A Study on the Hydration of Portland Limestone Cement by Means of TG

Subject of this paper is to investigate the hydration process of Portland limestone cement containing 10-35% limestone. Cements, produced by co-grinding of clinker, limestone and gypsum, were hydrated for periods 6 h to 28 d and were studied by means of TG and XRD. The Ca(OH)₂ content of the cements containing limestone is higher than in pure cements, specifically for 10% limestone content and ages more than 1 day. These results are in accordance with the strength development of the studied cements. In earlier ages the Ca(OH)₂ content is slightly lower in the limestone cements and independent of the limestone content. After 1 day curing, the increase of limestone addition causes a relative increase of the non evaporable water. The XRD patterns indicated the presence of carboaluminates in the hydrated limestone cements. This revised version was published online in July 2006 with corrections to the Cover Date.     

O2/CO2气氛下木醋调质石灰石直接硫化反应动力学研究

采用热分析法研究了O₂/CO₂气氛下石灰石及木醋调质石灰石的直接硫化反应过程。结果表明,在实验温度1 023~1 173 K,经木醋废液调质的石灰石直接硫化钙转化率显著提高。在1 173 K时,木醋调质石灰石直接硫化反应50 min后钙转化率可达89.55%。木醋调质石灰石的主要成分为水合醋酸钙,调质使石灰石的结构更为疏松,有利于硫化反应的进行。采用缩核模型对反应过程进行了表征,得到石灰石及木醋调质石灰石直接硫化反应速率常数k_s和扩散系数D_eff的Arrhenius表达式。动力学计算结果表明,相比于石灰石,扩散对木醋调质石灰石直接硫化反应过程的影响较小,说明木醋调质石灰石直接硫化反应性能显著提升的原因为硫化反应扩散阻力的减小。     

Effect of acid on morphology of calcite during acid enhanced defluoridation

Fluoride removal from water by lime materials is a promising defluoridation process. Acid enhanced limestone defluoridation (AELD) technique involves precipitation of CaF₂ as well as adsorption of fluoride on the surface of limestone which is capable of reducing fluoride concentration to below the WHO guideline value of 1.5 mg/L. Acids such as acetic acid and citric acid are added to the fluoride water before filtration through limestone column to enhance the Ca²⁺ activity in solution for precipitation of fluoride as CaF₂. This paper describes the effects of these acids on the quality of the limestone during the AELD process, which has been studied to evaluate the reusability of the limestone. The reaction products that formed during the AELD process have also been analyzed. The detail study of the morphology of the limestone before and after use have been done using various analytical techniques, viz., X-ray diffraction, infrared spectroscopy, thermogravimetric analysis and scanning electron microscopy combined with energy dispersive X-ray spectroscopy. The study reveals that the limestone degrades to some extent in the process due to dissolution of calcium carbonate by the acids and adsorption of fluoride by the limestone. While appreciable quantity of the citrate salt of calcium was formed in the column, the acetate salt mostly remained dissolved in the water. Since mainly the surface of the limestone particles take part in the reaction, the limestone particles can be reused for the defluoridation process after cleaning the outer surface. The limestone after use remains also suitable as raw material for cement.     

SO2 retention by highly cycled modified CaO-based sorbent in calcium looping process

The limestone modified by pyroligneous acid has been proved to have good CO₂ capture behavior in the calcium looping process. In this work, SO₂ retention of the highly cycled modified limestone in the carbonation/calcination cycles was investigated in a thermogravimetric analyzer (TG). The cyclic carbonation/calcination of the modified limestone was performed in a dual fixed-bed reactor and then the cycled modified limestone was sent for sulfation in TG. The effects of sulfation temperature, cycle number, and prolonged carbonation on SO₂ retention of the cycled modified limestone were discussed. The optimum temperature for sulfation of the cycled modified limestone should be in the range of 900–950 °C. The effect of sulfation temperature on SO₂ retention of the modified limestone drops with increasing cycle number. With increasing cycle number from 20 to 100, the sulfation conversion of the cycled modified limestone is stable and can reach ~0.4. The cycled modified limestone exhibits obviously higher SO₂ retention than the cycled raw one for the same number of cycles. The prolonged carbonation increases SO₂ retention of the modified limestone and the raw one after the subsequent cycles. The sulfation conversions of the modified limestone and the raw one at 118 min after 9-h carbonation in the 20th cycle increase 43 and 56 %, respectively. The cycled modified limestone shows a greater SO₂ retention than the cycled raw one after the same prolonged carbonation treatment. The prolonged carbonation increases the pores in 5–20 nm range which is considered the optimum pore size for sulfation of CaO-based sorbent, so it results in an improvement in SO₂ retention of the cycled sorbents.     

Influence of reservoir rock composition on the combustion kinetics of crude oil

In this research, the effect of different lithology (limestone and sandstone) on the combustion of light crude oils was investigated using thermal analysis techniques. Three distinct reaction regions were identified in all of the crude oil+limestone and sandstone mixtures, known as low temperature oxidation (LTO), fuel deposition (FD) and high temperature oxidation (HTO), respectively. Kinetic analysis of the crude oil+limestone and sandstone mixtures was performed using Coats and Redfern method and the results are discussed.     

石灰岩对褐煤模拟地下气化残焦物化性质的影响

基于煤炭地下气化过程中石灰岩可能影响煤焦的组成和结构,借助煤炭地下气化模拟实验系统对不同石灰岩掺量(质量分数为0-30%)的褐煤进行水蒸气气化,并采用低温N₂吸附-脱附、XRD和FT-IR等分析手段研究石灰岩对褐煤模拟地下气化残焦的组成、比表面积及孔结构特征、微晶结构和表面官能团等物理化学性质的影响。结果表明,石灰岩对煤焦的元素组成有较大影响。石灰岩可促使煤焦中的微孔向中孔发育,增大煤焦的比表面积和孔容积;当石灰岩掺量从0增加到30%时,煤焦的比表面积增大21.91%,介孔率增加21.49个百分点。XRD分析表明,钙的存在破坏煤焦的芳香结构,使煤焦无序化程度增加,晶面间距(d₀₀₂)增大,抑制煤焦的石墨化发展倾向。FT-IR分析表明,石灰岩存在下,煤焦的羟基官能团减少。     

Physico-chemical behaviour of the carbonate rocks of Western Son Valley Region,India

The techniques of DTA and TG were employed to study the thermal characteristics of unfossiliferous carbonate litho-units, viz. Fawn dolomitic limestone (microdolsparite) and Rohtas limestone (micrite) belonging to the Vindhyan Supergroup (PreCambrian) of India. The DTA of Fawn dolomitic limestone displayed two successive endothermic peaks at 725° and 860° whereas only one endothermic change at 910° was recorded in the DTA curve of Rohtas limestone. It was confirmed by chemical analyses, TG, IR and X-ray diffraction studies that the two peaks in the first case are due to dissociation of CO₂ from magnesium and calcium lattice positions, while the sole peak in the second case is due to complete decarbonation. A tentative correlation between the thermal characteristics and structural changes of these carbonate rocks at various transition temperatures is presented.     

山西典型高铝煤灰熔融及黏温特性改性实验研究

以山西典型高铝煤为研究对象,研究了工业助熔剂石灰石、黏土以及两者的复合助熔剂对其灰熔融特性及黏温特性的影响。结果表明,随着助熔剂含量的增加,煤灰熔融流动温度下降;石灰石的助熔效果优于黏土,复合助熔剂效果优于单一助熔剂。添加石灰石使灰渣临界黏度温度tcv显著降低,添加黏土使其渣型向玻璃渣转变,复合助熔剂较单一助熔剂存在显著协同作用,即能同时实现tcv的降低和渣型的有利转变。对山西典型高铝煤两渡煤,在复合助熔剂添加量为4%(2%石灰石+2%黏土)时,不仅其渣型向玻璃渣转变,且tcv较单独添加石灰石(2%)降低133℃,较单独添加黏土(6%)降低222℃。矿物质分析结果证实了助熔剂的助熔原理。添加复合助熔剂改性的山西高铝煤可达到工业气流床气化对煤种的要求。     

重量法测定灰岩中的二氧化碳

采用重量法对灰岩中的二氧化碳进行测定。首先用酸分解试样,在载气作用下,产生的二氧化碳被吸收液完全吸收,最后用重量法间接求出二氧化碳的含量。实验结果准确度高,矿石中的硫不干扰测定,可测定0.1%以上的二氧化碳。不经过复杂的气体净化步骤,操作准确、简单、易行,可用于灰岩中二氧化碳的测定。     

Spectroscopic characterization of natural calcite minerals

The FT-IR, FT-Raman, NMR spectral data of ten different limestone samples have been compared. FT-IR and FT-Raman spectral data show that calcium carbonate in limestone, principally in the form of calcite, as identified by its main absorption bands at 1426, 1092, 876 and 712 cm(-1). The sharp diffractions at the d-spacings, 3.0348, 1.9166 and 1.8796 confirm the presence of calcite structure and the calculated lattice parameters are: a=4.9781 A, c=17.1188 A. The range of 13C chemical shifts for different limestone samples is very small, varying from 198.38 to 198.42 ppm. The observed chemical shifts are consistent with the identical C-O bonding in different limestone samples. 27Al MAS NMR spectra of the samples exhibit a central line at 1 ppm and another line at 60 ppm corresponding to octahedral and tetrahedral Al ions, respectively. The five component resonances were observed in 29Si MAS NMR spectrum of limestone and these resonances were assigned to Si (4 Al), Si (3 Al), Si (2 Al), Si (1 Al) and Si (0 Al) from low field to high field.     

Limestone doses affecting mineral contents in tropical grass forage

Summary Field trial was performed at the experimental farm of Southeast Embrapa Cattle, São Carlos - SP, Brazil, on a 16 year old Brachiaria decumbens pasture, grown on a distrophic Hapludox (Oxisol), recovered by the use of limestone and fertilizer. The experiments were carried out in random blocks, with 6 replications and 5 treatments. The 100 m² blocks were established in the pasture. Each block received a sequence of limestone doses of 0, 1, 2, 4 and 8 t/ha. The forage samples were taken one year after limestone application on soil surface. Instrumental neutron activation analysis (INAA) followed by gamma-ray spectrometry was the analytical method used to determine mineral contents. The statistical analysis showed a negative linear correlation of Br, Co, Cr, Mn and Zn contents in forage with the limestone doses, while the uptake of Mg was affected in a positive way.     

Effect of liming and fertilizer on mineral content and productivity of <Emphasis Type="Italic">Brachiaria Decumbens</Emphasis> grass forage

To restore a degraded pasture of Brachiaria decumbens, located in São Carlos — SP, southeastern Brazil, under altitude tropical climate, an experiment was carried out to study the effects of limestone, buried or not buried in the soil, and fertilizer use on mineral content and forage yield, after 3 years of treatment. Limestone and phosphorus were applied once, one month before starting. NK were applied after each cutting, for fertilized plots, four to five times a year. Experimental design was a random block (100 m²), with 6 replications and 4 treatments. Each block received 4 t/ha of limestone, except the control. Forage samples were collected 14 cm above soil surface. Instrumental neutron activation analysis (INAA) followed by gamma-ray spectrometry was the analytical method used to determine the mineral contents. Dry matter yield was affected positively with liming when compared with the limestone control, but the effect of limestone use was more pronounced with the concomitant use of NK fertilizer. The contents of Ca, Cs, Fe, La, Mg, Rb, Sc, Sm and Th in forage were negatively affected with the NK use, perhaps due to a dilution effect, while a reverse were observed for K, Cl, perhaps due to input of KCl, besides Br, Mn and Se. It seems that limestone is not a key input to restore degraded tropical pastureland, grown on acid soils, when nitrogen is lacking. INAA allowed the monitoring of some not routine elements that may be under observation to avoid potential plant nutritional disorders in production systems with high limestone and fertilizer use.     

Ion-exchange of some elements in limestone, dolomite and chrome-iron ore

An ion-exchange procedure is described for the analysis of dolomite, limestone and chrome-iron ore. In dolomite and limestone, calcium and magnesium are separated by eluting with 1M acetate buffer (pH 6) ; in chrome-iron ore, chromium(VI) is first separated from other metals by passage through a cation-exchanger, Dowex 50W-X8 (H+ form), when chromium(VI) is not adsorbed. Iron, aluminium and magnesium are subsequently recovered from the resin and are determined by conventional methods.     

ICP-AES法测定石灰石、白云石中的Al2O3,CaO,TFe2 O3,MgO,MnO,SiO2,TiO2

采用无水碳酸钾+硼酸处理样品,电感耦合等离子体发射光谱法同时测定石灰石及白云石中7种组分,筛选了不同仪器参数条件,对各组分分别选用2条相对谱线强度适中的谱线进行分析,并以元素平均值的模式输出数据结果,测定的相对标准偏差小于0.60%.经对国家一级石灰石及白云石标准物质分析验证,结果与标准值吻合.     

Thermal analysis of fluidised bed combustion residues containing limestone scavenger

A method has been developed using thermoanalytical techniques for the analysis of residues from coal-burning fluidised bed plant where limestone is used as a sulphur scavenger. This completely eliminates the need for lengthy wet chemical analyses and allows the derivation of parameters necessary for efficient plant operation, such as limestone addition rate, calcium utilisation efficiency and calcium to sulphur mole ratio. The method also gives values for the unburned carbon content and the ratio of coal ash to limestone derivatives in the sample.     

A model for the absorption of sulphur dioxide into a limestone slurry

A model has been developed for the removal of sulphur dioxide from flue gas by absorption into a limestone slurry. The flue gas desulphurization unit consists of an absorber tower and an oxidation tank. Flue gas enters the absorption tower at the bottom and meets the limestone slurry. There are five important chemical reactions with a finite rate. The rate-limiting reactions are limestone dissolution, calcium sulphite precipitation and dissolution, gypsum precipitation, sulphur dioxide absorption and sulphite oxidation in the slurry. The model also accounts for the presence of chloride ions, magnesium ions and organic acids in the limestone slurry. The absorption rates of sulphur dioxide and carbon dioxide in the tower are calculated according to the two-film model. A non-uniform set of limestone particles is also included in the model. The model was tested against literature data and the agreement between the data and the model was satisfactory. A sensitivity analysis of the desulphurization process was carried out, the inputs to the model were changed and the results from the calculations were compared with the expected results. The response to the change in the inputs agreed well with the expected results.     

热重分析法研究贝壳固硫反应动力学

采用热分析法研究了贝壳和石灰石固硫反应过程, 用等效粒子模型对固硫反应过程进行了表征, 计算分析了其固硫反应动力学参数. 结果表明, 贝壳比石灰石含有较多的碱金属盐, 其作用是提高了贝壳固硫反应速率常数和有效扩散系数. 贝壳固硫反应中存在补偿效应. 根据等动力学温度判别固硫剂活性适用于不同反应控制区的活性判断. 碱金属成分对钙基固硫剂活性有正负两个方面的影响, 含量过大或过小都会削弱固硫剂活性, 因而存在最适含量. 在1 073～1 273 K温区固硫时, 钙基固硫剂中碱金属离子与钙离子摩尔比为1∶50左右时固硫活性较高.     

A MICROBIAL POLYMER THAT CHANGES THE SURFACE PROPERTIES OF LIMESTONE: EFFECT OF BIODISPERSAN IN GRINDING LIMESTONE AND MAKING PAPER

Biodispersan is an anionic heteropolysaccharide produced by Acinetobacter calcoaceticus A2, which is effective in dispersing limestone. The results presented in this report indicate that Biodispersan is also effective as a grinding aid. In laboratory ball mill experiments, addition of O·1% Biodispersan decreased by half the time necessary to grind limestone to fine particles. The Biodispersan-ground limestone was successfully used as a filler in paper made in the laboratory. These results indicate potential industrial uses for this new microbially-produced polymer.     

Application of calorimetry as a main tool in evaluation of the effect of carbonate additives on cement hydration

Calorimetry was applied to follow the hydration in the Portland cement–dolomite–limestone mixtures. In the experiments the limestone additive of various fineness (standard component of various common cements), as well as the dolomite additive (not a standard component) were used. The rate of hydration versus time for common cements reflects the proper setting and early hardening during the first days after mixing with water (two or three peaks and the induction period between them). The aim of measurements presented in this work was to show the course of heat evolution curve and the heat evolved values, equivalent to the acceleration/retardation of hydration, in case of the pastes produced from Portland cement and the carbonate additives mixed in variable proportions, as well as to verify the results by other methods. The rate of heat evolution accompanying cement paste hydration, total heat evolved, conductivity of hydrating suspension and rheological (flow) properties versus time are modified by the fine grained carbonate additives. This is due to the hypothetical nucleating effect of limestone and dolomite.     

Neutralization of acid waters containing aluminum ions by means of limestone

Acid waters containing aluminum ions have been contacted with limestone in a stirred tank reactor, in order to neutralize the solution and promote aluminum separation as hydroxide.The limestone dissolution rate has been measured over a wide range of experimental conditions. The influence of solid surface area, stirring rate, temperature, liquid composition and flowrate of the inert stripping gas have been studied.The results suggest that the limestone dissolution rate is limited by diffusion at the solid—liquid interface, and that the precipitation of aluminum hydroxide and the CO₂ desorption are also rate-determining steps. The presence of H₂CO₃ in the liquid, owing to the slowness of CO₂ desorption, plays a beneficial role in the overall rate of limestone dissolution.A model has been developed, based on the diffusion of ionic and molecular species towards and from the solid surface, which is able to predict the experimental data within the explored range of the variables.The conclusion is drawn that limestone might be a promising alternative to other neutralizing agents for acid waters.