Thesis Advisor李强
Degree Grantor中国科学院研究生院
Degree Name硕士
Degree Discipline环境工程

近年来,我国焦炭产量一直高居世界第一,与此同时其也是典型的高污染行业。而随着国内经济运行新常态以及2015年新环保法的实施,对焦化、钢铁行业污染物减排、供给侧改革提出更高要求。本研究针对焦化企业生产过程特点,以分析氮、硫元素迁移转化规律为目标,建立了适用于实际焦化生产系统的静态和动态物质流分析方法,将机理模拟和过程模拟相结合,系统开展了焦化生产系统的碳、氮、硫元素的动态物质流分析,明确了其迁移转化规律。取得主要进展如下:(1)以传统物质流分析方法为基础。针对焦化行业特点,以焦化生产地理区域为系统边界,建立静态物质流分析框架,确立关键流股流量指标、关键节点波动指标、转化效率指标来分析静态物质流及不同工况波动情况。在此基础上建立了机理模拟和过程模拟相结合的动态物质流分析框架,对核心节点焦炉通过机理模拟其热解过程,将CPD模型拓展应用到实际焦炉热解过程结合Aspen Plus实现整个焦化过程的动态模拟。(2)依托静态物质流分析方法,将其应用到案例企业。年产100万吨焦炭时,焦化生产系统输入煤135万吨;碳元素的输入占比为75.4%,大部分以焦炭产品形式输出;氮元素输入量占比为1.4%,大部分随焦炭产品、硫酸铵副产品输出;硫元素输入量占比为0.5%;不同季节(原料煤的输入、组成较大差别)工况下氮、硫元素转化效率差别最大可达9%。静态元素流分析结果表明,不同工况下氮、硫元素波动较大,核心转化环节集中在焦炉,有必要对其进行动态模拟。(3)依托动态物质流分析方法,对于焦炉的动态模拟发现,采用不同配煤比时炼焦过程焦炭、焦油、煤气的收率也不相同;假定焦油二次释放HCN和NH3的比例为3:1时,对CPD模型进行拓展,可以较为准确的模拟出炼焦过程氮元素的释放;假定煤中有机硫裂解生成H2S,黄铁矿硫裂解生成COS,和原CPD模型中氮的释放类似,采用一阶速率方程和分布式活化能对煤中硫的释放进行描述,有机质固硫作用比例去20%时,得出荒煤气中H2S和COS含量随煤种的变化。通过Aspen Plus结合CPD模型模拟数据对案例焦化企业全厂流程进行模拟,连续四个月焦炭的生产数据,模拟值和实际值的相对误差,NH3和H2S都在±20%以内。;In recent years, coke production in China has always been the highest in the world, and at the same time, it is also a typical high-pollution industry. With the new normal of China’s economy and the implementation of the new environmental protection law in 2015, it put forward more stringent environment requirement and supply side reform for the coking and steel industry. In order to analyze the characteristics of the production process of coking enterprises and to analyze the migration and transformation rules of nitrogen and sulfur elements, a static and dynamic analysis method suitable for the actual coking production system is established, which combines the mechanism simulation with the process simulation. Main contents and innovations are as follows:(1) Based on the traditional material flow analysis method. According to the characteristics of coking industry, the analysis frame of static material flow is set up with the geographical area of coking production as the system boundary, and the index of key flow, key node fluctuation and conversion efficiency are established to analyze the static material flow and the fluctuation of different working conditions. On this basis, a dynamic material flow analysis framework which combines the mechanism simulation with the process simulation is established. The pyrolysis process of the core coke oven through the mechanism is simulated. The CPD model is extended and applied to the actual coke oven pyrolysis process and Aspen Plus to realize the dynamic modeling of the whole coking process.(2) Relying on static material flow analysis method, it is applied to case enterprises. When the annual production of coke is 1 million tons, the coal input of coking production system is 135 million tons. The carbon element accounted for 75.4% of the input, and most of it was outputted as coke product. The nitrogen element accounted for 1.4% of the input, and most of it was outputted as coke and ammonium sulfate products. The sulfur element accounted for 0.5% of the input. The biggest difference of nitrogen and sulfur conversion efficiency can be 9%. The results of static element flow analysis show that the nitrogen and sulfur elements fluctuate greatly under different working conditions, and the core conversion is concentrated in the coke oven. It is necessary to simulate it dynamically.(3) Relying on dynamic material flow analysis method. The simulation of coke oven shows that the yield of coke, tar and gas is different under different coal blending ratio. Assuming that the ratio of HCN and NH3 is 3: 1, the CPD model can be extended, which can be used to simulate the release of nitrogen in the coking process. It is assumed that the organic sulfur cleaves to produce H2S and the pyrite sulfur cleaves to produce COS. It is similar to the release of nitrogen in the original CPD model. The first order rate equation and the distributed activation energy can be used to describe the release of sulfur in coal. The content of H2S and COS in the raw coal gas under different coal rank can be simulated. 

Document Type学位论文
Recommended Citation
GB/T 7714
刘文涛. 基于动态模拟的焦化过程污染迁移转化分析研究[D]. 中国科学院研究生院,2018.
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