摘 要

我国是能源消耗大国，随着经济社会的发展和工业水平的不断提升，我国对于能源的需求日益提高，煤炭、石油等不可再生矿物资源储量相继告急，寻找合适的替代能源成为当务之急。页岩气是一种清洁高效的非常规资源，且在我国的可采储量较大，具有较高的开发潜力。近年来，我国页岩气资源得到了大范围的开发，但与此同时，伴随页岩气的开采产生了大量的油基钻屑。油基钻屑中含有大量重金属元素和微生物，如果处理不当会对土壤、水体、大气环境造成严重破坏。热解是处理油基钻屑的常用手段之一，热解终温、升温速率、恒温时间及氮气流速都会对油基钻屑热解效果产生影响。另外，有研究表明油基钻屑的热解产物热解灰渣具有一定的燃烧性能，具备制备燃料的潜能，但是其H/C较低。生物质是一种可再生的优质清洁能源，H/C较低的油基钻屑与H/C较高的生物质混合后会具有更好的燃烧性能。因此本文以油基钻屑热解灰渣和桉树炭化物为原料，辅以一定的粘结剂、固硫剂、助燃剂等添加剂制备成型燃料。首先对热解终温、升温速率、恒温时间及氮气流速等热解条件进行优化，随后利用正交实验探究油基钻屑热解灰渣、桉树炭化物、水、粘结剂、固硫剂、助燃剂的最适比例，以期能够形成一套完整的成型燃料制备工艺组合系统，生产出一种具有较高的实用性、稳定性的成型燃料，实现对油基钻屑的规范处理和资源化利用。结果表明，热解终温400℃、终温时间60 min、升温速率 15℃·min^-1和氮气速率0.1 L·min^-1条件下热解处理含油率最低且热值较高；水量和总碳之比为为1.0:1，淀粉、羧甲基纤维素钠、氢氧化钠、高锰酸钾之比为20:2:1:0.1，采用蜂窝煤型模具人工压制时，样品具有最佳的成型效果、强度及孔隙率；当生物质炭与油基钻屑之比为2:1、总碳与粘结剂、固硫剂、助燃剂之比为1:0.6:1:0.2时，产品具有较高的热值、抗碎性、颗粒密度和较低的破损率。最终制成的成型燃料从热值、强度和环境友好性方面均符合国家对于燃料的基本要求。

关键词：油基钻屑；热解灰渣；桉树炭化物；添加剂；成型燃料

Abstract

China is a piece of energy consumption big country. With the development of economy and society and the continuous improvement of industrial level, China's demand for energy is increasing day by day. The reserves of non renewable mineral resources such as coal and oil are in urgent need one after another, so it is urgent to find suitable alternative energy. Shale gas is a kind of clean and efficient unconventional resource, and has a large recoverable reserves in China, with a high development potential. In recent years, shale gas resources in China have been widely developed, but at the same time, with the development of shale gas, a large number of oil-based cuttings have been produced. There are a lot of heavy metal elements and microorganisms in oil-based drilling cuttings. If not handled properly, it will cause serious damage to the soil, water and atmospheric environment. Pyrolysis is one of the common methods to treat oil-based cuttings. The final pyrolysis temperature, heating rate, constant temperature time and nitrogen flow rate all affect the pyrolysis effect of oil-based cuttings. Besides, studies show that the pyrolysis ash of oil-based drilling cuttings has a certain combustion performance, and has the potential to prepare fuel, but the H/C is lower, and the combustion performance is better when mixed with the biomass with higher H/C. So in this paper, oil-based drilling cuttings pyrolysis ash and Eucalyptus carbonization are used as raw materials, and some additives such as binder, sulfur fixing agent and combustion supporting agent are used to prepare shaping fuel. First of all, the pyrolysis conditions such as final temperature, heating rate, constant temperature time and nitrogen flow rate were optimized, and the optimal dosage and proportion of Eucalyptus carbonization substance, water, binder, sulfur fixing agent and combustion supporting agent were explored by orthogonal experiment, in order to form a complete set of molding fuel preparation process combination system and produce a molding fuel with high practicability and stability,realize the standard treatment and resource utilization of oil-based cuttings. The results show that the final pyrolysis temperature is 400℃, the final temperature time is 60 min, the heating rate is 20℃·min^-1 and the nitrogen rate is 0.1 Under the condition of L·min^-1, the oil content of pyrolysis treatment is the lowest and the calorific value is higher; the ratio of water and total carbon is 1.0:1; the ratio of starch, sodium carboxymethylcellulose, sodium hydroxide and potassium permanganate is 20:2:1:0.1; the samples have the best molding effect, strength and porosity when they are pressed manually by honeycomb coal mold; when the ratio of biochar to oil-based drilling cuttings is 2:1, the ratio of total carbon to binder, solid When the ratio of sulfur and combustion supporting agent is 1:0.6:1:0.2, the product has higher calorific value, crushing resistance, particle density and lower damage rate. The final fuel conforms to the basic requirements of the country in terms of calorific value, strength and environmental friendliness.

Key Words: oil-based drilling debris; pyrolysis ash; eucalyptus carbonization; additive;formed fuel

目 录

第1章 绪论 1

1.1 研究背景 1

1.2 研究目的及意义 2

1.3 国内外研究现状分析 2

1.4 研究内容 3

第2章 实验材料与方法 4

2.1 实验材料及仪器 4

2.1.1 实验材料 4

2.1.2 实验仪器 4

2.2 实验设计 5

2.2.1 热解效果的影响因素 5

2.2.2 燃料性质的影响因素 5

2.2.3 最佳热解条件探究实验设计 6

2.2.4 最佳原料配比实验设计 6

2.3 实验方案 7

2.3.1 油基钻屑热解方案 7

2.3.2 成型燃料制备预实验方案 7

2.3.3 成型燃料制备方案 8

2.3.4 分析测定方法 9

第3章 实验结果与分析 10

3.1 试验材料理化性质分析结果 10

3.1.1 X射线荧光光谱分析 10

3.1.2 有机元素分析 11

3.1.4 热值、含油率分析 11

3.2 热解条件的比选 12

3.3 成型燃料原料及添加剂最佳配比的选定 12

3.3.1 预实验结果及分析 12

3.3.2 热值分析 15

3.3.3 抗碎性分析 17

3.3.4 破损率分析 18

3.3.5 颗粒密度分析 19

3.3.6 综合分析 20

3.4 最终成型燃料的性质分析 21

第4章 结论 23

参考文献 24

致谢 26

第1章 绪论

1.1 研究背景

我国对于能源的需求正随着经济社会的发展而不断提高，由于不可再生能源储量有限，积极开发无污染的清洁能源势在必行。页岩气是一种非常规的天然气资源，具有清洁高效的特点，我国页岩气储量大，开发潜力高，目前正在被大范围开采^[1]。油基钻屑主要为油基钻井液钻井时现场固控设备、循环罐底以及甩干减量化设备等所产生的油基钻井液和岩屑的混合物，是一种含有基础油、表面活性剂、无机盐、钻屑、污水、沥青类和褐煤类添加剂、重金属等的复杂多相体系^[2]，一般具有较高的含水率（10%~20%）和含油率（6%~40%）^[3]。

油基钻屑中含有病原菌、寄生虫等微生物，铜、铅、汞、铬等重金属，以及一定量的苯系物、蒽、芘、酚类等有毒物质，甚至还伴有放射性物质，如果不经过处理直接排放，会占用大量的土地资源，破坏土壤，影响作物生长的营养环境条件及品质；油基钻屑会污染地表水和地下水，使水体COD_Cr和色度升高，阻碍水体复氧过程，严重破坏生态平衡；直接排放的废弃泥浆由于自然消解会散发有毒气态污染物，而重金属等有害物质会保留在土壤中，通过植物的富集作用，最终进入人体，危害健康^[4]，因此油基钻屑已被列入《国家危险废弃物名录》^[5]。