Dry reforming reaction over nickel catalysts supported on nanocrystalline calcium aluminates with different CaO/Al_2O_3 ratios

Nanocrystalline calcium aluminates with different CaO/Al2O3 ratios were prepared by a facile co-precipitation method using Poly（ethylene glycol）-block-poly（propylene glycol）-block-poly（ethylene glycol） （PEG-PPG-PEG, MW： 5800） as a surfactant. They were employed as catalyst support for nickel catalysts in methane reforming with carbon dioxide. The prepared samples were characterized by X-ray diffraction （XRD）, N2 adsorption （BET）, temperature-programmed reduction and oxidation （TPR-TPO）, and scanning electron microscopy （SEM） techniques. Catalysts showed a relatively high catalytic activity and stability. TPR analysis revealed that the catalysts with higher CaO content are more difficult to be reduced. TPO analysis showed that the 5 wt%Ni/CA and 5 wt%Ni/C12A7 catalysts with higher CaO amount were effective against coke deposition.

Calcium Carbonate and Ettringite Induced Efflorescence in CAC-Anhydrite Binary Systems

We focused on the efflorescence induced microstructural evolution of ettringite-rich systems prepared with calcium aluminate cement(CAC)and anhydrite.The effects of anhydrite on the visible efflorescence,and the corresponding capillary absorption of CAC-anhydrite mortars were revealed.The composition and microstructure of efflorescence-causing substances were investigated by optical microscope,in-situ Raman spectroscopy,scanning electron microscope,energy dispersive spectrometer,thermogravimetric analysis,and differential scanning calorimetry,at multi-scales.Results indicate that,besides the calcium carbonate,ettringite is another main component of efflorescence-causing substances.Compared with the neat CAC mortars,the addition of anhydrite has a significant effect on the degree of efflorescence by acting on the composition of hydration products and pore structure.In addition,methods are proposed for the prevention of efflorescence of CAC-anhydrite binary system.

Chloride Corrosion of Reinforced Calcium Aluminate Cement Mortar

This paper describes a study on the corrosion behavior of steel reinforcement in CAC mortars via electrochemical methods including corrosion potential,electrochemical impedance,and linear polarization evaluation.Results indicate that there is a non-linear relationship between the corrosion degree of steel reinforcement in CAC mortar and the concentration of NaCl solution.The electrochemical parameters of specimens immersed in 3%NaCl solution suddenly drop at 40 days,earlier than 60 days of the reference.And the charge transfer resistivity of the specimen has decreased by 11 orders of magnitude at 40 days,showing an evident corrosion on steel reinforcement.However,it is interesting to notice that the corrosion is delayed by high external chloride concentration.The specimens immersed in 9%and 15%NaCl solutions remain in a relatively stable state within 120 days with slight pitting.The great corrosion protection of CAC concrete to embedded steel bars enables its wide application in marine.

Effect of Hydrated Calcium Aluminate Cement on the Chloride Immobilization of Portland Cement Paste

To improve the efficiency and stability of chloride immobilization of portland cement paste,hydrated calcium aluminate cement(HCAC)prepared by wet grinding of CAC was added into portland cement paste as an additive.The immobilized chloride ratio(ICR)was evaluated,and the mechanism of chloride immobilization was researched by XRD,DTG,NMR,and MIP tests.The analysis results demonstrated that HCAC could improve the chloride immobilization capacity of portland cement paste.The mechanism was attributed to the following aspects:chemical binding capacity was enhanced via producing more Kuzel’s salt;physical adsorption capacity was reduced by decreasing the C-S-H gel;migration resistance was enhanced through refining the pore structure.

Effect of Na_2O on alumina leaching property and phase transformation of MgO-containing calcium aluminate slags

In order to remove or reduce the negative effect of MgO in calcium aluminate slags, the method of adding Na2O into calcium aluminate slags was studied and its effect on leaching mechanism was also analyzed. The results show that the alumina leaching efficiency of the calcium aluminate slag increases from 68.73% to 80.86% with Na2O content increasing from 0 to 4% when MgO content is 3%. The XRD results show that the quaternary compound C20A13M3S3 disappears when Na2O content increases to 4%. The addition of Na2O cannot remove the negative effect of MgO on leachability completely. XRD and EDS results indicate that Na2O can come into the lattice of 12CaO·7Al2O3 and promote the formation of 12CaO·7Al2O3

Secondary reaction mechanism of leaching process of calcium aluminate slag

SiO2 in calcium aluminate slag exists in the form of γ-2CaO·SiO2 which is more stable than β-2CaO·SiO2. However, it is decomposed by sodium carbonate solution during leaching process, leading to the secondary reaction. The extent of secondary reaction and reaction mechanism of calcium aluminate slag were studied using XRD. The results show that the decomposition rate of γ-2CaO·SiO2 increases with the increase in leaching time and sodium carbonate concentration. The main products of secondary reaction are the mixture of hydrogarnet and sodium hydrate alumina-silicate. SiO2 concentration rises firstly and then drops with the increase of leaching temperature. XRD results indicate that the stable product of secondary reaction at low temperature is hydrogarnet. But hydrogarnet is transformed into sodium hydrate alumina-silicate at high temperature.

Formation mechanism and crystal simulation of Na_2O-doped calcium aluminate compounds

Calcium aluminate clinkers doped with Na2O were synthesized using analytically pure reagents CaCO3, Al2O3, SiO2 and Na2CO3. The effects of Na2O-doping on the formation mechanism of calcium aluminate compounds and the crystal property of 12CaO·7Al2O3 (C12A7) cell were studied. The results show that the minerals containing Na2O mainly include 2Na2O·3CaO·5Al2O3 and Na2O·Al2O3, when the Na2O content in clinkers is less than 4.26% (mass fraction). The rest of Na2O is mainly doped in 12CaO·7Al2O3, which results in the decrease of the crystallinity of 12CaO·7Al2O3. The crystallinity of 2Na2O·3CaO·5Al2O3 is also inversely proportional to the Na2O content in clinkers. The formation processes of 2Na2O·3CaO·5Al2O3 and 12CaO·7Al2O3 can be divided into two ways, which are the direct reactions of raw materials and the transformation of CaO·Al2O3, respectively. The simulation shows that the covalency of O-Na bond in Na2O-doped 12CaO·7Al2O3 cell is weaker than those of O-Ca and O-Al bonds. The free energy of the unit cell increases because of Na2O doping, which results in the improvement of chemical activity of 12CaO·7Al2O3. The leaching efficiency of Al2O3 in clinker is improved from 34.81% to 88.17% when the Na2O content in clinkers increases from 0 to 4.26%.

Mineral transition and formation mechanism of calcium aluminate compounds in CaO-Al2O3-Na2O system during high-temperature sintering

The mineral transition and formation mechanism of calcium aluminate compounds in CaO-Al2O3-Na2O system during the hightemperature sintering process were systematically investigated using DSC-TG,XRD,SEM-EDS,FTIR,and Raman spectra,and the crystal structure of Na4Ca3(AlO2)10 was also simulated by Material Studio software.The results indicated that the minerals formed during the sintering process included Na4Ca3(AlO2)10,CaO·Al2O3,and 12 CaO·7 Al2O3,and the content of Na4Ca3(AlO2)10 could reach 92 wt%when sintered at 1200°C for 30 min.The main formation stage of Na4Ca3(AlO2)10 occurred at temperatures from 970 to 1100°C,and the content could reach82 wt%when the reaction temperature increased to 1100°C.The crystal system of Na4Ca3(AlO2)10 was tetragonal,and the cells preferred to grow along crystal planes(110)and(210).The formation of Na4Ca3(AlO2)10 was an exothermic reaction that followed a secondary reaction model,and its activation energy was 223.97 kJ/mol.

Effect of Curing Temperature on Intermediate Temperature Properties of Calcium Aluminate Cement Bonded Corundum Castables

In order to study the effect of the curing temperature on the intermediate temperature properties of calcium aluminate cement bonded corundum castables,the prepared castables were cured at 5,10,25,40 and 50℃,respectively,dried at 110℃ for 24 h and heat treated at 800 and 1100 ℃,respectively.Then the apparent porosity,the cold modulus of rupture and the cold crushing strength were measured.The phase composition of castable matrix specimens treated under the same conditions and the influence of the curing temperature on the intermediate temperature strength of the castables were also analyzed.The results show that with the increase of the curing temperature,the hydration degree of calcium aluminate cement increases,which promotes the uniform distribution of hydration products with AI203 after decomposition,thus enhancing the intermediate temperature strength of castables.

Effects of Nano Calcium Carbonate on Strength and Microstructure of Corundum-based Castables

The castables specimens were prepared using white fused alumina particle and powder, α-Al2O3 micropowder, hydrated alumina, nano calcium carbonate or calcium aluminate cement as starting materials. Effects of nano calcium carbonate addition on phase compositions, strength and microstructure of corundum based castables were studied. The calcium aluminate cement-containing corundum based castables with the same CaO amount was also tested for comparison. The results show that, when temperature is higher than 900 ℃ , the phase compositions of nano CaCO3-containing mixture and the calcium aluminate cement containing mixture are the same, but the forming mechanism, modality and distribution of new phases in the castables are different. With temperature rising, the hydration cement dehydrates and reacts inside cement forming calcium aluminate until the alumina in cement is not enough for the reaction （ternperature is 91 400 ℃ ） , then reacts with the surrounding alumina forming cluster CA6 in the castables. The change process of nano CaCO3 in corundum based enstables is that nano calcium carbonate decomposes to CaO after firing at 800℃ which reacts with Al2O3 forming amorphous calcium aluminate that causes an in-situ bonding. With temperature rising, the formed calcium aluminate reacts with Al2O3 in matrix and wholly forms tabular CA6 at 1 600 ℃ , which distributes uniformly in the castables. The cold and hot strength of the castables with nano calcium carbonate are obviously higher than those of the castables without nano calcium carbonate, especially at 800 -1 000 ℃ due to smaller size and higher dispersion of the nano calcium carbonate and its different reaction mechanism with Al2O3.

Effect of Different Kinds of Zinc (Ⅱ) on Early Hydration of Calcium Aluminate Cement

The early hydration of calcium aluminate cement (CAC) with different kinds of zinc (II),such as ZnSO4g7H2O,ZnO,Zn(NO3)2·6H2O and ZnCl2,was analyzed.Changes in consistency,setting time,hydration heat flow,hydration heat amount,ion concentration in solution,and hydration products were found upon the addition of different Zn^2+.The water consumption of standard consistency of CAC is decreased with different Zn^2+.Zn^2+ can delay the initial hydration of CAC.The induction period of cement with Zn^2+ is longer than that of CAC,especially the reaction time of the acceleration period is extended.Zn^2+ can promote hydration hydrate of CAC at 24 h.The characteristic diffraction peaks of CA and CA2 in CAC with different Zn^2+ are significantly reduced.It can inhibit the formation of CAH10 and promote the formation C3AH6 and AH3 in hydration products at 24 h.

Recovery of iron and calcium aluminate slag from high-ferrous bauxite by high-temperature reduction and smelting process

A high-temperature reduction and smelting process was used to recover iron and calcium aluminate slag from high-ferrous bauxite. The effects of w（CaO）/w（SiO_2） ratio, anthracite ratio, and reduction temperature and time on the recovery and size of iron nuggets and on the Al_2O_3 grade of the calcium aluminate slag were investigated through thermodynamic calculations and experiments. The optimized process conditions were the bauxite/anthracite/slaked lime weight ratio of 100：16.17：59.37, reduction temperature of 1450°C and reduction time of 20 min. Under these conditions, high-quality iron nuggets and calcium aluminate slag were obtained. The largest size and the highest recovery rate of iron nuggets were 11.42 mm and 92.79wt%, respectively. The calcium aluminate slag mainly comprised Ca_2 SiO_4 and Ca_（12）Al_（14）O_（33）, with small amounts of Fe Al_2O_4, CaAl_2O_4, and Ca_2Al_2SiO_7.

Crystallization Kinetics of Calcium Aluminate Glasses Studied by Non-isothermal Techniques

The crystallization kinetics of 38.0CaO-38.0Al2O3-10.5BaO-6.5MgO-6.0Y2O3-1.0（Na2O＋K2O） （wt%） glass was studied by differential scanning calorimeter （DSC） and X-ray diffraction （XRD） techniques. Tile results showed that DSC curves of calcium aluminate glass have a single glass transition temperature followed by one crystallization peak for the heating rates β = 5 K/min and two crystallization temperatures T1 and T2 for β≥ 10 K/min. The activation energies of crystallization obtained from the Gao-Wang model of the first exothermal peak and the second exothermal peak of calcium aluminate glass are 340 and 662 kJ/mol, respectively. The Avrami exponents of the both crystallization peaks are approximately 2, indicating the two- dimensional crystalline growth during its transformation from amorphous to crystalline. Ca12Al14O33, Ca3Al2O6 and unknown crystalline phases firstly appear when calcium aluminate glass is heat-treated. With the extending of heat-treatment duration, BaAl2O4 phase comes out.

Effect of Calcium Aluminate Cement Variety on the Hydration of Portland Cement in Blended System

Two kinds of CACs with different monocalcium aluminate（CA） contents were used in the PC/CAC（PAC） mixtures. Effects of CA and CACs on the properties of PAC were analyzed by setting times and the compressive strength tests, and also by means of calorimetry, XRD, DTA-TG and ESEM. The experimental results show that the compressive strength of the PAC mortars decreases with increasing content of CAC while it declines sharply with a higher content of CA in CAC. Compared with neat PC paste, the content of calcium hydroxide in hydrates of PAC paste decreases significantly, and the hydration time of PC is prominently prolonged. Additionally, the higher the content of CA in CAC, the more obviously the hydration of PC is delayed, confi rming that the CA phase in CAC plays an important role in the delay of PC hydration.

Preparation and characterization of calcium aluminate by chemical synthesis

Saturated Ca（OH）2 and AlCl3 solutions were used to synthesize calcium aluminate hydrate precipitates at room temperature; high purity calcium aluminate powders with stable phases were made by calcination of the precursors at a temperature as low as 1100℃. PSD and BET analysis revealed the particles with sizes ranging from submicrometer to several micrometers and with a specific area of 13 m^2/g. The measurement of hydraulic exotherm revealed that the exothennal rate is in peak for about 2 h. The exothermal quantities are 449.24 J/g at 12 h and 488.38 J/g at 24 h. Its strength development is quick and the 1 day curing strength is almost equal to 100% of the 3 days curing strength in the mortar test.

Effect of Microsilica on Chemical Bond of Calcium Aluminate Cement Bonded Corundum Castable at Low and Intermediate Temperatures

Calcium aluminate cement bonded corundum castable specimens were prepared using brown fused corundum （8 - 5, 5 - 3, 3 - 1 mm ） , white fused corundum （ ≤ 1, ≤0. 045 mm）, micro-sized α-Al2O3 and microsilica as starting materials. This work focused on investigating the relationship between the bond change in the castable matrix and the strength of the castable with 5 mass% microsilica or without microsilica after heat treatment at 110, 800 and 1 000 ℃, respectively. Chemical bond changes between the microsilica and hy- drates of calcium aluminate cement after drying at 110 ℃ or firing at 800 ℃ were investigated by XPS and FTIR. The results show that Si-O-Al bonds form be- tween the microsilica and hydrates of calcium aluminate cement after drying at 110 ℃ or firing at 800 ℃. Therefore, the increased strength of castable specimens is attributed to the formation of Si-O-Al bonds from 110 ℃ to 800 ℃.

Effect of ZnO Precursor on Properties of Calcium Aluminate Cement Bonded Corundum Castables

Calcium aluminate cement(CAC)bonded corundum based castables were prepared using tabular corundum and activated alumina as the starting materials,CAC as the binder,zinc hydroxide(Zn(OH)_(2))and basic zinc carbonate(BZC)as the ZnO precursors.The effects of the two ZnO precursors on the phase composition and the microstructure of the CAC bonded corundum based castable matrix specimens were analyzed,and the reasons affecting the hot performance of the castables were studied.The results show that Zn(OH)_(2) with a smaller particle size(d_(50)=1.26μm)is prone to agglomerate during sample preparation and generates ZnAl_(2)O_(4) spinel grains after firing,hindering the growth of CA_(6),thus decreasing the mechanical strength of the castables.BZC with a larger particle size(d_(50)=2.91μm),which shows a sound dispersity,in-situ generates nano-sized ZnO after firing,and ZnO or Zn^(2+)diffuses into calcium aluminates,promoting the sintering of CA_(2) and CA_(6),thereby enhancing the hot properties of the CAC-bonded corundum based castables.

Effect of Ga_2O_3 on Structure and Properties of Calcium Aluminate Glasses

The effect of Ga_2O_3 on the structure and properties of calcium aluminate glasses fabricated by vacuum melting process was investigated by Raman spectrum, differential scanning calorimeter（DSC）, and infrared spectrum methods. The results show that calcium aluminate glass network only consists of [AlO_4] tetrahedral units. With the gradual addition of Ga_2O_3, the quantity of [GaO_4] tetrahedral units increases. Substitution of Ga_2O_3 for Al_2O_3 results in a decrease in Tg, Tx, and Tp, and an increase in the thermal stable index ΔT. Similarly, the absorption band around 3.0 μm obviously reduces and the transparency in 4.0-6.0 μm rapidly increases with increasing Ga_2O_3 content. However, the chemical stability of calcium aluminate glasses decreases if Ga_2O_3 is introduced due to the increasing of [GaO_4] units in the glass network.

Effect of Calcium Aluminate Cement Addition on Properties of Al_(2)O_(3)-SiO_(2) Based Gunning Mixes

Al_(2)O_(3)-SiO_(2) based gunning mixes were prepared with electric porcelain waste,silica fume,bauxite,quartz powder,and calcium aluminate cement(CAC)of different additions as raw materials firing at different temperatures to research the effect of the CAC addition on their phase change and properties.The results show that:from theoretical analysis of the phase diagram,with the CAC addition increasing from 8%to 14%,anorthite increases from 40.0%to 77.7%,by mass.With the rising CAC addition,the permanent linear change on heating of specimens increases;for the specimens dried at 110℃or hot-treated at 1000℃,the bulk density and the mechanical properties increase,and the apparent porosity decreases;and for those hottreated at 1300℃,the bulk density and the mechanical properties firstly increase,and then decrease,while the apparent porosity shows an opposite trend.Taking into account the phases at high temperatures and the properties,the optimal CAC addition of Al_(2)O_(3)-SiO_(2) based gunning mixes is 12%.

Role of Calcium Magnesium Aluminate in Carbon-containing Bricks for Steel Ladle

Calcium magnesium aluminate,with the commercial name of MagArmour,is a synthetic material consisting of 70 mass%Al_(2)O_(3),20 mass%MgO and 10 mass%CaO,approximately.It is characterized by porous microstructure,intergranular aluminates phases and micro-crystalline spinel.Since globally launched in 2017,MagArmour has been successfully applied to various carbon-containing refractories serving for steel refining process.Lots of cases have demonstrated the role of MagArmour in enhancing the service life of carbon containing bricks for ladle lining.The benefits embody in formation of protective coating on hot surface,relief of drilling corrosion in joint positions,and elimination of grooves or cracks caused by mechanical stress concentration.In addition,MagArmour is effective in protecting graphite from deep oxidization so as to be capable of replacing the metallic or carbide anti-oxidants in carbon-containing bricks entirely.By means of chemical analysis and microstructural dissection,postmortem investigations on the used MgO-C bricks from both metal and slag zones of 120t steel refining ladle were conducted to clarify the working mechanism of MagArmour.The formation of protective coating on hot face is attributed to the dissolution of micro-crystalline spinel into contacting slag,which changes the slag chemistry so as to enhance viscosity.The improvement in corrosion/erosion resistance is highly related to the porous microstructure and dispersive aluminates.As well known,evaporation of Mg,Al and SiO,and/or internal migration,occurs in MgO-C bricks at elevated temperatures.The gaseous phases are absorbed by MagArmour particles due to the high surface area of porous microstructure and condense as corresponding oxides.These oxides react with the intergranular calcium aluminates forming liquid phase.With increasing temperature,the liquid phase seeps into the matrix under capillary force.The increased liquid amount improves the flexibility of the matrix and thus releases the internal stresses concentration resulting from mechanical stress and temperature gradient.Meanwhile,densification of the matrix microstructure occurs under the static pressure generated by liquid steel and molten slag,which blocks the channels of oxygen infiltration.