硫石膏在碱土改良中的无机固碳作用对实现“碳中和”具有重要意义。以新疆阜康三工河流域的荒漠碱土为研究对象,以脱硫石膏为钙源物对0~20 cm土层进行改良。探究不同时间0~40 t·hm^(-2)脱硫石膏施用量下土壤无机碳(SIC)和土壤无机碳密度(SICD)的变化,从而研究碱土改良中的无机固碳作用。结果表明:施用脱硫石膏能显著减轻土壤碱害(pH下降),增加土壤盐分,同时具有无机固碳作用(SIC和SICD上升)(P<0.05)。脱硫石膏最佳施用量为30 t·hm^(-2),此时改良土层pH降至最低(8.24)。改良后0~46 d SIC含量相较对照组增加0.93 g·kg^(–1),SICD增加0.29 kg·m^(-2)(即CO_(2)固定量为1.06 kg·m^(-2))。改良过程中,脱硫石膏施用量与SIC、SO_(4)^(2–)和Ca^(2+)呈显著正相关(P<0.05),与pH、CO_(3)^(2–)、HCO_(3)^(–)和Na^(+)呈显著负相关(P<0.05)。气候因子对土壤无机固碳存在影响,增大相对湿度和降水量会抑制SIC含量和SICD增加,而增大风速、温度和太阳总辐射则有促进作用。研究结果为施用脱硫石膏改良碱土能增加土壤固碳潜力提供了直接证据。

十二烷基三甲基溴化铵改性纳米CaCO_(3)对刚果红的吸附性能

以固体废弃物脱硫石膏为原料,在加氨水、通CO_(2)气体条件下制备纳米CaCO_(3),用表面活性剂十二烷基三甲基溴化铵(DTAB)对纳米CaCO_(3)进行改性,对改性材料DTAB-CaCO_(3)进行表征。研究刚果红在DTAB-CaCO_(3)表面的吸附行为,考察影响DTAB-CaCO_(3)对刚果红吸附性能的因素,数学拟合吸附过程,计算热力学参数。结果表明,ρ(刚果红)=50 mg/L、m(DTAB-CaCO_(3))∶V(刚果红)=0.20 g/L、pH=2、t=120 min,吸附率为95%。该吸附过程为自发放热,符合Langmuir等温式的单分子层吸附模型和二级吸附动力学模型。

含钙镁煤基固废CO_(2)矿化封存及其产物性能研究进展

随着化石碳资源的过度消耗,导致CO_(2)等温室气体的大量排放,全球气候变化已经成为全人类面对的重大挑战之一,同时,煤炭资源开发利用过程中会产生大量的粉煤灰、脱硫石膏等含钙镁煤基固废。如何实现CO_(2)高效捕集与封存是当下面临的极具挑战性课题,粉煤灰、煤气化灰渣等大宗重污染工业固废的大规模综合利用仍亟待突破。在“双碳”目标下,利用煤基固废矿化封存CO_(2)是一项具有巨大潜力的高效应对全球变暖的策略,利用含钙镁煤基固废进行矿物碳酸化对于二氧化碳捕集与封存(CCS)以及固废的资源化处置都具有很大前景。然而,它的工业应用瓶颈依旧无法突破。综述了以典型煤基固废粉煤灰(FA)、脱硫石膏(FGDG)以及煤气化灰渣(CGS)为原料的CO_(2)矿化技术的发展现状,旨在探讨其技术局限性的原因。首先,简要阐述了煤基固废CO_(2)矿化的途径,揭示了煤基固废CO_(2)矿化反应过程和原理。其次,重点讨论了典型煤基固废的矿化潜力和工艺,明晰CO_(2)矿化过程中工艺参数对产物性能的调控机理。最后,总结了煤基固废CO_(2)矿化产物的性能并且利用全生命周期评估(Life Cycle Assessment,LCA)阐明矿化工艺的可行性及其对环境的影响。研究将对煤基固废CO_(2)矿化的工艺技术提供优化建议,以期推动煤炭工业的低碳转型战略目标。

盐溶液法制备半水石膏的工艺研究及探讨

这是一篇矿物材料领域的论文。利用脱硫石膏制备应用更为广泛的半水石膏对工业副产石膏的资源化利用有非常重要的作用,不仅可以避免对天然石膏的大量开采,还能实现对脱硫石膏的资源化利用。在脱硫石膏转化为半水石膏的过程中,以氯化钠和添加剂作为反应溶液,在常压下加热搅拌反应。研究了氯化钠浓度、添加剂浓度、固液比、转速和反应温度等因素对二水到半水石膏的相转化时间和晶体粒度的影响,氯化钠和添加剂浓度的增大,不仅会加快相转化过程,还对半水石膏晶体的平均长度和平均长径比有一定的抑制作用,而较高或较低的转速则会阻碍半水石膏晶体的成核和生长,过快或过慢的转速都会影响Ca^(2+)和SO_(4)^(2-)的碰撞频率,继而影响半水石膏的生成。降低固液比和升高温度也对相转化过程有一定的促进作用,在较低的温度下,由于相转化过程的驱动力不足,脱硫石膏难以转化为半水石膏。确定了脱硫石膏制备半水石膏的较佳工艺条件为:氯化钠浓度10%,添加剂浓度10%,固液比1:5,转速300 r/min,反应温度100℃。在较佳的工艺条件下,60 min即可完成反应。所制得的半水石膏晶体的平均长度高达127μm,平均长径比高达19。同时,研究了溶液中水分子活度、过饱和度和反应温度的关系,确定了相转化过程由温度和过饱和度所决定。