轻质燃料油蒸发损耗控制软浮顶油罐技术研究
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摘要
轻质燃料油的蒸发损耗，造成了能源浪费、环境污染、健康危害、安全隐患和油品质量的下降。本课题以控制轻质燃料油蒸发损耗的软浮顶油罐技术作为研究对象，首先对影响油品蒸发损耗的两个主要因素，油品蒸发表面积和油品表面温度，开展了相关的理论和实验研究。其次系统的考察了软浮顶的表面氟化性能，以及憎水憎油等阻隔性能。再根据软浮顶的相变材料控温实验，分析了软浮顶减少小呼吸的过程。最后利用自主设计的气相色谱油气在线检测系统和软浮顶模拟油罐，分别在室内和室外研究了软浮顶油罐技术控制轻质燃料油蒸发损耗的实际效果。
1、深入分析了轻质燃料油蒸发实质和蒸发影响因素，研究了油罐气体空间油气浓度的分布情况。推导出基于表面覆盖的蒸发损耗修正公式，实例验证结果与实际损耗量相比，用瓦廖夫斯基—契尔尼金公式计算损耗量相对实际损耗量误差为21%，推导公式计算损耗量相对实际损耗量误差为7.7%，误差优于原公式。计算所得损耗量与实际损耗量存在的出入，主要是由罐内介质等物理量的非稳状态引起的。
2、济空某场站立式固定顶油罐24h各部位的温度变化表明，油罐罐壁温度基本不变，油品上部温差为4.5oC，油面10cm以下基本无温差，罐顶金属表面温差高达32oC，油气空间温差呈梯度下降，上部约为20oC，中部约为17oC，下部约为13oC。实验表明，立式金属油罐油气空间的温度变化主要来自于太阳辐射，大气环境、罐壁及罐壁基础对油气空间仅具有季节性温度变化的影响。对济空和成空两个机场油库油罐内部油气温度进行Matlab曲线拟合，结果呈现余弦变化规律，且相关系数均为0.8左右。大气和罐内气体温度的初相位，济空机场油罐为-0.4左右，成空机场油罐为-0.8左右。通过ANSYS建立一维稳态传热模型，列出温度变化方程，利用趋势逼近方法获取油罐内部温度场分布规律，模型表明油罐内油气和油品温度在竖直方向上呈线性关系，油气温度的线性倾斜程度较大，且油品表面温度变化主要受油气温度影响。
3、利用傅立叶红外光谱（FT-IR）、扫描电镜（SEM）、X射线光电子能谱分析仪（XPS）和接触角仪（CA）深入研究了软浮顶空心球的化学官能团和表面性能，同时结合常温和升温阻隔实验，考察了软浮顶空心球的阻隔性能。结果表明，直接氟化软浮顶HDPE空心球在1000-1200cm-1处出现碳氟键C-F的特征吸收峰，表面层依次出现氟化层、边界层和未氟化层三层结构；随着氟化浓度、氟化温度和氟化时间的增大，氟化层厚度出现非线性的增加，但浓度和温度的过度增大将引起氟化层的氟化厚度不均匀和平滑性变差；软浮顶空心球直接氟化后，氟化HDPE表面F/C率的增大，HDPE表面憎水性增强，氟化前接触角为78.5°，氟化后接触角增大到90.0°。同时，随着氟化厚度从5.07μm增加到7.86μm，接触角也由90.0°增大到104.5°；常温和升温阻隔实验表明，随着氟化层氟含量的增加，其抗渗透性阻隔能力增强，硬度变化减少。
4、软浮顶空心球内添加的相变材料平抑了油品表面的温度波动，减少油罐小呼吸的发生，降低了轻质燃料油的蒸发损耗。与空白实验对比，加软浮顶后的升温曲线在28oC左右发生了很明显的变化，降温效果随水浴温度的升高而略有提高，外界温度越高，降温效果越明显，而软浮顶空心球数量的增加对降耗效果并不明显；恒温浴温度在35oC到45oC之间变动时，相同升温时间条件下的油温最大降低了1.5oC到4.1oC。
5、通过对模拟油罐常温、恒温、控温和变温等系列试验，建立了气相色谱油气在线检测系统。实验表明，在恒温条件下，油气含量的变化曲线呈线性关系；在控温条件下，油气含量变化呈“S”型；在常温和变温条件下，油气含量变化呈余弦关系。计算软浮顶空心球模拟油罐油蒸气达到饱和的时间效率，恒温30oC时效率为71%，恒温50oC为62%，控温时为71%。油液温度对油气的蒸发存在着正比例关系，油液温度的滞后性引起了油气含量的滞后性。
6、通过软浮顶模拟油罐检测系统，研究了室外真实环境（温度、湿度、大气压等）下软浮顶对轻质燃料油的蒸发抑制效果。试验数据表明，覆盖软浮顶空心球的模拟油罐抑制油品蒸发损耗的效果明显，其油品蒸发损耗抑制率最高值达到了71.4%，随着油品中轻质组分的减少而不断降低，最终维持在30%左右。在室外环境条件下，软浮顶模拟油罐受日照、温差等因素影响较大。
The evaporation loss of light fuel oil results in energy waste, environmental pollution,health hazards, safety hazards and oil quality reduction. First, in this paper the soft-floatingroof tank technology about the evaporation loss of light fuel oil regarded as the object of study,relevant theoretical and experimental researches were done for the two main influencingfactors of oil evaporation loss, i.e. oil evaporation surface area and the oil surface temperature.Secondly, surface fluorination property, hydrophobic property, oleophobic property and otherbarrier properties of the soft-floating roofs were systematically studied. Then the process ofbreathing loss reduction by the soft-floating roof was analyzed through a phase-changingtemperature control test. Finally, independence-designed gas chromatographic oil-gas onlinedetection system and the soft-floating roof simulation tank were used indoors and outdoors tostudy the actual effect of the soft-floating roof tank technology in controlling the evaporationloss of light fuel oil.
1. In line with essential and influencing factors of the evaporation of light fuel oil,distribution of the oil-gas concentration in the gas space of a tank was analyzed. A evaporationloss correction formula based on surface coverage was deducted. According to the result ofcomparison between the example verification result and the practical loss, the loss calculatedthrough the Waliophsis formula and the practical loss had a difference of21%; the losscalculated through the deduced formula and the practical loss had a difference of7.7%,presenting a difference smaller than the difference based on the original formula. Thedifferences between the losses obtained through calculation and the practical loss were mainlybecause of a non-stable state of physical quantities of substances such as mediums in the tank.
2. The24-hour temperature changes of all positions of each vertical tank on the airfieldbelong to jinan air force were measured. The tank wall temperature remained basicallyunchanged. There is a temperature difference of4.5oC in the top oil, and no temperaturedifference below the oil line about10cm. There ia a temperature difference up to32oC in themetallic surface of the tank top. The temperature difference in the oil-gas space dropped in agradient way, which was about20oC at the top, about17oC in the middle and about13oC atthe bottom. According to the experiment result, temperature change of the oil-gas space of thevertical metallic tank was mainly contributed by solar radiation and seasonally influenced bythe atmospheric environment, the tank wall and the tank wall foundation. Matlab curve fittingwas done for the internal oil-gas temperatures of tanks of the airport oil terminals of Air Forceof the Jinan Military Area Command and Air Force of the Chengdu Military Area Command. According to the curve fitting result, the oil-gas temperatures showed a cosine change law andthe correlation coefficient was about0.8. The initial phase between the air temperature and thetank gas temperature is about-0.4for the tanks on the airport oil terminal of Air Force of theJinan Military Area Command, or about-0.8for the tanks on the airport oil terminal of AirForce of the Chengdu Military Area Command. Through ANSYS, a one-dimensional steadyheat transfer model was established and a temperature change equation was obtained. Thedistribution law of internal temperature field of the tank was obtained through a trendapproaching method. According to the model, the oil-gas temperature and the oil temperaturein the tank have a linear relation in the vertical direction; the oil-gas temperature is greatlylinearly graded; the oil surface temperature is mainly influenced by the oil-gas temperature.
3. Chemical functional group and surface properties of the soft-floating roof hollow ballswere analyzed with the help of an FTIR (FT-IR) spectrometer, a scanning electron microscopy(SEM), an X-ray photoelectron spectroscopy (XPS) analyzer and a contact angle (CA) analyzer.A room-temperature barrier test and a temperature-rising barrier test were done to check barrierproperty of the soft-floating roof hollow ball. According to the analysis and test results, afterthe soft-floating roof HDPE hollow balls were directly fluorinated, characteristic absorptionpeak of the carbon-fluorine (C-F) bond would appear in the position of1,000-1,200cm-1and afluorinated layer, a boundary layer and an un-fluorinated layer would appear on the surfacelayer; with increase of concentration, temperature and time of the fluorination, the fluorinatedlayer increased non-linearly, but excessive increases of concentration and temperature of thefluorination would result in uneven thickness and poor smoothness of the fluorinated layer;after the direct fluorination, the fluorinated HDPE surface had a larger F/C ratio and becamemore hydrophobic and the contact angle increased from78.5°to90.0°. Meanwhile, withincrease of the fluorinated thickness from5.07μm to7.86μm, the contact angle furtherincreased from90.0°to104.5°. According to results of the room-temperature barrier test andthe temperature-rising barrier test, with increase of its fluorine content, the fluorinated layerhad better penetration resistance and less frequent hardness change.
4. Temperature change of the oil surface was suppressed, breathing loss and theevaporation loss of the light fuel oil was reduced with the help of the phase-changing materialsadded in the soft-floating roof hollow balls. Compared with data of the blank test, the heatingcurve added with soft-floating changed dramatically at about28oC; the cooling effect was alittle better with rise of the bath temperature (the higher the external temperature, the better thecooling effect would be); increase of quantity of the breathing floating roof hollow balls didnot reduce the evaporation loss significantly; when temperature of the constant temperaturebath kept at35oC to45oC, the oil temperature dropped by1.5oC to4.1oC at most in the same heating condition.
5. A gas chromatographic oil-gas online detection system was established and tests weredone with it in the conditions of room temperature, constant temperature, controlledtemperature, changing temperautre, etc. According to the test results, in the constanttemperature condition, the oil-gas content change curve showed a linear relation; in thecontrolled temperature condition, the curve was S-shaped; in the room temperature conditionor the changing temperature condition, the curve showed a cosine relation. Time efficiency wascalculated when oil vapor was saturated in the soft-floating roof simulation tank covered withhollow balls: It was71%at a constant temperature of30oC, or62%at a constant temperatureof50oC, or71%in the controlled temperature condition. The oil temperature and the oil-gasevaporation was directly proportional: posterity of the oil temperature resulted in posterity ofthe oil-gas content.
6. Evaporation suppression effect of soft-floating roofs for light fuel oil was studied inreal outdoor conditions (such as temperature, humidity and air pressure) through a soft-floatingroof simulation tank detection system. According to the test data, the simulation tanks coveredwith the floating roof hollow balls showed an obvious effect in suppressing the oilevaporation loss, the maximum value of oil evaporation supperession rate was71.4%and thefinal value was kept on around30%after dropping with decrease of light component in the oil.In outdoor conditions, the simulation tanks were mainly influenced by factors such as solarradiation and temperature difference.
1、深入分析了轻质燃料油蒸发实质和蒸发影响因素，研究了油罐气体空间油气浓度的分布情况。推导出基于表面覆盖的蒸发损耗修正公式，实例验证结果与实际损耗量相比，用瓦廖夫斯基—契尔尼金公式计算损耗量相对实际损耗量误差为21%，推导公式计算损耗量相对实际损耗量误差为7.7%，误差优于原公式。计算所得损耗量与实际损耗量存在的出入，主要是由罐内介质等物理量的非稳状态引起的。
2、济空某场站立式固定顶油罐24h各部位的温度变化表明，油罐罐壁温度基本不变，油品上部温差为4.5oC，油面10cm以下基本无温差，罐顶金属表面温差高达32oC，油气空间温差呈梯度下降，上部约为20oC，中部约为17oC，下部约为13oC。实验表明，立式金属油罐油气空间的温度变化主要来自于太阳辐射，大气环境、罐壁及罐壁基础对油气空间仅具有季节性温度变化的影响。对济空和成空两个机场油库油罐内部油气温度进行Matlab曲线拟合，结果呈现余弦变化规律，且相关系数均为0.8左右。大气和罐内气体温度的初相位，济空机场油罐为-0.4左右，成空机场油罐为-0.8左右。通过ANSYS建立一维稳态传热模型，列出温度变化方程，利用趋势逼近方法获取油罐内部温度场分布规律，模型表明油罐内油气和油品温度在竖直方向上呈线性关系，油气温度的线性倾斜程度较大，且油品表面温度变化主要受油气温度影响。
3、利用傅立叶红外光谱（FT-IR）、扫描电镜（SEM）、X射线光电子能谱分析仪（XPS）和接触角仪（CA）深入研究了软浮顶空心球的化学官能团和表面性能，同时结合常温和升温阻隔实验，考察了软浮顶空心球的阻隔性能。结果表明，直接氟化软浮顶HDPE空心球在1000-1200cm-1处出现碳氟键C-F的特征吸收峰，表面层依次出现氟化层、边界层和未氟化层三层结构；随着氟化浓度、氟化温度和氟化时间的增大，氟化层厚度出现非线性的增加，但浓度和温度的过度增大将引起氟化层的氟化厚度不均匀和平滑性变差；软浮顶空心球直接氟化后，氟化HDPE表面F/C率的增大，HDPE表面憎水性增强，氟化前接触角为78.5°，氟化后接触角增大到90.0°。同时，随着氟化厚度从5.07μm增加到7.86μm，接触角也由90.0°增大到104.5°；常温和升温阻隔实验表明，随着氟化层氟含量的增加，其抗渗透性阻隔能力增强，硬度变化减少。
4、软浮顶空心球内添加的相变材料平抑了油品表面的温度波动，减少油罐小呼吸的发生，降低了轻质燃料油的蒸发损耗。与空白实验对比，加软浮顶后的升温曲线在28oC左右发生了很明显的变化，降温效果随水浴温度的升高而略有提高，外界温度越高，降温效果越明显，而软浮顶空心球数量的增加对降耗效果并不明显；恒温浴温度在35oC到45oC之间变动时，相同升温时间条件下的油温最大降低了1.5oC到4.1oC。
5、通过对模拟油罐常温、恒温、控温和变温等系列试验，建立了气相色谱油气在线检测系统。实验表明，在恒温条件下，油气含量的变化曲线呈线性关系；在控温条件下，油气含量变化呈“S”型；在常温和变温条件下，油气含量变化呈余弦关系。计算软浮顶空心球模拟油罐油蒸气达到饱和的时间效率，恒温30oC时效率为71%，恒温50oC为62%，控温时为71%。油液温度对油气的蒸发存在着正比例关系，油液温度的滞后性引起了油气含量的滞后性。
6、通过软浮顶模拟油罐检测系统，研究了室外真实环境（温度、湿度、大气压等）下软浮顶对轻质燃料油的蒸发抑制效果。试验数据表明，覆盖软浮顶空心球的模拟油罐抑制油品蒸发损耗的效果明显，其油品蒸发损耗抑制率最高值达到了71.4%，随着油品中轻质组分的减少而不断降低，最终维持在30%左右。在室外环境条件下，软浮顶模拟油罐受日照、温差等因素影响较大。
The evaporation loss of light fuel oil results in energy waste, environmental pollution,health hazards, safety hazards and oil quality reduction. First, in this paper the soft-floatingroof tank technology about the evaporation loss of light fuel oil regarded as the object of study,relevant theoretical and experimental researches were done for the two main influencingfactors of oil evaporation loss, i.e. oil evaporation surface area and the oil surface temperature.Secondly, surface fluorination property, hydrophobic property, oleophobic property and otherbarrier properties of the soft-floating roofs were systematically studied. Then the process ofbreathing loss reduction by the soft-floating roof was analyzed through a phase-changingtemperature control test. Finally, independence-designed gas chromatographic oil-gas onlinedetection system and the soft-floating roof simulation tank were used indoors and outdoors tostudy the actual effect of the soft-floating roof tank technology in controlling the evaporationloss of light fuel oil.
1. In line with essential and influencing factors of the evaporation of light fuel oil,distribution of the oil-gas concentration in the gas space of a tank was analyzed. A evaporationloss correction formula based on surface coverage was deducted. According to the result ofcomparison between the example verification result and the practical loss, the loss calculatedthrough the Waliophsis formula and the practical loss had a difference of21%; the losscalculated through the deduced formula and the practical loss had a difference of7.7%,presenting a difference smaller than the difference based on the original formula. Thedifferences between the losses obtained through calculation and the practical loss were mainlybecause of a non-stable state of physical quantities of substances such as mediums in the tank.
2. The24-hour temperature changes of all positions of each vertical tank on the airfieldbelong to jinan air force were measured. The tank wall temperature remained basicallyunchanged. There is a temperature difference of4.5oC in the top oil, and no temperaturedifference below the oil line about10cm. There ia a temperature difference up to32oC in themetallic surface of the tank top. The temperature difference in the oil-gas space dropped in agradient way, which was about20oC at the top, about17oC in the middle and about13oC atthe bottom. According to the experiment result, temperature change of the oil-gas space of thevertical metallic tank was mainly contributed by solar radiation and seasonally influenced bythe atmospheric environment, the tank wall and the tank wall foundation. Matlab curve fittingwas done for the internal oil-gas temperatures of tanks of the airport oil terminals of Air Forceof the Jinan Military Area Command and Air Force of the Chengdu Military Area Command. According to the curve fitting result, the oil-gas temperatures showed a cosine change law andthe correlation coefficient was about0.8. The initial phase between the air temperature and thetank gas temperature is about-0.4for the tanks on the airport oil terminal of Air Force of theJinan Military Area Command, or about-0.8for the tanks on the airport oil terminal of AirForce of the Chengdu Military Area Command. Through ANSYS, a one-dimensional steadyheat transfer model was established and a temperature change equation was obtained. Thedistribution law of internal temperature field of the tank was obtained through a trendapproaching method. According to the model, the oil-gas temperature and the oil temperaturein the tank have a linear relation in the vertical direction; the oil-gas temperature is greatlylinearly graded; the oil surface temperature is mainly influenced by the oil-gas temperature.
3. Chemical functional group and surface properties of the soft-floating roof hollow ballswere analyzed with the help of an FTIR (FT-IR) spectrometer, a scanning electron microscopy(SEM), an X-ray photoelectron spectroscopy (XPS) analyzer and a contact angle (CA) analyzer.A room-temperature barrier test and a temperature-rising barrier test were done to check barrierproperty of the soft-floating roof hollow ball. According to the analysis and test results, afterthe soft-floating roof HDPE hollow balls were directly fluorinated, characteristic absorptionpeak of the carbon-fluorine (C-F) bond would appear in the position of1,000-1,200cm-1and afluorinated layer, a boundary layer and an un-fluorinated layer would appear on the surfacelayer; with increase of concentration, temperature and time of the fluorination, the fluorinatedlayer increased non-linearly, but excessive increases of concentration and temperature of thefluorination would result in uneven thickness and poor smoothness of the fluorinated layer;after the direct fluorination, the fluorinated HDPE surface had a larger F/C ratio and becamemore hydrophobic and the contact angle increased from78.5°to90.0°. Meanwhile, withincrease of the fluorinated thickness from5.07μm to7.86μm, the contact angle furtherincreased from90.0°to104.5°. According to results of the room-temperature barrier test andthe temperature-rising barrier test, with increase of its fluorine content, the fluorinated layerhad better penetration resistance and less frequent hardness change.
4. Temperature change of the oil surface was suppressed, breathing loss and theevaporation loss of the light fuel oil was reduced with the help of the phase-changing materialsadded in the soft-floating roof hollow balls. Compared with data of the blank test, the heatingcurve added with soft-floating changed dramatically at about28oC; the cooling effect was alittle better with rise of the bath temperature (the higher the external temperature, the better thecooling effect would be); increase of quantity of the breathing floating roof hollow balls didnot reduce the evaporation loss significantly; when temperature of the constant temperaturebath kept at35oC to45oC, the oil temperature dropped by1.5oC to4.1oC at most in the same heating condition.
5. A gas chromatographic oil-gas online detection system was established and tests weredone with it in the conditions of room temperature, constant temperature, controlledtemperature, changing temperautre, etc. According to the test results, in the constanttemperature condition, the oil-gas content change curve showed a linear relation; in thecontrolled temperature condition, the curve was S-shaped; in the room temperature conditionor the changing temperature condition, the curve showed a cosine relation. Time efficiency wascalculated when oil vapor was saturated in the soft-floating roof simulation tank covered withhollow balls: It was71%at a constant temperature of30oC, or62%at a constant temperatureof50oC, or71%in the controlled temperature condition. The oil temperature and the oil-gasevaporation was directly proportional: posterity of the oil temperature resulted in posterity ofthe oil-gas content.
6. Evaporation suppression effect of soft-floating roofs for light fuel oil was studied inreal outdoor conditions (such as temperature, humidity and air pressure) through a soft-floatingroof simulation tank detection system. According to the test data, the simulation tanks coveredwith the floating roof hollow balls showed an obvious effect in suppressing the oilevaporation loss, the maximum value of oil evaporation supperession rate was71.4%and thefinal value was kept on around30%after dropping with decrease of light component in the oil.In outdoor conditions, the simulation tanks were mainly influenced by factors such as solarradiation and temperature difference.
引文
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