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.     

茂名油页岩流化床燃烧排放SO2的实验研究

在间歇式流化床反应器中进行了茂名油页岩的燃烧脱硫实验，考察了床温、油页岩粒度、油页岩含水量、钙硫摩尔比和外加灰分／页岩重量比等因素对ＳＯ２排放指标的影响程度。实验结果表明，在本实验范围中，上述因素对二氧化硫排放量影响的强弱程度为：油页岩含水量＞钙硫比＞灰岩比＞床温＞油页岩粒度。通过对实验现象的分析，本文发现工业流化床固硫要求Ｃａ／Ｓ摩尔比远大于１的另一个重要原因是：油页岩热解、挥发分燃烧释放二氧化硫的本征速率远大于石灰石固硫的本征速率。     

用于流化床燃烧脱硫的石灰石固硫反应模型

在模拟流化床燃烧脱硫气氛和温度条件下，建立了石灰石煅与固硫反应同时进行的数学模型。描述了两反应过程之间的相互影响及石灰石内部晶粒大小、孔隙率和运行参数对反应过程的影响。模型的合理性通过理论计算和实验结果的比较得到验证。     

Phase Analysis of High-calcium Lime by TG

A thermogravimetric method has been developed and is suggested for both the qualitative and quantitative phase analyses of high-calcium lime and calcium speciation as well. Two complementary TG measurements are proved to be satisfactory for the determination of moisture, calcium oxide, calcium hydroxide and calcium carbonate contents as well as total mineral impurities in high-calcium limes: quicklime, hydrated lime and limestone. This revised version was published online in August 2006 with corrections to the Cover Date.     

O2/CO2气氛下木醋调质石灰石再燃/先进再燃脱硝性能研究

在O₂/CO₂气氛下利用沉降炉脱硝实验台,对木醋调质石灰石和醋酸钙的再燃/先进再燃脱硝特性以及氨气的选择性非催化还原脱硝特性进行了研究。结果表明,木醋调质石灰石和醋酸钙的再燃脱硝效率随温度的升高先提高后降低,1 323 K时获得最高脱硝效率分别为82.70%和78.52%;再燃脱硝氧浓度不宜过高,合适的再燃比为14%~17%,停留时间为0.8 s。氨气选择性非催化还原脱硝在1 173 K时获得最高脱硝效率为95.41%,温度窗口为1 142~1 335 K;随着氧浓度的增大,脱硝效率不断降低,反应适宜的氨氮比为1.5,停留时间为1.2 s。按氨氮比0.75向再燃区喷入氨气可显著提高木醋调质石灰石和醋酸钙的再燃脱硝效率,同时脱硝反应适宜的温度区间也得到显著拓宽,1 323 K时两者获得的先进再燃脱硝效率分别为93.49%和92.79%。     

Determination of sulphur content in drill core samples by backscattered beta-particles and gamma-ray absorption

A relatively simple method of sulphur determination in drill cores of calcium carbonate matrix is described. The method is based on the combination of measurements of backscattered beta-particles and transmitted low energy gamma-radiation intensities. The transmitted gamma-radiation measurement corrects the errors of sulphur determination caused by the varying strontium sulphate and silicon dioxide content. The method has been tested on 170 samples. It was estimated that the standard deviation of sulphur determination does not exceed 2.5% of sulphur. The apparatus for routine absorption measurement is also described.     

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.     

Wet ashing of coal with perchloric acid mixed with periodic acid for the determination of sulphur and certain other constituents

A method is described for the determination of sulphur and some other inorganic constituents of coal. Organic matter is destroyed by wet combustion with perchloric acid and periodic acid. The method is rapid and efficient. Silica and sulphur are determined gravimetrically, iron, aluminium, vanadium, titanium, phosphorus, and arsenic spectrophotometrically, and calcium and magnesium volumetrically. No loss occurred by volatilisation. The complete analysis scheme devised was applied to a bituminous coal of Iowa origin.     

Determination of total sulphur in soil and plant material

A rapid and accurate method for the determination of the total sulphur content of soil or plant material is described. The sample is heated with sodium bicarbonate and silver oxide at 550° for ₃h, and the sulphur content of the whole residue is reduced to hydrogen sulphide and determined as methylene blue. The results compare favourably with those of other methods.In routine use, at least 30 analyses may be completed in a day.     

The effect of limestone on the combustion of fuel blends

Combustion profiles of coal-limestone-paper blends were studied using thermogravimetric/ Fourier transform infrared spectroscopy (TG/FTIR). The role of limestone in promoting the initial combustion of coal-paper blends and its ability to absorb sulphur oxides were examined.     

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。     

多元线性回归同时测定钙镁的研究及应用

用多元线性回归电位滴定法，同时测定两种金属离子的混合溶液并加以应用，讨论了测定原理和实验方法，选择了最佳条件，将其应用于自来水和石灰石中钙镁的测定，结果可达到化学分析准确度的要求。对批量样品的分析具有省时省力的特点，是很有应用前景的方法。     

Determination of acid volatile sulphur in river sediments by ICP-OES coupled with purge and trap method

The developed and tested method is based on the acid volatile sulphur (AVS) releasing from a sample of sediment by acidification with hydrochloric acid and sequential absorption of released hydrogen sulphide into the absorption solution of sodium hydroxide. Total sulphur absorbed in the absorption solution is subsequently determined by inductively coupled plasma optical emission spectrometry (ICP-OES) technique. The method was tested using both model and real samples of the river sediment. Obtained results were compared with the results of iodometric determination as the method routinely used for the AVS determination. In case of using ICP-OES with purge and trap, there is no spectral interference of calcium; therefore for the determination of sulphur, it is possible to use atomic emission line of sulphur S I 180.7 nm. The tested method provides the results comparable with the iodometric method within the range of tested concentrations. The detection limit (LOD) of this method is 0.09 mg· S^2? ? L^?1 in the absorption solution which corresponds to 0.23 mg S^2?·kg^?1 in a sediment. Value of LOD is comparable with the iodometric determination.     

无机钙材料在石灰岩文物表面防护中的应用

由于碳酸盐矿物的质地特点,石灰岩文物在露天环境中极易发生表面溶蚀,其上赋存文化信息的文字、纹饰和符号等雕刻痕迹也随之湮灭,对其文物价值造成了严重减损。从耐候性和兼容性角度考虑,无机保护材料显然更适合于石灰岩文物的表面防护处理。近年来,基于草酸钙、磷灰石和碳酸钙等钙基材料的石灰岩文物表面防护研究逐渐兴起并开始走向应用。本文就上述钙基保护材料的特点、防护膜制备和应用实践等做了归纳和评述,以期为石灰岩文物保护研究提供参考和借鉴。     

无机钙材料在石灰岩文物表面防护中的应用

由于碳酸盐矿物的质地特点,石灰岩文物在露天环境中极易发生表面溶蚀,其上赋存文化信息的文字、纹饰和符号等雕刻痕迹也随之湮灭,对其文物价值造成了严重减损。从耐候性和兼容性角度考虑,无机保护材料显然更适合于石灰岩文物的表面防护处理。近年来,基于草酸钙、磷灰石和碳酸钙等钙基材料的石灰岩文物表面防护研究逐渐兴起并开始走向应用。本文就上述钙基保护材料的特点、防护膜制备和应用实践等做了归纳和评述,以期为石灰岩文物保护研究提供参考和借鉴。     

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。     

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.     

Determination of calcium and magnesium in limestone and dolomite by enthalpimetric flow-injection analysis

A flow-enthalpimetric method for the determination of calcium and magnesium in limestone and dolomite is described. Calcium is determined by measuring the heat evolved from the substitution reaction with Mg-EDTA. The amount of magnesium is calculated from the calcium content and the enthalpimetric signal for the reaction of the sample solution with disodium-EDTA, which gives the total concentration of calcium and magnesium. Analysis of reference materials and other samples indicates an error not exceeding 0.3% of CaO and MgO, and a sampling rate of 100 samples per hour.     

Barium oxalate as a selective solid reagent for the absorption of sulphur trioxide

Barium and calcium oxalate monohydrates have been shown to be more suitable absorbents for sulphur trioxide than either anhydrous or hydrated oxalic acid. All four compounds are selective absorbents for the trioxide and do not absorb sulphur dioxide. Similarly all are elective absorbents for sulphuric acid aerosol, although the calcium salt may be decarboxylated under these conditions. Lead oxalate and formate may be suitable for the absorption of SO(3) and H(2)S, and SO(3), H(2)S and SO(2) respectively.     

Compleximetric determination of calcium in impure calcium carbonate and limestone

Calcium is determined in impure calcium carbonate and limestone samples by titrating with 0.01 M disodium EGTA at pH 12 in the presence of at least 0.6 mg of magnesium and a maximum of 500 μg of iron(III), using a pH 12.5 sodium hydroxide-potassium cyanide-sodium sulfide buffer and Calcon indicator. The results of such titrations are compared with those obtained by titrating at pH 10 the calcium perchlorate solutions derived from calcium oxalate, and with those of a modified LEWIS AND MELNICK method. The results for magnesium (% MgO) obtained by difference are in fair agreement. Magnesium can be titrated compleximetrically as magnesium perchlorate, but the reagent blank must be determined.