酸焦油的催化处理

G. Krymets, M. Litynska, O. Melnychuk
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摘要

酸焦油是煤、石油和石化产品(炼油、苯精炼和石油馏分精炼以及异丁烷与丁烯的烷基化)加工过程中产生的废物。酸焦油组成包括树脂物质、有机物和不饱和烃的聚合产物。酸焦油中游离硫酸的含量通常达到70%(重量计)。石油中的金属几乎全部集中在焦油中,其中钒和镍的含量分别可达0.046%和0.014%。许多国家将酸焦油放在露天的采石场、储存池、谷仓、泻湖或垃圾填埋场附近。由于土壤、水和空气污染,它对人类和附近的环境构成风险甚至潜在威胁。因此,酸焦油的处理是一项非常重要的生态和工业任务。本文研究了催化裂化和精馏两种方法对酸性焦油的利用。由于无水AlCl3在许多有机反应中具有催化活性,因此在石油渣油裂解得到挥发性汽油馏分的过程中,使用无水AlCl3作为催化剂。催化剂配比(0.15 g/g焦油或0.1 g/g焦油)对酸焦油裂解过程中挥发分数和沸点温度的影响非常显著。根据1H NMR研究结果,催化裂化过程中挥发分的主要成分为烷烃CH3-(CH2)n-CH3。这些馏分的组成与汽油和柴油的组成相似。一系列的蒸馏实验(对预先脱酸和离心的焦油进行蒸馏,对未经脱酸和离心的酸焦油进行蒸馏,对未经离心的预先脱酸的焦油进行蒸馏)对每种材料给出了不同的结果。脂肪族烃是挥发油的主要成分(分别为~ 80%、~ 60%和~ 90%),脂肪族s -有机物含量也很高(分别为~ 10%、~ 30%和~ 8%)。因此,无论是催化裂化还是焦油蒸馏,脂肪烃都是挥发分的主要成分。在焦油蒸馏过程中,焦油脱酸增加了脂肪烃的产量,并由于其与碳酸钙的反应而减少了s -有机化合物的产量。这是在燃料生产的背景下的观点。
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Catalytic processing of the acid tars
Acid tars are wastes from the processing of coal, petroleum, and petrochemicals (oil refining, benzene refining and petroleum fractions refining and alkylation of isobutane with butenes). Acid tar compositions include resinous substances, organic matter, and polymerization products of unsaturated hydrocarbons. The presence of free sulfuric acid in acid tars often reaches 70 % by weight. Almost all metals from oil are concentrated in tars, and the content of vanadium and nickel can reach 0.046 and 0.014 %, respectively. A lot of countries keep acid tar in the open air in spent quarries, storage ponds, barns, lagoons or near landfills. It poses a risk or even potential threat to people and to the environment nearby due to soil, water, and air pollution. Thus, disposal of the acid tars is a very important ecological and industrial task. In this study, we have researched catalytic cracking and distillation as the utilization methods for acid tar. Anhydrous AlCl3 was used as a catalyst during the cracking of petroleum residues to obtain volatile gasoline fractions due to its catalytic activity in many organic reactions. The catalyst ratios (0.15 g/g of tar or 0.1 g/g of tar) had a very significant influence on the number of volatile fractions and boiling temperature in the acid tar cracking process. According to the results of 1H NMR research, the main components of volatile fractions in the case of catalytic cracking were alkanes CH3-(CH2)n-CH3. The compositions of these fractions were similar to the compositions of gasoline and diesel fuel. A series of distillation experiments (distillation of previously deacidified and centrifuged tar, acid tar without deacidification and centrifugation, and previously deacidified tar without centrifu-gation) gave different results for each type of material. Aliphatic hydrocarbons were the main components of volatile fractions (~ 80, ~ 60 and ~ 90 %, respectively) and the contents of aliphatic S-organic compounds were also significant (~ 10, ~ 30 and ~ 8 %). Thus, both for catalytic cracking and for tar distillation, aliphatic hydrocarbons were the main component of volatile fractions. Deacidification of tar increased the yield of aliphatic hydrocarbons during tar distillation and decreased production of S-organic compounds due to its reactions with calcium carbonate. It is perspective in the context of fuel production.
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