微波作用下含油污泥有机物的转化过程及微波处理工艺
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摘要
作为当今世界的主要能源之一，石油的开采与加工必不可少，由此带来的环境污染问题也越来越受到重视。含油污泥作为工业危险废弃物，其处理已经成为能源和环境领域的重点。
本文对采用微波加热技术对含油污泥进行热处理，通过对其热处理过程中油泥温度、升温速率和油泥形态变化的相关变化研究，结合热重分析技术，揭示了油泥微波热处理过程的特征与强化机制。通过对油泥微波热处理产物产出过程特征以及各阶段产物的特性分析，研究了微波热处理油泥的有机物转化过程，经过与传统热源处理油泥对比，发现采用微波技术热处理含油污泥具有广阔的工业应用前景。最后，在实验研究的基础上，以资源化和无害化处理油泥为原则，提出了含油污泥微波热处理工艺。
研究结果表明：在油泥微波热处理过程中存在水与轻质油组分的蒸发物理过程和重质油组分热解与油泥煅烧碳化的化学反应过程。其中，热解过程耗时长，随着温度升高，油泥在微波热处理过程中形态发生了显著变化。残渣作为微波吸收剂的加入，促进了油泥中大分子有机物的热解，使微波热解时间缩短了58.10%，最终强化油泥微波热处理过程，实现了油泥的节能处理，在提高处理效率的同时，适宜的添加量还能增加油回收率，做到了资源化处理油泥。
含油污泥微波热处理生成冷凝液相油品中，200℃~400℃温度段生成冷凝液相油品汽柴重油含量分别为22.46%、48.55%和21.46%，400℃~800℃温度段生成冷凝液相油品汽柴重油含量分别为22.89%、34.85%和33.39%。200℃~400℃温度段相比400℃~800℃温度段油品中分子量更广，但重油含量较少，说明油泥中有机物转化为油品以微波热解为主。油泥微波热处理生成不凝气以化学过程为主，微波热解阶段与微波煅烧阶段产生不凝气占到重量的94.12%。微波热解阶段C_2~C_5组分含量最多，H_2、N_2和O_2组分相对较少。经微波热处理后生成残渣的重金属溶出量达到了国家排放标准。
与电加热技术相比，微波热处理油泥有机物转化率更高，回收油品具有更好的品质，不凝气含有更多的可燃组分，产物总热值高出11.88%。
油泥微波热处理工艺流程包含6个模块：含油污泥预处理和进料系统、微波热处理系统、烟气冷凝和馏分分离系统、不凝气净化与利用系统、工艺检测与控制系统和其他配套辅助系统。具有先进性、可靠性、安全性和环保型的特点。其主要影响因素为含油污泥的组成，进料形态与速度，加热方式与反应温度，馏分冷却温度。含油污泥微波热处理工艺流程的提出有利于技术的工程化应用。
With the development of mining and processing petroleum,environmental pollution caused becomes more and more serious, resulting incontracting more and more attention all over the world. How to treat oilysludge with recovery and harmless low energy oily sludge, whichcontains poisonous and harmful substances, has become the focus of energyand the environment.
The treatment of oily sludge by microwave technology was studied. Inconjunction of thermogravimetric analysis technique, the process feature andacceleration mechanism of microwave thermal treatment of oily sludge werestudied firstly. Then, the output features of products during microwave thermaltreatment were studied by gas chromatography. Finally, on the basis ofthe experimental data, the technological process of microwave treatment ofoily sludge was put up for recycling oils from oily sludge.
The appearance of oily sludge changed significantly during microwavethermal treatment, and that there were two important processes: theevaporation process of hydrocarbons and water, the microwave pyrolysis andcalcining processes of heavy component. The former was physical process andthe later was chemical process. The pyrolysis process of heavy componenttook too long time, leading to the whole time of microwave treatment of oilysludge was very long. However, if the residues as microwave absorbent, whichgenerated from the microwave thermal treatment of oil sludge were mixedwith oily sludge, for example2%, can effectively mainly accelerat pyrolysisprocess of macromolecular organic material, resulting in decreasing the timeof pyrolysis process at58.10%. Furthermore, the appropriate amount ofresidues can increase the recovery of oil. This indicated that residues used asmicrowave absorbent can speed up the process of microwave treatment of oilysludge with the higher treatment efficiency. At the same time, this method cansave energy with resource utilization of oily sludge.
The oil generated from200℃~400℃during the microwave thermaltreatment of oil sludge was composed of22.46%gasoline,48.55%diesel and21.46%heavy oil. It consisted of22.89%gasoline,34.85%diesel and33.39%heavy oil from400℃~800℃. This indicated that the transformation of organicmatters in oily sludge into oil mainly happened in microwave pyrolysis stage.The non-condensable gases from microwave pyrolysis stage and calciningstage were accounted for94.12%and were composed of C_2~C_5and less H_2, N_2, O_2. The residues which were generated from the microwave thermaltreatment of oil sludge can be discharged in accordance with Chinese GBstandard.
Compared with traditional electrical heating treatment, oily sludge wastreated by microwave technology with higher efficiency of the transformationof organic matters, better quality of oils, more combustible gases and highercalorific value of product.
Finally, the technology process of microwave thermal treatment of oilysludge from preprocessing material to recovering and analysis product was putup. This technology process divided into six parts: pretreatment and feedsystem, microwave treatment system, gas condensing and fluid separationsystem, purification and utilization of non-condensable gas system, detectionand control system, accessory system. Some key factors should be consideredfor process design, for examples, composition of oily sludge, feeding form andspeed, heating method and reaction temperature, cooling temperature offraction. This technological process would be beneficial to the engineeringapplication of microwave thermal treatment of oily sludge.
本文对采用微波加热技术对含油污泥进行热处理，通过对其热处理过程中油泥温度、升温速率和油泥形态变化的相关变化研究，结合热重分析技术，揭示了油泥微波热处理过程的特征与强化机制。通过对油泥微波热处理产物产出过程特征以及各阶段产物的特性分析，研究了微波热处理油泥的有机物转化过程，经过与传统热源处理油泥对比，发现采用微波技术热处理含油污泥具有广阔的工业应用前景。最后，在实验研究的基础上，以资源化和无害化处理油泥为原则，提出了含油污泥微波热处理工艺。
研究结果表明：在油泥微波热处理过程中存在水与轻质油组分的蒸发物理过程和重质油组分热解与油泥煅烧碳化的化学反应过程。其中，热解过程耗时长，随着温度升高，油泥在微波热处理过程中形态发生了显著变化。残渣作为微波吸收剂的加入，促进了油泥中大分子有机物的热解，使微波热解时间缩短了58.10%，最终强化油泥微波热处理过程，实现了油泥的节能处理，在提高处理效率的同时，适宜的添加量还能增加油回收率，做到了资源化处理油泥。
含油污泥微波热处理生成冷凝液相油品中，200℃~400℃温度段生成冷凝液相油品汽柴重油含量分别为22.46%、48.55%和21.46%，400℃~800℃温度段生成冷凝液相油品汽柴重油含量分别为22.89%、34.85%和33.39%。200℃~400℃温度段相比400℃~800℃温度段油品中分子量更广，但重油含量较少，说明油泥中有机物转化为油品以微波热解为主。油泥微波热处理生成不凝气以化学过程为主，微波热解阶段与微波煅烧阶段产生不凝气占到重量的94.12%。微波热解阶段C_2~C_5组分含量最多，H_2、N_2和O_2组分相对较少。经微波热处理后生成残渣的重金属溶出量达到了国家排放标准。
与电加热技术相比，微波热处理油泥有机物转化率更高，回收油品具有更好的品质，不凝气含有更多的可燃组分，产物总热值高出11.88%。
油泥微波热处理工艺流程包含6个模块：含油污泥预处理和进料系统、微波热处理系统、烟气冷凝和馏分分离系统、不凝气净化与利用系统、工艺检测与控制系统和其他配套辅助系统。具有先进性、可靠性、安全性和环保型的特点。其主要影响因素为含油污泥的组成，进料形态与速度，加热方式与反应温度，馏分冷却温度。含油污泥微波热处理工艺流程的提出有利于技术的工程化应用。
With the development of mining and processing petroleum,environmental pollution caused becomes more and more serious, resulting incontracting more and more attention all over the world. How to treat oilysludge with recovery and harmless low energy oily sludge, whichcontains poisonous and harmful substances, has become the focus of energyand the environment.
The treatment of oily sludge by microwave technology was studied. Inconjunction of thermogravimetric analysis technique, the process feature andacceleration mechanism of microwave thermal treatment of oily sludge werestudied firstly. Then, the output features of products during microwave thermaltreatment were studied by gas chromatography. Finally, on the basis ofthe experimental data, the technological process of microwave treatment ofoily sludge was put up for recycling oils from oily sludge.
The appearance of oily sludge changed significantly during microwavethermal treatment, and that there were two important processes: theevaporation process of hydrocarbons and water, the microwave pyrolysis andcalcining processes of heavy component. The former was physical process andthe later was chemical process. The pyrolysis process of heavy componenttook too long time, leading to the whole time of microwave treatment of oilysludge was very long. However, if the residues as microwave absorbent, whichgenerated from the microwave thermal treatment of oil sludge were mixedwith oily sludge, for example2%, can effectively mainly accelerat pyrolysisprocess of macromolecular organic material, resulting in decreasing the timeof pyrolysis process at58.10%. Furthermore, the appropriate amount ofresidues can increase the recovery of oil. This indicated that residues used asmicrowave absorbent can speed up the process of microwave treatment of oilysludge with the higher treatment efficiency. At the same time, this method cansave energy with resource utilization of oily sludge.
The oil generated from200℃~400℃during the microwave thermaltreatment of oil sludge was composed of22.46%gasoline,48.55%diesel and21.46%heavy oil. It consisted of22.89%gasoline,34.85%diesel and33.39%heavy oil from400℃~800℃. This indicated that the transformation of organicmatters in oily sludge into oil mainly happened in microwave pyrolysis stage.The non-condensable gases from microwave pyrolysis stage and calciningstage were accounted for94.12%and were composed of C_2~C_5and less H_2, N_2, O_2. The residues which were generated from the microwave thermaltreatment of oil sludge can be discharged in accordance with Chinese GBstandard.
Compared with traditional electrical heating treatment, oily sludge wastreated by microwave technology with higher efficiency of the transformationof organic matters, better quality of oils, more combustible gases and highercalorific value of product.
Finally, the technology process of microwave thermal treatment of oilysludge from preprocessing material to recovering and analysis product was putup. This technology process divided into six parts: pretreatment and feedsystem, microwave treatment system, gas condensing and fluid separationsystem, purification and utilization of non-condensable gas system, detectionand control system, accessory system. Some key factors should be consideredfor process design, for examples, composition of oily sludge, feeding form andspeed, heating method and reaction temperature, cooling temperature offraction. This technological process would be beneficial to the engineeringapplication of microwave thermal treatment of oily sludge.
引文
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