Controlled rate thermal analysis of hydromagnesite

The reaction of magnesium minerals such as brucite with CO₂ is important in the sequestration of CO₂. The study of the thermal stability of hydromagnesite and diagenetically related compounds is of fundamental importance to this sequestration. The understanding of the thermal stability of magnesium carbonates and the relative metastability of hydrous carbonates including hydromagnesite, artinite, nesquehonite, barringtonite and lansfordite is extremely important to the sequestration process for the removal of atmospheric CO₂. This work makes a comparison of the dynamic and controlled rate thermal analysis of hydromagnesite and nesquehonite. The dynamic thermal analysis of synthetic hydromagnesite proves that dehydration takes place in two steps at 135 and 184°C, dehydroxylation at 412°C and decarbonation at 474°C. Controlled rate thermal analysis shows the first dehydration step is isothermal and the second quasi-isothermal at 108 and 145°C, respectively. In the CRTA experiment both water and carbon dioxide are evolved in an isothermal decomposition at 376°C. CRTA technology offers better resolution and a more detailed interpretation of the decomposition processes of magnesium carbonates such as nesquehonite via approaching equilibrium conditions of decomposition through the elimination of the slow transfer of heat to the sample as a controlling parameter on the process of decomposition. Constant-rate decomposition processes of non-isothermal nature reveal partial nesquehonite structure.     

Conventional and controlled rate thermal analysis of nesquehonite Mg(HCO<Subscript>3</Subscript>)(OH)·2(H<Subscript>2</Subscript>O)

The understanding of the thermal stability of magnesium carbonates and the relative metastability of hydrous carbonates including hydromagnesite, artinite, nesquehonite, barringtonite and lansfordite is extremely important to the sequestration process for the removal of atmospheric CO₂. The conventional thermal analysis of synthetic nesquehonite proves that dehydration takes place in two steps at 157, 179°C and decarbonation at 416 and 487°C. Controlled rate thermal analysis shows the first dehydration step is isothermal and the second quasi-isothermal at 108 and 145°C. In the CRTA experiment carbon dioxide is evolved at 376°C. CRTA technology offers better resolution and a more detailed interpretation of the decomposition processes of magnesium carbonates such as nesquehonite via approaching equilibrium conditions of decomposition through the elimination of the slow transfer of heat to the sample as a controlling parameter on the process of decomposition. Constant-rate decomposition processes of non-isothermal nature reveal partial collapse of the nesquehonite structure.     

High-efficiency enrichment of uranium(VI) from aqueous solution by hydromagnesite and its calcination products

The removal of uranium from aqueous solution by hydromagnesite and its calcination products was investigated. Through the study, we found that the adsorption capacities of hydromagnesite, magnesium carbonate and magnesium oxide for uranium could reach 342.96, 493.79, 2154.14 mg g^?1, respectively. The high temperature will reduce the activity of magnesium oxide, resulting in the adsorption capacity decrease. The results indicate that the optimum pH for the heat-treated samples was 3.0–4.5 and for hydromagnesite 6.0–7.0. Thermodynamic parameters such as ?G, ?H and ?S, indicated that the adsorption processes are spontaneous and endothermic.     

Characterization of light and heavy hydrated magnesium carbonates using thermal analysis

Upon heating, hydrated magnesium carbonates (HMCs) undergo a continuous sequence of decomposition reactions. This study aims to investigate the thermal decomposition of various commercially produced HMCs classified as light and heavy, highlight their differences, and provide an insight into their compositions in accordance with the results obtained from thermal analysis and microstructure studies. An understanding of the chemical compositions and microstructures, and a better knowledge of the reactions that take place during the decomposition of HMCs were achieved through the use of SEM, XRD, and TG/differential thermal analysis (DTA). The quantification of their CO₂ contents was provided by TG and dissolving the samples in HCl acid. Results show that variations exist within the microstructure and decomposition patterns of the two groups of HMCs, which do not exactly fit into the fixed stoichiometry of the known HMCs in the MgO–CO₂–H₂O system. The occurrence of an exothermic DTA peak was only observed for the heavy HMCs, which was attributed to their high CO₂ contents and the relatively delayed decomposition pattern.     

Thermal decomposition of hydromagnesite

Non isothermal decomposition of synthetically prepared hydromagnesite phase with two different morphologies (2-D micro sheets and nests) was studied in dynamic nitrogen atmosphere by thermogravimetric analysis, differential thermogravimetric analysis, and differential scanning calorimetric techniques. Two different kinetic models, i.e. the Friedman isoconversion and the Flynn–Wall methods were employed for the analysis of thermal decomposition. The apparent activation energy (E _a) of the hydromagnesite phases having 2-D micro sheet and nest morphology were calculated and compared. The activation energy of nest morphology was found to be relatively higher than 2-D micro sheets. The higher activation energy for the relatively close packed ‘nest’ morphology is attributed to the difficulty of thermal transport in the core.     

Hydration of medium reactive industrial magnesium oxide with magnesium acetate

Medium reactive magnesium oxide reacts incompletely with available water to form magnesium hydroxide. To enhance the hydration of medium reactive magnesium oxide, the effect of magnesium acetate as hydrating agent was studied. The extent to which different parameters (concentration of magnesium acetate, solution temperature and solid to liquid ratio of MgO to magnesium acetate) influence the hydration rate of a medium reactive industrial sample of magnesium oxide were evaluated. The degree of rehydration measured as percentage Mg(OH)₂being formed, increases from approximately 56% using 0.5 M magnesium acetate solutions at 25°C to 64% at 50°C, to more than 70% at 70°C. The major part of rehydration of the medium reactive MgO sample occurs within the first few minutes of the reaction for all three temperatures studied. This revised version was published online in July 2006 with corrections to the Cover Date.     

Basic ionic liquids promoted chemical transformation of CO<Subscript>2</Subscript> to organic carbonates

Ionic liquids (ILs), especially basic ILs with unique physicochemical properties, have wide application in catalysis. Using basic ILs as catalysts for the conversion of cheap, abundant, nontoxic, and renewable CO₂ into value-added organic carbonates is highly significant in view of environmental and economic issues. This review aims at giving a detailed overview on the recent advances on basic ILs promoted chemical transformation of CO₂ to cyclic and linear carbonates. The structures of various basic ILs, as well as the basic ILs promoted reactions for the transformation of CO₂ to organic carbonates are discussed in detail, including the reaction conditions, the yields of target products, the catalytic activities of basic ILs and the reaction mechanism.     

微波对碱式碳酸镁结晶过程的影响

在微波外场作用下,利用氯化镁和碳酸钠溶液反应结晶法直接合成碱式碳酸镁晶体。通过对比微波、水浴两种加热方式下镁离子变化曲线和产物的差异,XRD、FTIR,SEM等对相转移过程的物相分析表征,探索微波对反应的强化影响。结果表明,反应结晶直接合成碱式碳酸镁过程分为絮状物→出现晶体→完全转变为球状碱式碳酸镁3个阶段。微波对反应3个阶段中都有强化作用,促进絮状物的形成,加快相转变,提高反应转化率,微波加热条件下在粒径分布与组装方式与水浴加热方式均有不同,微波作用下较小颗粒是由纳米片层平行组装而成,而较大颗粒可能是无定形物在球状小颗粒表面继续转变,形成交错的表层纹理的大颗粒碱式碳酸镁。     

Determination of mechanism of thermal decomposition of Mg,Ca and Zn hydrazidocarbonates by evolved gas analysis

Hydrazo-carbonates are complex compounds and products of the reactions between solutions of metal ion and solutions of hydrazido-carbonic acid. The decomposition of Mg(N₂H₃COO)₂. 2H₂O, Ca(N₂H₃COO)₂·H₂O and Zn(N₂H₃COO)₂ in inert atmosphere were studied. By classical thermoanalytical methods and data on the composition of the intermediates and final products the mechanisms of the thermal decomposition could not be resolved therefore also evolved gas analysis was used (EGA). The first step of thermal decomposition of Ca and Mg hydrazidocarbonates is dehydration. With the heating the decomposition of the hydrazido-carbonates proceeds under evolution of the ammonia, carbon monoxide and/or nitrogen and carbon dioxide giving as the intermediates for calcium and magnesium compounds the corresponding carbonates oxides as the final products. The zinc compound decomposes to the oxide, ZnO but also zinc cyanamide was detected during to the thermal treatment.     

Green synthesis of hydrotalcite from untreated magnesium oxide and aluminum hydroxide

The influence of reaction temperature and time on the hydrothermal dissolution-precipitation synthesis of hydrotalcite was investigated. Untreated MgO, Al(OH)₃ and NaHCO₃ were used. An industrially beneficial, economically favourable, environmentally friendly, zero effluent synthesis procedure was devised based on green chemistry principles, in which the salt-rich effluent typically produced was eliminated by regenerating the sodium bicarbonate in a full recycle process. It was found that the formation of hydromagnesite dominates at low temperatures independent of reaction time. With an increase in reaction time and temperature, hydromagnesite decomposes to form magnesite. At low temperatures, the formation of hydrotalcite is limited by the solubility of the Al(OH)₃. To achieve a hydrotalcite yield of 96%, a reaction temperature of 160°C for 5?h is required. A yield higher than 99% was achieved at 180°C and 5?h reaction time, producing an layered double hydroxide with high crystallinity and homogeneity.     

Zinc‐Catalysed Hydroboration of Terminal and Internal Alkynes

A regioselective hydroboration of alkynes has been developed by using commercially available zinc triflate as a catalyst, in the presence of catalytic amount of NaBHEt₃. The reaction tolerates a wide range of terminal alkynes having several synthetically useful functional groups and proceeds regioselectively to furnish hydroborated products in moderate to excellent yields. This system shows moderate chemoselectivity towards terminal C≡C bond over terminal and internal C=C bond and internal C≡C bond.     

Synthetic Hydromagnesite as Flame Retardant. A Study of the Stearic Coating Process

A synthetic hydromagnesite obtained from an industrial by-product rich in magnesium oxide was employed and evaluated as a non-halogenated flame retardant for poly(ethylene-co-vinyl acetate). The filler was characterized with different techniques (such as specific surface area, TGA, particle morphology and size measurements, WAXS). Significant differences were found between the synthetic hydromagnesite and the natural one. Synthetic hydromagnesite was coated with stearic acid and the effectiveness of the coating process was studied by the dye adsorption method and sedimentation volume measurements. The amount of coating agent ranged from 1 to 4.5%. This factor was found to have a significant effect on the thermal decomposition behaviour of the filler. A poly(ethylene-co-vinyl acetate) (27% of VA) was filled with the coated synthetic grades of hydromagnesite as well as with two commercial flame retardants and different physicochemical properties were evaluated, including their flame retardant effect.     

Silver(I)‐Catalyzed Three‐Component Reaction of Propargylic Alcohols,Carbon Dioxide and Monohydric Alcohols: Thermodynamically Feasible Access to β‐Oxopropyl Carbonates

A silver(I)‐catalyzed three‐component reaction of propargylic alcohols, CO₂, and monohydric alcohols was successfully developed for the synthesis of β‐oxopropyl carbonates. As such, a series of β‐oxopropyl carbonates were exclusively produced in excellent yields (up to 98 %), even under atmospheric pressure of CO₂. The silver catalyst works efficiently for both the carboxylative cyclization of propargylic alcohols with CO₂ and subsequent transesterification of α‐alkylidene cyclic carbonates with monohydric alcohols; thus this tandem process performs smoothly under mild conditions. This work provides a versatile and thermodynamically favorable approach to dissymmetric dialkyl carbonates.     

Study of hydromagnesite and magnesium hydroxide based fire retardant systems for ethylene-vinyl acetate containing organo-modified montmorillonite

A new flame retardant (FR) system for ethylene-vinyl acetate, mainly based on the combination of hydromagnesite (HM, obtained from an industrial by-product) and organo-modified montmorillonite (oMMT) has been compared with a magnesium hydroxide (MDH) and oMMT flame retardant system. The presence of oMMT in association with both hydrated minerals gave a strong decrease of heat release rate in cone calorimeter tests. Moreover, the HM/oMMT combination leads to a better improvement of resistance to ignition and self-extinguishability in comparison with the MDH/oMMT one. The study of residues formed during thermal decomposition revealed the formation of forsterite (Mg₂SiO₄) when either MDH or HM was used in combination with oMMT. SEM observations of residues showed sintering of the mineral particles at high temperature particularly in the case of HM/oMMT composition.     

十二烷基硫酸钠辅助下低温合成碱式碳酸镁微球

在SDS辅助下,利用氯化镁和碳酸钠溶液在较低温度下(<55℃)反应结晶直接合成碱式碳酸镁微球。利用XRD、FTIR,SEM等技术研究了SDS加入量,反应温度,反应物浓度以及NaCl浓度等合成条件对产物的影响。结果表明:在反应温度低于55℃时,控制反应物浓度小于0.20 mol.L-1,加入一定量的SDS,可以有效抑制无定形颗粒向MgCO3.3H2O生长,促使无定形纳米颗粒通过相转移与自组装直接向碱式碳酸镁4MgCO3.Mg(OH)2.4H2O转变。SDS加入量,反应温度,反应物浓度以及NaCl浓度对碱式碳酸镁微球尺寸和微观形貌均起到调节作用。     

The reactions of some compounds of zinc,cadmium and mercury with the molten lithium carbonate-sodium carbonate-potassium carbonate eutectic

The reactions of ZnCl₂, CdCl₂, CdCO₃, CdSO₄, Hg₂Cl₂, Hg₂SO₄, HgCl₂ and HgSO₄ with the molten alkali metal carbonate eutectic were investigated by thermogravimetry. Reaction products were analysed by various techniques.Zinc and cadmium compounds were found to react with the eutectic showing one weight-loss step in their thermograms for the evolution of carbon dioxide and produced corresponding metal oxides. Mercury compounds, on the other hand, reacted with the eutectic exhibiting two or three weight-loss steps due to the formation of stable intermediates consisting of various basic mercury carbonates which ultimately decomposed to give a mixture of metallic mercury, oxygen and carbon dioxide. The temperature ranges of the reactions and their Stoichiometries have been established.     

Dynamic and controlled rate thermal analysis of hydrozincite and smithsonite

The understanding of the thermal stability of zinc carbonates and the relative stability of hydrous carbonates including hydrozincite and hydromagnesite is extremely important to the sequestration process for the removal of atmospheric CO₂. The hydration-carbonation or hydration-and-carbonation reaction path in the ZnO-CO₂-H₂O system at ambient temperature and atmospheric CO₂ is of environmental significance from the standpoint of carbon balance and the removal of green house gases from the atmosphere. The dynamic thermal analysis of hydrozincite shows a 22.1% mass loss at 247°C. The controlled rate thermal analysis (CRTA) pattern of hydrozincite shows dehydration at 38°C, some dehydroxylation at 170°C and dehydroxylation and decarbonation in a long isothermal step at 190°C. The CRTA pattern of smithsonite shows a long isothermal decomposition with loss of CO₂ at 226°C. CRTA technology offers better resolution and a more detailed interpretation of the decomposition processes of zinc carbonate minerals via approaching equilibrium conditions of decomposition through the elimination of the slow transfer of heat to the sample as a controlling parameter on the process of decomposition. The CRTA technology offers a mechanism for the study of the thermal decomposition and relative stability of minerals such as hydrozincite and smithsonite.     

The effect of calcining conditions on the rehydration of dead burnt magnesium oxide using magnesium acetate as a hydrating agent

Summary Magnesium oxide was produced through calcination of magnesite ore. A rehydration percentage of MgO to Mg(OH)₂ of higher than 60% is obtained using calcination temperatures of 1000°C and below. At these temperatures medium reactive MgO was formed. The extend to which dead burnt MgO (obtained after calcination at 1200°C and higher) may be rehydrated is dependent on the calcination time, but even after 1 h and using magnesium acetate as a hydrating agent only 40% of the initial product has rehydrated to Mg(OH)₂. After 4 and more hours of calcinations at 1200°C, a maximum of approximately 14% of the initial MgO is rehydrated back to Mg(OH)₂. Thermogravimetric analysis was performed on the various compounds to determine the amounts of Mg(OH)₂ that formed.     

Fire retardant action of mineral fillers

Endothermically decomposing mineral fillers, such as aluminium or magnesium hydroxide, magnesium carbonate, or mixed magnesium/calcium carbonates and hydroxides, such as naturally occurring mixtures of huntite and hydromagnesite are in heavy demand as sustainable, environmentally benign fire retardants. They are more difficult to deploy than the halogenated flame retardants they are replacing, as their modes of action are more complex, and are not equally effective in different polymers. In addition to their presence (at levels up to 70%), reducing the flammable content of the material, they have three quantifiable fire retardant effects: heat absorption through endothermic decomposition; increased heat capacity of the polymer residue; increased heat capacity of the gas phase through the presence of water or carbon dioxide. These three contributions have been quantified for eight of the most common fire retardant mineral fillers, and the effects on standard fire tests such as the LOI, UL 94 and cone calorimeter discussed. By quantifying these estimable contributions, more subtle effects, which they might otherwise mask, may be identified.     

Analysis of products of the thickening reaction between polyesters and magnesium oxide

The products of the reaction between MgO and polypropylene-glycol adipates of different acid values and water contents were analyzed for the water generated and the magnesium reacted into the resin by means of Karl Fischer titration and atomic absorption spectroscopy, respectively. The results conclusively show that both basic and neutral salts are present in the products. The ratio of the amounts of basic and neutral salts present in the mixture, r_B/N, could also be calculated from the results. It was found that as R, the moles of MgO added per mole of acid groups, is increased both the amount of oxide reacted and r_B/N increase while these are relatively unaffected by the water content of the resin. The minimum value of R at which basic salt exists in the reaction products was found to increase with decreasing acid value. It is proposed that diffusional effects account for these observations as well as those reported in literature.