作者：魏军晓^1,2, 耿元波¹, 沈镭¹, 岑况²

作者单位：1. 中国科学院地理科学与资源研究所, 北京 100101;
2. 中国地质大学(北京)地球科学与资源学院, 北京 100083

关键词：水泥生料;有机碳;碳排放因子;K₂Cr₂O₇容量法

摘要：

采用K2Cr2O7容量法测定水泥生料中有机碳的方法, 先以碳酸盐岩国家一级标准物质样品(GBW07135)进行条件试验, 结果与标准值相符后再进行生料样品的测定。结果表明, 在180 ℃下持续沸腾25~30 min, 有机碳回收率最高;该方法测定结果与元素分析仪和TOC分析仪的测定结果相关性较高, 相关系数分别为0.992 6和0.997 7;该法测得的新型干法窑和立窑生料有机碳的95%置信区间分别为0.17%~0.25%和4.36%~7.48%。由于成本低, 操作简便, K2Cr2O7容量法是廉价、快速并且精确测定生料有机碳的首选方法。

Determination of organic carbon in the cement raw material

WEI Junxiao^1,2, GENG Yuanbo¹, SHEN Lei¹, CEN Kuang²

1. Institute of Geographic Sciences and Natural Resources Research, Chinese Academy of Science, Beijing 100101, China;
2. School of the Earth Sciences and Resources, China University of Geosciences(Beijing), Beijing 100083, China

Abstract: This paper introduces the detection of organic carbon in cement raw materials by using the Walkley-Black method for soil and sedimentary rock. Firstly, used the carbonatite samples of national first-level standard materials (GBW07135) to carry out the condition test; secondly, after the experimental results match with the standard value, detected the raw material samples. The results show that the organic carbon that is boiling for 25 to 30 minutes at 180 ℃ has the highest recovery rate. The test results of the above method are highly correlated with those of the elemental analyzer and the TOC(total organic carbon) analyzer. The correlation coefficients are 0.992 6 and 0.997 7 respectively. According to the Walkley-Black method applied to new suspension pre-heater and per-calciner(NSP) kilns and vertical shaft kilns(VSKs), the 95% confidence intervals of the organic carbon in cement raw materials are 0.17%-0.25% and 4.36%-7.48% respectively. Characterized by low cost, easy operation and fast and accurate determination, the Walkley-Black method is the first choice for testing organic carbon in raw materials.

Keywords: cement raw material;organic carbon;carbon emission factor;Walkley-Black method

2015, 41(6): 34-38  收稿日期: 2014-11-20;收到修改稿日期: 2015-1-15

基金项目: 中国科学院战略性先导科技专项课题(XDA05010400)

作者简介: 魏军晓(1988-),男,河北衡水市人,硕士研究生,专业方向为环境生物地球化学。

参考文献

[1] Deja J, Uliasz-Bochenczyk A, Mokrzycki E. CO₂ emissions from Polish cement industry[J]. International Journal of Greenhouse Gas Control, 2010, 4(4):583-588.
[2] Mikulčic H, Vujanovic M, Duic N. Reducing the CO₂ emissions in Croatian cement industry[J]. Applied Energy, 2013(101):41-48.
[3] 何宏涛. 水泥生产二氧化碳排放分析和定量化探讨[J].水泥工程, 2009(1):70-71.
[4] 汪澜. 水泥生产企业CO₂排放量的计算[J]. 中国水泥, 2009(11):21-22.
[5] CSI. CO₂ and Energy Accounting and Reporting Standard for the Cement Industry[EB/OL].2011[2014-04-17]. http:∥www.wbcsdcement.org/pdf/tf1_co2%20protocol %20v3.pdf.
[6] Kakali G, Tsivilis S, Kolovos K, et al. Use of secondary mineralizing raw materials in cement production the case study of a stibnite ore[J]. Materials Letters, 2003, 57(20):3117-3123.
[7] Benhelal E, Zahedi G, Hashim H. A novel design for green and economical cement manufacturing[J]. Journal of Cleaner Production, 2012, 22(1):60-66.
[8] Engin T, Ari V. Energy auditing and recovery for dry type cement rotary kiln systems——A case study[J]. Energy Conversion and Management, 2005, 46(4):551-562.
[9] 徐荣, 吴小缓, 崔源声. 中国水泥工业的二氧化碳排放现状和展望[C]∥2012年中国水泥技术年会论文集, 2012:124-128.
[10] Wang Y, Zhu Q, Geng Y. Trajectory and driving factors for GHG emissions in the Chinese cement industry[J]. Journal of Cleaner Production, 2013(53):252-260.
[11] CSI. CO₂ Accounting and Reporting Standard for the Cement Industry. World Business Council for Sustainable Development.[EB/OL]. 2005[2014-04-17]. http:∥www.ghg protocol.org/files/ghgp/tools/co2_CSI_Cement_Protocol-V2.0.pdf.
[12] 鲁如坤. 土壤农业化学分析方法[M]. 北京:中国农业科技出版社, 2000:107-109.
[13] Schumacher B A. Methods for the determination of total organic carbon (TOC) in soils and sediments[S]. Washington DC:US Environmental Protection Agency, 2002.
[14] GB/T 19145—2003沉积岩中总有机碳的测定[S]. 北京:中国标准出版社, 2003.
[15] 刘昌岭, 朱志刚, 贺行良, 等. 重铬酸钾氧化——硫酸亚铁滴定法快速测定海洋沉积物中有机碳[J]. 岩矿测试, 2007, 26(3):205-208.
[16] 劳家柽. 土壤农化分析手册[M]. 北京:农业出版社, 1988: 233-234.
[17] Frangipane G, Pistolato M, Molinaroli E, et al. Comparison of loss on ignition and thermal analysis stepwise methods for determination of sedimentary organic matter[J]. Aquatic Conservation: Marine and Freshwater Ecosystems, 2009, 19(1):24-33.
[18] Byers S C, Mills E L, Stewart P L. A comparison of methods of determining organic carbon in marine sediments, with suggestions for a standard method[J]. Hydrobiologia, 1978, 58(1):43-47.
[19] 邓锦兰, 郭振平, 李枫. 介绍一种有机碳测试方法[J]. 土壤肥料, 1991(5):47-48.
[20] 梁重山, 党志, 刘丛强. 土壤/沉积物样品中有机碳含量的快速测定[J]. 土壤学报, 2002, 39(1):135-139.
[21] Su Z Y, Xiong Y M, Zhu J Y, et al. Soil organic carbon content and distribution in a small landscape of Dongguan, South China[J]. Pedosphere, 2006, 16(1):10-17.
[22] LY/T 1250—1999森林土壤碳酸钙的测定[S]. 北京:中国林业出版社, 1999.
[23] 魏军晓, 耿元波, 沈镭, 等. 基于国内水泥生产现状的碳排放因子测算[J]. 中国环境科学, 2014, 34(11):2970-2975.
[24] Chan Y, Vowles P, McTainsh G H, et al. Use of a modified Walkley-Black method to determine the organic and elemental carbon content of urban aerosols collected on glass fibre filters[J]. Chemosphere, 1995, 31(11):4403-4411.
[25] 《实用化学手册》编写组. 实用化学手册[M]. 北京:科学出版社, 2001:130-197.
[26] 《常用化学手册》编写组. 常用化学手册[M]. 北京:地质出版社, 1997:63-81.
[27] 王冲, 刘勇兵, 曹占义, 等. 白云石煅烧组织的转变过程[J]. 材料热处理学报, 2013, 34(2):23-26.