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 invest...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.展开更多
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...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.展开更多
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 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.展开更多
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 ...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.展开更多
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) preparatio...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)<sup>2</sup> (R<sup>2</sup> = 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.展开更多
Phosphogypsum(PG) is a solid waste produced in the phosphate fertilizer industry and is environmentally harmful.The decomposition of PG to recycle calcium and sulfur is a proper way to reutilize PG. Current work aims ...Phosphogypsum(PG) is a solid waste produced in the phosphate fertilizer industry and is environmentally harmful.The decomposition of PG to recycle calcium and sulfur is a proper way to reutilize PG. Current work aims at enriching the basic theory of coal decomposition process of PG. The emphasis was laid on the exploration of impact of main impurities on the process. On the other hand, according to Reaction Module, Equilib Module, and Phase Diagram Module of FactS age, the simulation computation was done on the systems of pure gypsum mixed with coal,with or without impurities for avoiding other impurities interference. Later, possible reactions in the process were deduced. Additionally, experiments were conducted in a TG-DTA integrated thermal gravimetric analyzer and a tube furnace. The products from the experiments were characterized and analyzed to verify the accuracy of theoretical calculations. The results showed that these impurities can change the decomposition process of PG. For example, aluminum oxide was transformed to calcium sulfoaluminate, while iron oxide was transformed to dicalcium ferrite. Furthermore, the results help to further improve the basic theory of phosphogypsum decomposition.展开更多
The distribution of water channels in the crystal morphology of type-α hemi-hydrated gypsum(α-HH) was theoretically detected to investigate the effect of water channels on the hydration reactivity of hemi-hydrate ph...The distribution of water channels in the crystal morphology of type-α hemi-hydrated gypsum(α-HH) was theoretically detected to investigate the effect of water channels on the hydration reactivity of hemi-hydrate phosphogypsum(HPG). Results showed that water channels were mainly distributed in the cylinders of α-HH crystal,whereas no water channel existed in the conical surfaces parallel to the z-axis. Increasing the number of water channels was critical to enhance the hydration activity of HPG compared with the hydration reactivity of industrial HPG and type-α high-strength gypsum. Controlling the technological parameters of crystallization by concentration of liquid-phase SO_4^(2-) made it possible to obtain HPG which had the stumpy crystals of α-HH and high hydration reactivity.展开更多
Carbide slag was used as an activator to improve the activity of anhydrous phosphogypsum.Carbide slag could greatly improve the mechanical strength of anhydrous phosphogypsum than K_(2)SO_(4).The compressive strength ...Carbide slag was used as an activator to improve the activity of anhydrous phosphogypsum.Carbide slag could greatly improve the mechanical strength of anhydrous phosphogypsum than K_(2)SO_(4).The compressive strength of 11 wt%carbide slag and 1 wt%K_(2)SO_(4)activated anhydrous phosphogypsum increased greatly to 8.6 MPa at 3 d,and 11.9 MPa at 7 d,and 16.0 MPa at 28 d,respectively.The rate of hydration heat was accelerated and the total hydration heat was increased,and more calcium sulfate dihydrate was formed and cross-linked with other parts which improved the compressive strength of anhydrous phosphogypsum under the effects of different activators.It was indicated that carbide slag was a highly effective and cost-efficient activator.The result provides a highly effective and low-cost method which results in a novel and high value-added method for the utilization of phosphogypsum in the future.展开更多
Phosphogypsum(PG)is a typical by-product of phosphoric acid and phosphate fertilizers during acid digestion.The application of cemented paste backfill(CPB)has been feasibly investigated for the remediation of PG.The p...Phosphogypsum(PG)is a typical by-product of phosphoric acid and phosphate fertilizers during acid digestion.The application of cemented paste backfill(CPB)has been feasibly investigated for the remediation of PG.The present study evaluated fluorine immobilization mechanisms and attempted to construct a related thermodynamic and geochemical modeling to describe the related stabilization performance.Physico-chemical and mineralogical analyses were performed on PG and hardened PG-based CPB(PCPB).The correlated macro-and micro-structural properties were obtained from the analysis of the combination of unconfined compressive strength and scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy imaging.Acid/base-dependent leaching tests were performed to ascertain fluoride leachab-ility.In addition,Gibbs Energy Minimization Software and PHREEQC were applied as tools to characterize the PCPB hydration and deduce its geochemical characteristics.The results proved that multiple factors are involved in fluorine stabilization,among which the calcium silicate hy-drate gel was found to be associated with retention.Although the quantitative comparison with the experimental data shows that further modi-fication should be introduced into the simulation before being used as a predictive implement to determine PG management options,the im-portance of acid/base concentration in regulating the leaching behavior was confirmed.Moreover,the modeling enabled the identification of the impurity phases controlling the stability and leachability.展开更多
Phosphogypsum-based materials (PBM) were synthesized with varied phase compositions of phosphogypsum,portland cement and fly ash.Effects of fractal growth characteristics on physicochemical properties,pore structure,c...Phosphogypsum-based materials (PBM) were synthesized with varied phase compositions of phosphogypsum,portland cement and fly ash.Effects of fractal growth characteristics on physicochemical properties,pore structure,compressive strength,as well as the hydration behaviour and mineralogical conversion of mortars were examined by a multitechnological approach,including mercury intrusion porosimetry,rietved phase analysis,thremal analysis,calorimetry and Fourier transforminfrared spectroscopy analysis.Expermental results indicate that the specimens cured with mosite resulted in higher strength and lower porosity compared with those cured in the drying chamber.In addition,a more complicated course of the aluminate and silicate reactions during the hydration process has been published,with the hydration products mainly consisting of calcium silicate hydrate (C-S-H),portlandite,ettringite,hemicarbonate,monocarboaluminate,calcite,quartz,a mixed AFm passed with carbonate,and hydroxide.After all,the nucleation process is a reaction that can be defined as a solid,liquid and gaseous phases that goes through the four stages of materialization mixing and modification,i e,hydration of low calcium content,secondary hydration,high calcium condensation and geoplymensation,respectively.The rupture,recombination,polymerization reactions of Si-O,Ca-O,Al-O bonds contribute to the nucleation mechanism that serves as the formation of C-S-H in hydration products.展开更多
The phosphogypsum particles coated with organic emulsion were prepared by coating three kinds of organic emulsion of silicone-acrylic,styrene-acrylic and acrylic.The structure and mineralogical characteristics,acid an...The phosphogypsum particles coated with organic emulsion were prepared by coating three kinds of organic emulsion of silicone-acrylic,styrene-acrylic and acrylic.The structure and mineralogical characteristics,acid and alkali resistance,water resistance and dissociation degree of coated phosphogypsum were studied by means of SEM-EDAX,optical microscope,gravimetric analysis and chemical detection.The results showed that the initial emulsion can be used directly for coating and granulation of phosphogypsum.The spray re-coating was carried out by using diluted emulsion with the water-to-emulsion mass ratio of 1∶1.The organic emulsion coated phosphogypsum crystal can be clearly observed,and the mixing zone at internal boundary between the organic emulsion and phosphogypsum crystal was distinguishable under the optical microscope.SEM photos showed that the surface of coated phosphogypsum particles was smooth.And the basic elements of C,O,S and Ca can be detected by EDAX.Organic emulsion can be solidified into film-network between the phosphogypsum crystals inside of the coated particles,and it can play a protective role in improving the acid resistance,alkali resistance and water resistance of phosphogypsum,and reduce the degree of dissociation of phosphogypsum in water.展开更多
The research used industrial by-products original phosphogypsum(PG)as the main raw material,slag(SG)and Portland cement(PC)as auxiliary materials,and the optimal additive amount was determined according to the compres...The research used industrial by-products original phosphogypsum(PG)as the main raw material,slag(SG)and Portland cement(PC)as auxiliary materials,and the optimal additive amount was determined according to the compressive strength value of the sample.Comprehensively evaluate the water resistance and volume stability of the samples,and determine the best formula for new roadbed stabilized materials.The results showed that when the weight ratio of PG,slag and cement was OPG:SG:PC=6:3:1,and mixed with 5%micro silica fume(MSF)and 3‰hydroxypropyl methyl cellulose(HPMC),the sample’s comprehensive performance was the best,specifically,the sample’s compressive strength in 60 days reached 28.8 MPa,the softening coefficient reached 0.9,and the expansion rate was stable at about−0.2%.In addition,the mechanism of action of enhancers MSF and HPMC was analyzed according to use Vicat device,X-ray diffractometer and scanning electron microscope.The best formula SP3GH3 has the best curing effect on soil.The 28-day unconfined compressive strength(UCS)of the sample reached 2.4 MPa,the expansion rate was less than 0.09%,and the water stability coefficient was above 0.79,which was higher than that of the samples cured by traditional cement and lime during the same period.展开更多
In order to decrease energy consumption for phosphogypsum( PG) pyrolysis process,a pilot-scale vertical-retort furnace was designed initiatively,and then mineralization agent was added to pyrolysis mixture. Calcium fl...In order to decrease energy consumption for phosphogypsum( PG) pyrolysis process,a pilot-scale vertical-retort furnace was designed initiatively,and then mineralization agent was added to pyrolysis mixture. Calcium fluoride( CaF_2) was proven to be a suitable mineralization agent, and the optimal parameters were: pyrolysis temperature 960 ℃,carbon-sulfur mole ratio 0. 7,reaction time 50 min,and CaF_2 dosage 4% by weight. Under this condition,PG decomposition and sulfur dioxide( SO_2) conversion were up to 89. 6% and 67. 3%,respectively. CaF_2 could lead to the formation of fluosilicate complexes,and facilitate PG decomposition at a low temperature. During pyrolysis process, calcium sulfide( CaS) was an inevitable intermediate substance,and only a part of total sulfur in the feedstock could be converted to SO_2.展开更多
As a by-product from the phosphate fertilizer industry Phosphogypsum (PG) was considered a potentially valuable source of the rare earth elements (REEs). Because of trace concentration of REEs in the PG (normally <...As a by-product from the phosphate fertilizer industry Phosphogypsum (PG) was considered a potentially valuable source of the rare earth elements (REEs). Because of trace concentration of REEs in the PG (normally <0.1% wt) and also their tiny and complex occurrence phases the recovery process would be highly challenging in both technology and economy. The studies on occurrences of REEs, REE recovery by physical methods and leaching using different lixiviants such as inorganic acids, H2SO4, HCl and HNO3, and organic chemicals, the effects of mechanical treatment of PG by microwaving and grinding on leaching efficiency of REEs, and resin-in-leach process were reviewed in the paper.展开更多
Phosphogypsum (PG) derived from the dissolution of phosphate ore in H2SO4 has been characterized by using chemical and thermogravimetric analyses, X-ray difFraction and infrared spectrum to give an idea about the futu...Phosphogypsum (PG) derived from the dissolution of phosphate ore in H2SO4 has been characterized by using chemical and thermogravimetric analyses, X-ray difFraction and infrared spectrum to give an idea about the future utifization of this waste material. The PG under the investigation was free from the radioactive elements and Cd and contained about 141 × 10-6 rare earth elements in total, which favours the utilization of this material. PG was formed mainIy of gypsum, little anhydrite and quartz and rare kaolinite. It exhibited two large endothermic peaks corresponding to the dehydration of the sample and a small one which may be attributed to the Iiberation of the residual water that may be found in the soluble anhydrite. Also, an exothermic peak was observed which may be related to the transformation of soluble (γ-anhydrite) to insoluble β-anhydrite. PG exhibited the same absorption bands as that observed for chemical CaSO4.2H2O and natural gypsum samples besides the appearance of a weak band at 840 cm-1 which characterizes the vibration of H2PO4-展开更多
In order to reduce the influence of impurities in hemihydrate phosphogypsum(HPG)on the environment and improve the workability of HPG,the effects of the content of quicklime and types of biopolymer(hydroxypropyl methy...In order to reduce the influence of impurities in hemihydrate phosphogypsum(HPG)on the environment and improve the workability of HPG,the effects of the content of quicklime and types of biopolymer(hydroxypropyl methylcellulose,xanthan gum,sodium polyacrylate(PAANa))on the compressive strength,softening coefficient and ultrasonic velocity of HPG were evaluated.When the content of quicklime was 1.5%and the content of PAA-Na was 0.2%,HPG had the best mechanical properties and workability,its water retention rate can be increased by 5.8%,and unconfined compressive strength of 3 days increased by 10.3%and 7 days increased by 13.1%.Through the analysis of scanning electron microscope and X-ray diffraction,it was found that the hydration reac-tion of HPG was more sufficient,the pores size and number decreased,the number of impurities on the crystal surface decreased obviously,and CaF2 and other substances were formed by the reaction after the addition of quicklime.After adding quicklime and PAANa,the indicators of gypsum self-leveling mortar prepared by HPG meet the requirements of the standard.展开更多
The aim of this work was to describe the conversion of raw phosphogypsum, issued from the manufacture of H3PO4 by dissolving the phosphate rock in H2SO4, into (NH4)2SO4 and CaCO3.The thermal analysis technique was use...The aim of this work was to describe the conversion of raw phosphogypsum, issued from the manufacture of H3PO4 by dissolving the phosphate rock in H2SO4, into (NH4)2SO4 and CaCO3.The thermal analysis technique was used to estimate the yield of conversion. (NH4)2CO3 or (NH4)2CO3 with excess NH4OH or (NH4)2CO3 with NH3 gas were used in the preparation of (NH4)2SO4 from phosphogypsum. The obtained samples were separated and tested by chemical and thermogravimetric analyses, infrared spectrum and X-ray diffraction and the optimum conditions of conversion were determined. The results indicated that the yield of conversion equals to 83.37 and 86.70% in case of using (NH4)2CO3 or (NH4)2CO3 with excess ammoniarespectively, while by using NH3 gas the percentage of conversion increased to 94.2% at a flow rate of 6 ml/min. Chemical analysis, infrared spectrum and X-ray diffraction patterns of the yield, (NH4)2SO4 were nearly similar to the standard sample.展开更多
The paper describes an investigation into the volume change of cement mortar specimen at the three kinds of different curing schedules including 20℃ and 5% Na2SO4 solution curing, tap water standard curing, 50% RH cu...The paper describes an investigation into the volume change of cement mortar specimen at the three kinds of different curing schedules including 20℃ and 5% Na2SO4 solution curing, tap water standard curing, 50% RH curing for 90 days. The testing results of hydration heat, chemical shrinking and XRD prove that calcined phosphogypsum has evident excitation effect on the activity of high calcium ash and steel slag. Simultaneously, calcined phosphogypsum has the function of decreasing volume shrinkage to blended cement possessing steel slag and high calcium ash. In sulfate curing, calcined phosphogypsum can avoid the phenomenon of protrude apex of the blended cement.展开更多
Phosphogypsum is a solid waste sourced from the wet-process phosphoric acid industry,which causes severe environmental damages.Its utilization was limited by its high decomposition temperature and high energy consumpt...Phosphogypsum is a solid waste sourced from the wet-process phosphoric acid industry,which causes severe environmental damages.Its utilization was limited by its high decomposition temperature and high energy consumption.Herein,an Fe-P slag,which is a solid waste that mainly comprises iron phosphide(FeP)and diiron phosphide(Fe_(2)P),can dramatically decrease the decomposition temperature of phosphogypsum.It was found that the Fe-P slag and CaSO_(4) can react as shown in the following reaction equation:2Fe_(1.5)P+3CaSO_(4)+6CO_(2)→Ca_(3)(PO_(4))_(2)+Fe_(3)O_(4)+3SO_(2)+6CO.Its reaction mechanism was further determined using the thermodynamic method.It was found that CaS was the key intermediate for this reaction.The CaSO_(4) conversion for this method can reach approximately 97%under the optimized roasting conditions:the molar ratio between Fe_(1.5) P and CaSO_(4) of 2:3,roasting temperature of 900℃,a roasting time of 8 h.展开更多
The aim of this work is to make use of phosphogypsum （PG） waste material, which is produced in phosphoric acid and phosphate fertilizer manufactures. A number of wood adhesive formulations based on polyvinyl acetate...The aim of this work is to make use of phosphogypsum （PG） waste material, which is produced in phosphoric acid and phosphate fertilizer manufactures. A number of wood adhesive formulations based on polyvinyl acetate （PVAc） polymer and phosphogypsum as a filler have been prepared. using different percentages of phosphogypsum, ranging between 5-20 wt pct. The prepared formulations were tested for adhesion strength and compared with both natural and pure gypsum fillers. The results indicate that PG improves the adhesion strength when 5 wt pct added, and that may be due to filling the porous surface of wood with the fine particles of PG, as well as coating the particles of the filler （PG） with PVAc units. Also, a number of formulations based on urea-formaldehyde polymer have been prepared using phosphogypsum as an active filler in the ratio of 40-75 wt pct to prepare composite materials used for some decoration purposes and construction. Mechanical, physical, and thermal properties of these formulations were studied. Also, the activation energy was calculated. The results indicate that PG without acid hardener can be used for preparation of composite materials based on urea-formaldehyde between 40-63.64 wt pct for construction purposes in the humid atmosphere, while between 63.64-75 wt pct for decoration purposes. The improvement of the physical, mechanical and thermal properties of the composite material may be attributed to the simultaneous hydration hardening action of phosphogypsum and the presence of 0.8% P2O5. These effects act as an active hardener for urea-formaldehyde resin and accelerate the cross-linking and network formation reinforced by the fine dusty inorganic particles of PG. The advantage of this method is to prepare composite material gypsum-urea-formaldehyde, which achieves the utilization of large amount of PG, reducing the price of the main product phosphate, minimizing the pollution and producing new materials which possess high thermal resistance, good mechanical properties and water resistance that are suitable for construction panels.展开更多
基金jointly supported by the National Key Research and Development Program of China (2019YFC1905800)the National Key Research & Development Program of China (2018YFC1903500)+4 种基金the commercial project by Beijing Zhong Dian Hua Yuan Environment Protection Technology Co., Ltd. (E01211200005)the Regional key projects of the science and technology service network program (STS program) of the Chinese Academy of Sciences (KFJ-STS-QYZD-153)the Ningbo Science and Technology Innovation Key Projects (2020Z099, 2022Z028)the Ningbo Municipal Commonweal Key Program (2019C10033)the support of Mineral Resources Analytical and Testing Center, Institute of Process Engineering, Chinese Academy of Science
文摘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.
基金financial support from the school-enterprise cooperation projects(2019-KYY-508101-0078).
文摘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.
基金This research was financially supported by the National Natural Science Foundation of China(Grant Nos.52178328 and 52178361)the Fundamental Research Funds for the Open-end Research Fund of State Key Laboratory for Geomechanics and Deep Underground Engineering(Grant No.SKLGDUEK2114).
文摘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.
基金financially supported by the National Natural Science Foundation of China (22279122,52042403)the Zhejiang Provincial Natural Science Foundation of China (LZ22B030004)+2 种基金the Ministry of Education,Singapore,under its Academic Research Fund Tier 1 (RG10/22)the National Institute of Education,Singapore,under its Academic Research Fund (RI 1/21 EAH)National Institute of Education,Singapore,under its Start-Up Grant (NIE-SUG4/20AHX)。
文摘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.
文摘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)<sup>2</sup> (R<sup>2</sup> = 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.
基金Supported by the National Natural Science Foundation of China(21666016)
文摘Phosphogypsum(PG) is a solid waste produced in the phosphate fertilizer industry and is environmentally harmful.The decomposition of PG to recycle calcium and sulfur is a proper way to reutilize PG. Current work aims at enriching the basic theory of coal decomposition process of PG. The emphasis was laid on the exploration of impact of main impurities on the process. On the other hand, according to Reaction Module, Equilib Module, and Phase Diagram Module of FactS age, the simulation computation was done on the systems of pure gypsum mixed with coal,with or without impurities for avoiding other impurities interference. Later, possible reactions in the process were deduced. Additionally, experiments were conducted in a TG-DTA integrated thermal gravimetric analyzer and a tube furnace. The products from the experiments were characterized and analyzed to verify the accuracy of theoretical calculations. The results showed that these impurities can change the decomposition process of PG. For example, aluminum oxide was transformed to calcium sulfoaluminate, while iron oxide was transformed to dicalcium ferrite. Furthermore, the results help to further improve the basic theory of phosphogypsum decomposition.
基金Supported by the Guizhou Province Fund Project(2014)7618
文摘The distribution of water channels in the crystal morphology of type-α hemi-hydrated gypsum(α-HH) was theoretically detected to investigate the effect of water channels on the hydration reactivity of hemi-hydrate phosphogypsum(HPG). Results showed that water channels were mainly distributed in the cylinders of α-HH crystal,whereas no water channel existed in the conical surfaces parallel to the z-axis. Increasing the number of water channels was critical to enhance the hydration activity of HPG compared with the hydration reactivity of industrial HPG and type-α high-strength gypsum. Controlling the technological parameters of crystallization by concentration of liquid-phase SO_4^(2-) made it possible to obtain HPG which had the stumpy crystals of α-HH and high hydration reactivity.
基金Funded by Innovation Group Fund Project of Hubei Province(No.2020CFA039)the Key Research and Development Program of Hubei Province(No.2020BCA077)。
文摘Carbide slag was used as an activator to improve the activity of anhydrous phosphogypsum.Carbide slag could greatly improve the mechanical strength of anhydrous phosphogypsum than K_(2)SO_(4).The compressive strength of 11 wt%carbide slag and 1 wt%K_(2)SO_(4)activated anhydrous phosphogypsum increased greatly to 8.6 MPa at 3 d,and 11.9 MPa at 7 d,and 16.0 MPa at 28 d,respectively.The rate of hydration heat was accelerated and the total hydration heat was increased,and more calcium sulfate dihydrate was formed and cross-linked with other parts which improved the compressive strength of anhydrous phosphogypsum under the effects of different activators.It was indicated that carbide slag was a highly effective and cost-efficient activator.The result provides a highly effective and low-cost method which results in a novel and high value-added method for the utilization of phosphogypsum in the future.
基金This work was financially supported by the Natural Science Foundation of Hunan Province,China(No.2020JJ5718)a scholarship granted by the China Scholarship Council(No.CSC201906370062)the National Natural Science Foundation of China(Nos.52004330 and 52074351).
文摘Phosphogypsum(PG)is a typical by-product of phosphoric acid and phosphate fertilizers during acid digestion.The application of cemented paste backfill(CPB)has been feasibly investigated for the remediation of PG.The present study evaluated fluorine immobilization mechanisms and attempted to construct a related thermodynamic and geochemical modeling to describe the related stabilization performance.Physico-chemical and mineralogical analyses were performed on PG and hardened PG-based CPB(PCPB).The correlated macro-and micro-structural properties were obtained from the analysis of the combination of unconfined compressive strength and scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy imaging.Acid/base-dependent leaching tests were performed to ascertain fluoride leachab-ility.In addition,Gibbs Energy Minimization Software and PHREEQC were applied as tools to characterize the PCPB hydration and deduce its geochemical characteristics.The results proved that multiple factors are involved in fluorine stabilization,among which the calcium silicate hy-drate gel was found to be associated with retention.Although the quantitative comparison with the experimental data shows that further modi-fication should be introduced into the simulation before being used as a predictive implement to determine PG management options,the im-portance of acid/base concentration in regulating the leaching behavior was confirmed.Moreover,the modeling enabled the identification of the impurity phases controlling the stability and leachability.
文摘Phosphogypsum-based materials (PBM) were synthesized with varied phase compositions of phosphogypsum,portland cement and fly ash.Effects of fractal growth characteristics on physicochemical properties,pore structure,compressive strength,as well as the hydration behaviour and mineralogical conversion of mortars were examined by a multitechnological approach,including mercury intrusion porosimetry,rietved phase analysis,thremal analysis,calorimetry and Fourier transforminfrared spectroscopy analysis.Expermental results indicate that the specimens cured with mosite resulted in higher strength and lower porosity compared with those cured in the drying chamber.In addition,a more complicated course of the aluminate and silicate reactions during the hydration process has been published,with the hydration products mainly consisting of calcium silicate hydrate (C-S-H),portlandite,ettringite,hemicarbonate,monocarboaluminate,calcite,quartz,a mixed AFm passed with carbonate,and hydroxide.After all,the nucleation process is a reaction that can be defined as a solid,liquid and gaseous phases that goes through the four stages of materialization mixing and modification,i e,hydration of low calcium content,secondary hydration,high calcium condensation and geoplymensation,respectively.The rupture,recombination,polymerization reactions of Si-O,Ca-O,Al-O bonds contribute to the nucleation mechanism that serves as the formation of C-S-H in hydration products.
基金Funded by the National Natural Science Foundation of China(No.51164004)the Chunhui Plan of the National Department of Education of China(No.Z2006-1-52003)。
文摘The phosphogypsum particles coated with organic emulsion were prepared by coating three kinds of organic emulsion of silicone-acrylic,styrene-acrylic and acrylic.The structure and mineralogical characteristics,acid and alkali resistance,water resistance and dissociation degree of coated phosphogypsum were studied by means of SEM-EDAX,optical microscope,gravimetric analysis and chemical detection.The results showed that the initial emulsion can be used directly for coating and granulation of phosphogypsum.The spray re-coating was carried out by using diluted emulsion with the water-to-emulsion mass ratio of 1∶1.The organic emulsion coated phosphogypsum crystal can be clearly observed,and the mixing zone at internal boundary between the organic emulsion and phosphogypsum crystal was distinguishable under the optical microscope.SEM photos showed that the surface of coated phosphogypsum particles was smooth.And the basic elements of C,O,S and Ca can be detected by EDAX.Organic emulsion can be solidified into film-network between the phosphogypsum crystals inside of the coated particles,and it can play a protective role in improving the acid resistance,alkali resistance and water resistance of phosphogypsum,and reduce the degree of dissociation of phosphogypsum in water.
基金This work was supported by the Jiangsu Provincial Science and Technology Department’s Social Development-Major Science and Technology Demonstration Project(Grant No.BE2018697)the Jiangsu Provincial Science and Technology Department Social Development Project(Grant No.BE2017704)the Scientific Research Project of the Suqian Municipal Transportation Bureau.
文摘The research used industrial by-products original phosphogypsum(PG)as the main raw material,slag(SG)and Portland cement(PC)as auxiliary materials,and the optimal additive amount was determined according to the compressive strength value of the sample.Comprehensively evaluate the water resistance and volume stability of the samples,and determine the best formula for new roadbed stabilized materials.The results showed that when the weight ratio of PG,slag and cement was OPG:SG:PC=6:3:1,and mixed with 5%micro silica fume(MSF)and 3‰hydroxypropyl methyl cellulose(HPMC),the sample’s comprehensive performance was the best,specifically,the sample’s compressive strength in 60 days reached 28.8 MPa,the softening coefficient reached 0.9,and the expansion rate was stable at about−0.2%.In addition,the mechanism of action of enhancers MSF and HPMC was analyzed according to use Vicat device,X-ray diffractometer and scanning electron microscope.The best formula SP3GH3 has the best curing effect on soil.The 28-day unconfined compressive strength(UCS)of the sample reached 2.4 MPa,the expansion rate was less than 0.09%,and the water stability coefficient was above 0.79,which was higher than that of the samples cured by traditional cement and lime during the same period.
基金State Key Laboratory of Pressure Hydrometallurgical Technology of Associated Nonferrous Metal Resource,China(No.yy2016004)Research Center for Analysis and Measurement Kunming University of Science and Technology,China(No.2017M20162207026)
文摘In order to decrease energy consumption for phosphogypsum( PG) pyrolysis process,a pilot-scale vertical-retort furnace was designed initiatively,and then mineralization agent was added to pyrolysis mixture. Calcium fluoride( CaF_2) was proven to be a suitable mineralization agent, and the optimal parameters were: pyrolysis temperature 960 ℃,carbon-sulfur mole ratio 0. 7,reaction time 50 min,and CaF_2 dosage 4% by weight. Under this condition,PG decomposition and sulfur dioxide( SO_2) conversion were up to 89. 6% and 67. 3%,respectively. CaF_2 could lead to the formation of fluosilicate complexes,and facilitate PG decomposition at a low temperature. During pyrolysis process, calcium sulfide( CaS) was an inevitable intermediate substance,and only a part of total sulfur in the feedstock could be converted to SO_2.
文摘As a by-product from the phosphate fertilizer industry Phosphogypsum (PG) was considered a potentially valuable source of the rare earth elements (REEs). Because of trace concentration of REEs in the PG (normally <0.1% wt) and also their tiny and complex occurrence phases the recovery process would be highly challenging in both technology and economy. The studies on occurrences of REEs, REE recovery by physical methods and leaching using different lixiviants such as inorganic acids, H2SO4, HCl and HNO3, and organic chemicals, the effects of mechanical treatment of PG by microwaving and grinding on leaching efficiency of REEs, and resin-in-leach process were reviewed in the paper.
文摘Phosphogypsum (PG) derived from the dissolution of phosphate ore in H2SO4 has been characterized by using chemical and thermogravimetric analyses, X-ray difFraction and infrared spectrum to give an idea about the future utifization of this waste material. The PG under the investigation was free from the radioactive elements and Cd and contained about 141 × 10-6 rare earth elements in total, which favours the utilization of this material. PG was formed mainIy of gypsum, little anhydrite and quartz and rare kaolinite. It exhibited two large endothermic peaks corresponding to the dehydration of the sample and a small one which may be attributed to the Iiberation of the residual water that may be found in the soluble anhydrite. Also, an exothermic peak was observed which may be related to the transformation of soluble (γ-anhydrite) to insoluble β-anhydrite. PG exhibited the same absorption bands as that observed for chemical CaSO4.2H2O and natural gypsum samples besides the appearance of a weak band at 840 cm-1 which characterizes the vibration of H2PO4-
基金This study was financially supported by National Natural Science Foundation of China(GrantNo.51834001)Fundamental Research Funds for the Central University(Grant No.FRF-BD-20-01B).
文摘In order to reduce the influence of impurities in hemihydrate phosphogypsum(HPG)on the environment and improve the workability of HPG,the effects of the content of quicklime and types of biopolymer(hydroxypropyl methylcellulose,xanthan gum,sodium polyacrylate(PAANa))on the compressive strength,softening coefficient and ultrasonic velocity of HPG were evaluated.When the content of quicklime was 1.5%and the content of PAA-Na was 0.2%,HPG had the best mechanical properties and workability,its water retention rate can be increased by 5.8%,and unconfined compressive strength of 3 days increased by 10.3%and 7 days increased by 13.1%.Through the analysis of scanning electron microscope and X-ray diffraction,it was found that the hydration reac-tion of HPG was more sufficient,the pores size and number decreased,the number of impurities on the crystal surface decreased obviously,and CaF2 and other substances were formed by the reaction after the addition of quicklime.After adding quicklime and PAANa,the indicators of gypsum self-leveling mortar prepared by HPG meet the requirements of the standard.
文摘The aim of this work was to describe the conversion of raw phosphogypsum, issued from the manufacture of H3PO4 by dissolving the phosphate rock in H2SO4, into (NH4)2SO4 and CaCO3.The thermal analysis technique was used to estimate the yield of conversion. (NH4)2CO3 or (NH4)2CO3 with excess NH4OH or (NH4)2CO3 with NH3 gas were used in the preparation of (NH4)2SO4 from phosphogypsum. The obtained samples were separated and tested by chemical and thermogravimetric analyses, infrared spectrum and X-ray diffraction and the optimum conditions of conversion were determined. The results indicated that the yield of conversion equals to 83.37 and 86.70% in case of using (NH4)2CO3 or (NH4)2CO3 with excess ammoniarespectively, while by using NH3 gas the percentage of conversion increased to 94.2% at a flow rate of 6 ml/min. Chemical analysis, infrared spectrum and X-ray diffraction patterns of the yield, (NH4)2SO4 were nearly similar to the standard sample.
基金Funded by the National Hi-Tech Research and Development Program ("863" Project) of China (No. 2005AA332010)
文摘The paper describes an investigation into the volume change of cement mortar specimen at the three kinds of different curing schedules including 20℃ and 5% Na2SO4 solution curing, tap water standard curing, 50% RH curing for 90 days. The testing results of hydration heat, chemical shrinking and XRD prove that calcined phosphogypsum has evident excitation effect on the activity of high calcium ash and steel slag. Simultaneously, calcined phosphogypsum has the function of decreasing volume shrinkage to blended cement possessing steel slag and high calcium ash. In sulfate curing, calcined phosphogypsum can avoid the phenomenon of protrude apex of the blended cement.
基金financially supported by the National Natural Science Foundation of China (22108185, 51702027)the Fundamental Research Funds for the Central University in China(20826041B4126)project of Sichuan Chengdu Science and Technology Bureau (2019-YF05-02170-SN)
文摘Phosphogypsum is a solid waste sourced from the wet-process phosphoric acid industry,which causes severe environmental damages.Its utilization was limited by its high decomposition temperature and high energy consumption.Herein,an Fe-P slag,which is a solid waste that mainly comprises iron phosphide(FeP)and diiron phosphide(Fe_(2)P),can dramatically decrease the decomposition temperature of phosphogypsum.It was found that the Fe-P slag and CaSO_(4) can react as shown in the following reaction equation:2Fe_(1.5)P+3CaSO_(4)+6CO_(2)→Ca_(3)(PO_(4))_(2)+Fe_(3)O_(4)+3SO_(2)+6CO.Its reaction mechanism was further determined using the thermodynamic method.It was found that CaS was the key intermediate for this reaction.The CaSO_(4) conversion for this method can reach approximately 97%under the optimized roasting conditions:the molar ratio between Fe_(1.5) P and CaSO_(4) of 2:3,roasting temperature of 900℃,a roasting time of 8 h.
文摘The aim of this work is to make use of phosphogypsum （PG） waste material, which is produced in phosphoric acid and phosphate fertilizer manufactures. A number of wood adhesive formulations based on polyvinyl acetate （PVAc） polymer and phosphogypsum as a filler have been prepared. using different percentages of phosphogypsum, ranging between 5-20 wt pct. The prepared formulations were tested for adhesion strength and compared with both natural and pure gypsum fillers. The results indicate that PG improves the adhesion strength when 5 wt pct added, and that may be due to filling the porous surface of wood with the fine particles of PG, as well as coating the particles of the filler （PG） with PVAc units. Also, a number of formulations based on urea-formaldehyde polymer have been prepared using phosphogypsum as an active filler in the ratio of 40-75 wt pct to prepare composite materials used for some decoration purposes and construction. Mechanical, physical, and thermal properties of these formulations were studied. Also, the activation energy was calculated. The results indicate that PG without acid hardener can be used for preparation of composite materials based on urea-formaldehyde between 40-63.64 wt pct for construction purposes in the humid atmosphere, while between 63.64-75 wt pct for decoration purposes. The improvement of the physical, mechanical and thermal properties of the composite material may be attributed to the simultaneous hydration hardening action of phosphogypsum and the presence of 0.8% P2O5. These effects act as an active hardener for urea-formaldehyde resin and accelerate the cross-linking and network formation reinforced by the fine dusty inorganic particles of PG. The advantage of this method is to prepare composite material gypsum-urea-formaldehyde, which achieves the utilization of large amount of PG, reducing the price of the main product phosphate, minimizing the pollution and producing new materials which possess high thermal resistance, good mechanical properties and water resistance that are suitable for construction panels.
