Investigation on high-volume fly ash pastes modified with micro-size metakaolin subjected to high temperatures

Portland cement(PC) containing high-volume fly ash(HVFA) is usually used to obtain economical and more sustainable merits, but these merits suffer from dramatically low compressive strength especially at early ages. In this work, the possibility of using micro-size metakaolin(MSK) particles to improve the compressive strength of HVFA paste before and after subjecting to high temperatures was studied. To produce HVFA paste, cement was partially substituted with 70% fly ash(FA), by weight. After that, FA was partially substituted with MSK at ratios fluctuating from 5% to 20% with an interval of 5%, by weight. The effect of MSK on the workability of HVFA mixture was measured. After curing, specimens were subjected to different high temperatures fluctuating from 400 to 1000 ℃ with an interval of 200 ℃ for 2 h. The results were analyzed by different techniques named X-ray diffraction(XRD), thermogravimetry(TGA) and scanning electron microscopy(SEM). The results showed that the incorporation of MSK particles into HVFA mixture exhibited a negative effect on the workability and a positive effect on the compressive strength before and after firing.

Effects of high-volume hemofiltration on alveolar- arterial oxygen exchange in patients with refractory septic shock

BACKGROUND：High-volume hemofiltration （HVHF） is technically possible in severe acute pancreatitis （SAP） patients complicated with multiple organ dysfunction syndrome （MODS）. Continuous HVHF is expected to become a beneficial adjunct therapy for SAP complicated with MODS. In this study, we aimed to explore the effects of fluid resuscitation and HVHF on alveolar- arterial oxygen exchange, the Acute Physiology and Chronic Health Evaluation II （APACHE II） score in patients with refractory septic shock. METHODS：A total of 89 refractory septic shock patients, who were admitted to ICU, the Provincial Hospital affiliated to Shandong University from August 2006 to December 2009, were enrolled in this retrospective study. The patients were randomly divided into two groups： fluid resuscitation （group A, n=41）, and fluid resuscitation plus high-volume hemofiltration （group B, n=48）, The levels of O2 content of central venous blood （CcvO2）, arterial oxygen content （CaO2）, alveolar-arterial oxygen pressure difference P（A-a）DO2, ratio of arterial oxygen pressure/alveolar oxygen pressure （PaO2/ PAO2）, respiratory index （RI） and oxygenation index （OI） were determined. The oxygen exchange levels of the two groups were examined based on the arterial blood gas analysis at different times （0, 24, 72 hours and 7 days of treatment） in the two groups. The APACHE II score was calculated before and after 7-day treatment in the two groups. The levels of CcvO2, CaO2 on day 7 in group A were significantly lower than those in group B （CcvO2：0.60±0.24 vs, 0.72±0.28, P〈0.05; CaO2：0.84±0.43 vs. 0.94±0.46, P〈0.05）. The level of oxygen extraction rate （O2ER） in group A on the 7th day was significantly higher than that in group B （ 28.7±2.4 vs. 21.7±3.4, P〈0.01）. The levels of P（A-a）DO2 and RI in group B on the 7th day were significantly lower than those in group A. The levels of PaO2/PAO2 and OI in group B on 7th day were significantly higher than those in group A （P〈0.05 or P〈0.01）. The APACHE II score in the two groups reduced gradually after 7-day treatment, and the APACHE II score on the 7th day in group B was significantly lower than that in group A （8.2±3.8 vs. 17.2±6.8, P〈0.01）. HVHF combined with fluid resuscitation can improve alveolar- arterial-oxygen exchange, decrease the APACHE II score in patients with refractory septic shock, and thus it increases the survival rate of patients.

Accelerated Carbonation Assessment of High-Volume Fly Ash Concrete

The issue of concrete carbonation has gained importance in recent years due to the increase use in supplementary cementing materials (SCMs) in concrete mixtures. While there is general agreement that concrete carbonation progresses at maximum at a relative humidity of about 60%, the rate may differ in the case of cements blended with SCMs, especially with high-volume fly ash replacements. In this study, the effect of high-volume fly ash concrete exposed to low ambient relative humidity (RH) conditions (57%) and accelerated carbonation (4% CO2) is investigated. Twenty-three concrete mixtures were produced varying in cementitious contents (310, 340, 370, and 400 kg/m3), water-to-cementitious materials ratio (0.45 and 0.50), and fly ash content (0%, 15%, 30%, and 50%) using a low and high-calcium fly ash. The specimens were allowed 1 and 7 days of moist curing and monitored for their carbonation rate and depth through phenolphthalein measurements up to 105 days of exposure. The accelerated carbonation test results indicated that increasing the addition of fly ash also led to increasing the depth of carbonation. Mixtures incorporating high-calcium fly ash were also observed to be more resistant against carbonation than low-calcium fly ash due to the higher calcium oxide (CaO) content. However, mixtures incorporating high-volume additions (50%) specimens were fully carbonated regardless of the type of fly ash used. It was evident that the increase in the duration of moist curing from 1 day to 7 days had a positive effect, reducing the carbonation depth for both plain and blended fly ash concrete mixes, however, this effect was minimal in high-volume fly ash mixtures. The results demonstrated that the water-to-cementitious ratio (W/CM) had a more dramatic impact on carbonation resistance than the curing age for mixtures incorporating 30% or less fly ash replacement, whereas those mixtures incorporating 50% showed minor differences regardless of curing age or W/CM. Based on the compressive strength results, carbonation depth appeared to decrease with increase in compressive strength, but this correlation was not significant.

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.

High-Volume Fly Ash Concrete-A Relevant Step to Sustainable Development

HVFA （high-volume fly ash） concrete could be a sustainable way for by-product utilization to conserve natural resources and protect environment. HVFA concrete can play the role of a high-performance material that may be comparable to the conventional Portland cement concrete. The results of the research programme concerning the relationships between the composition of concrete （w/b ratio, fly ash content and type of cement） and their physical and mechanical properties are presented and discussed in the paper. It is found that the introduction of high-volume fly ash into concrete has caused a decrease in compressive strength at the early age of storage. The significant increase in strength was observed between 28 days and 90 days of curing. The high-volume fly ash concretes were characterized with lower water absorbability and sorptivity than control concrete.

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.

Effect of Lightweight Aggregates Incorporation on the Mechanical Properties and Shrinkage Compensation of a Cement-Ground Granulated Blast Furnace Slag-Phosphogypsum Ternary System

Shrinkage-induced cracking is a common issue in concrete structures,where the formation of cracks not only affects the aesthetic appearance of concrete but also potentially reduces its durability and strength.In this study,the effect of ceramsite sand addition on the properties of a ternary system of cement-ground granulated blast furnace slag(GGBFS)-phosphogypsum(PG)is investigated.In particular,the fluidity,rheology,hydration heat,compressive strength,autogenous shrinkage,and drying shrinkage of the considered mortar specimens are analyzed.The results indicate that an increase in PG content leads to a decrease in fluidity,higher viscosity,lower exothermic peak,and lower compressive strength.However,the shrinkage of the mortar specimens is effectively compensated.The incorporation of internal curing water from ceramsite sand improves fluidity,decreases both yield stress and viscosity,enhances the degree of hydration,and induces mortar expansion.However,the inferior mechanical properties of the ceramsite sand generally produce a decrease in the compressive strength.

Investigation of Al2O3 and Fe2O3 transmission and transformation during the decomposition of phosphogypsum

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.

Activation of Anhydrate Phosphogypsum by K_2SO_4 and Hemihydrate Gypsum

Lime pretreated phosphogypsum（PG） was calcined at 500 ℃ to produce anhydrate gypsum cement. Due to the slow hydration of anhydrate gypsum, additives, K2SO4 and hemihydrate gypsum were selected to accelerate the hydration of anhydrate. The hydration characteristics, the resistance to hydrodynamic water, and the mineralogical studies were investigated. The experimental results suggest that activated by K2SO4 and hemihydrate, anhydrate PG hydrates much more rapidly than that in the presence of only K2SO4 or in the absence of additives. The binder has proper setting time, good strength development, and relatively better resistance to water. The hardened binder has hydrated products of rod or stick like shaped dihydrate gypsum crystals.

Effect of phosphogypsum on saline-alkalinity and aggregate stability of bauxite residue

A column experiment was conducted to investigate the effect of phosphogypsum(PG)on the salinealkalinity,and aggregate stability of bauxite residue.Results showed that:with increasing leaching time,the concentrations of saline−alkali ions decreased while the SO_(4)^(2-)concentration increased in bauxite residue leachate;compared with CK(control group)treatment,pH,electric conductivity(EC),exchangeable sodium percentage(ESP),sodium absorption ratio(SAR),and exchangeable Na+content of bauxite residue were reduced following PG treatment;average particle sizes in aggregates following CK and PG treatments were determined to be 155 and 193 nm,respectively.SR-μCT test results also confirmed that bauxite residue following PG treatment acquired larger aggregates and larger pore diameter.These results indicate that the PG treatment could significantly modulate the saline-alkalinity,and simultaneously enhance aggregate stability of bauxite residue,which provides a facile approach to reclaim bauxite residue disposal areas.

Hydration of Activated Anhydrate Phosphogypsum

Phosphogypsum（PG） calcined at 500 ℃ was activated by K2SO4 and salt lime with loose structure as seed crystal. To determine the effect of activation, hydration of the anhydrate PG activated was investigated by examination of the setting time, the proportion of hydrated anhydrate PG, the microstructure of the hardenite and the resistance to water. Results show that activated anhydrate PG hydrates much more rapidly than that in the absence of activators. The activated anhydrate PG has proper setting time and hydrated proportion. The resistance to water was greatly improved. SEM photos show that the set activated PG has hydrated products of rod-like and closely connected crystals. The different addition of activator leads to different compact structure.

Effect of Sodium Hydroxide on the Properties of Phosphogypsum based Cement

The effect of sodium hydroxide （NaOH） amount on phosphogypsum based cement was investigated. The mechanical performances and hydration mechanism of the phosphogypsum-based cement with different proportions of NaOH and steel slag were analyzed based on setting time, volume stability, strength test, XRD and SEM analyses. The experimental results show that, NaOH as an alkali activator significantly reduces the cement setting time and improves the cement early strength. But the acceleration of hydration proces produces coarse crystalline hydration products and the osteoporosis structure of hardened paste, which has a negative effect on later age strength. The combination of 1% NaOH and 5% steel slag as alkali activating agents is optimal with respect to early and later age strengths. Overdose of NaOH not only decreases the cement strength at later age, but also may cause problem of volume stability.

Variation of alkaline characteristics in bauxite residue under phosphogypsum amendment

Aiming at alkaline problem of bauxite residue,this work focused variation of alkaline characteristics in bauxite residue through phosphogypsum treatment.The results demonstrated that the pH of bauxite residue reduced from initial 10.83 to 8.70 when 1.50 wt%phosphogypsum was added for 91 d.The removal rates of free alkali and exchangeable sodium were 97.94%and 75.87%,respectively.Meanwhile,significant positive correlations(P<0.05)existed between pH and free alkali,exchangeable sodium.The effect of free alkali composition was CO3^2–>OH^–>AlO2^–>HCO3^–.In addition,alkaline phase decreased from 52.81%to 48.58%and gypsum stably presented in bauxite residue which continuously provided Ca^2+to inhibit dissolution of combined alkali.Furthermore,phosphogypsum promoted formation of macroaggregate structure,increased Ca^2+,decreased Na+and Al^3+on the surface of bauxite residue significantly,ultimately promoting soil formation in bauxite residue.

Enhancing the hydration reactivity of hemi-hydrate phosphogypsum through a morphology-controlled preparation technology

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.

Development of a Soil Stabilizer for Road Subgrade Based on Original Phosphogypsum

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.

Immobilization and leaching characteristics of fluoride from phosphogypsumbased cemented paste backfill

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.

Performace of a Kind of Organic Emulsion Coated Phosphogypsum Particles

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.

Phosphogypsum Processing for Rare Earths Recovery—A Review

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.