高碳烃氧化裂解制低碳烯烃的研究
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摘要
低碳烯烃在石化工业中起着举足轻重的作用。目前，其仍以高能耗、高CO_2排放的热裂解生产过程为主，热裂解的强吸热特性使其进一步发展的空间变小。
本论文以正己烷、环己烷、异辛烷和正癸烷为模型化合物，对高碳烷烃经氧化裂解过程制低碳烯烃进行了研究。侧重对不同烷烃经气相氧化裂解(GOC)制低碳烯烃并联产一氧化碳过程及铂基催化剂催化的正己烷临氢氧化裂解催化过程进行了研究。论文的主要目的是，通过将氧气、氢气(或合成气)引入低碳烯烃生产过程，实现低碳烯烃生产的低能耗、低CO_2排放和高碳资源利用率；并试图为共同加工天然气和重质原料烃过程寻找结合点。
不同原料烃的气相氧化裂解实验表明，与热裂解相比，气相氧化裂解在较低温度下就具有很高的烷烃转化率和高的烯烃收率；对难开环热裂解的环烷烃仍具有优良的裂解性能，所以适合加工富环烷烃的重烃组分。气相氧化裂解是一个高碳资源利用率的生产过程，除低碳烯烃外，其产物中的CO_x主要为CO，而CO_2的选择性低于1％。热力学计算结果表明，气相氧化裂解过程可在自热条件下进行，这将大大降低因燃料燃烧而向大气排放出的CO_2量。由于产物中相当量CO的存在，气相氧化裂解过程不适合生产纯的低碳烯烃，更适合为诸如加氢甲酰化等同时需要CO和低碳烯烃的过程提供原料。
典型催化剂催化下的正己烷催化氧化裂解实验表明，CO_x的选择性很难控制，且烷烃转化率和烯烃选择性与气相氧化裂解相比不具竞争性。铂基催化剂存在条件下，向原料中添加氢气可大大降低产物中CO_x的选择性，进而提高烯烃选择性。合成气(H_2/CO)可代替纯氢作为氢源，这不但解决了氢源问题，而且还便于调节产物中氢气、CO和烯烃的比例，为天然气和重质原料的共同加工提供结合点。
Light alkenes play a significant role in the petrochemical industry. They are commercially prepared by the traditional pyrolysis with the characteristics of high-energy consumption and high CO2 emission. Due to its strong endothermic nature, the further development in the pyrolysis is inhibited.
The oxidative cracking of model compounds, such as hexane, cyclohexane, isooctane and decane, were investigated in this paper. Emphases were put on the co-production of light alkenes and CO by the gas phase oxidative cracking (GOC) of above hydrocarbons and the oxidative cracking of hexane with the addition of hydrogen over platinum based catalysts. The aim of this paper is to decrease the energy consumption, reduce CO2 emission and realize the high efficient utilization of carbon resource during the process for the production of light alkenes by the introduction of oxygen, hydrogen (or syngas) and to find out if there exists a relationship between the utilization of natural gas and the processing of heavy feed.
It had been demonstrated by our experiments that higher conversion of hydrocarbons and yield of light alkenes could be obtained in the GOC of various hydrocarbons than those in the pyrolysis. The GOC process was also fit for the cycloalkanes, the ring cleavage of which was known to be hard in the pyrolysis process. Therefore, the GOC process could process naphthenes rich heavy feed. Apart from light alkenes, CO prevailed in the produced COX while the selectivity to CO2 was always below 1 %, so the efficient utilization of carbon resources in the GOC process is high. Based on the thermodynamic calculations, the GOC process
could proceed in an autothermic way, which would reduce greatly the discharging of
CO2 from the external burning of fuel. Due to the considerable CO in the products, the GOC process would be fit for offering raw materials to such process as hydroformylation, which demands for a mixture of light alkenes and CO instead of pure light alkenes.
In the catalytic oxidative cracking of hexane with three typical catalysts, the selectivity to COX could not be low enough and the conversion of hexane and yield of light alkenes could not compete with those in the GOC process. With the platinum based catalysts, the selectivity to COX could be significantly depressed and the selectivity to light alkenes could be correspondingly enhanced in the oxidative cracking of hexane with the addition of hydrogen. However, the hydrogen produced in the reactions could not compensate for that added in the feed. Syngas (H2 / CO) could replace the pure hydrogen in the oxidative cracking of hexane with the addition of hydrogen, which not only acted as a hydrogen resource but also adjusted the ratio of light alkenes / H2 / CO in the products. The usage of syngas in the oxidative cracking of hexane enlightens a way to co-process natural gas and heavy feed.
本论文以正己烷、环己烷、异辛烷和正癸烷为模型化合物，对高碳烷烃经氧化裂解过程制低碳烯烃进行了研究。侧重对不同烷烃经气相氧化裂解(GOC)制低碳烯烃并联产一氧化碳过程及铂基催化剂催化的正己烷临氢氧化裂解催化过程进行了研究。论文的主要目的是，通过将氧气、氢气(或合成气)引入低碳烯烃生产过程，实现低碳烯烃生产的低能耗、低CO_2排放和高碳资源利用率；并试图为共同加工天然气和重质原料烃过程寻找结合点。
不同原料烃的气相氧化裂解实验表明，与热裂解相比，气相氧化裂解在较低温度下就具有很高的烷烃转化率和高的烯烃收率；对难开环热裂解的环烷烃仍具有优良的裂解性能，所以适合加工富环烷烃的重烃组分。气相氧化裂解是一个高碳资源利用率的生产过程，除低碳烯烃外，其产物中的CO_x主要为CO，而CO_2的选择性低于1％。热力学计算结果表明，气相氧化裂解过程可在自热条件下进行，这将大大降低因燃料燃烧而向大气排放出的CO_2量。由于产物中相当量CO的存在，气相氧化裂解过程不适合生产纯的低碳烯烃，更适合为诸如加氢甲酰化等同时需要CO和低碳烯烃的过程提供原料。
典型催化剂催化下的正己烷催化氧化裂解实验表明，CO_x的选择性很难控制，且烷烃转化率和烯烃选择性与气相氧化裂解相比不具竞争性。铂基催化剂存在条件下，向原料中添加氢气可大大降低产物中CO_x的选择性，进而提高烯烃选择性。合成气(H_2/CO)可代替纯氢作为氢源，这不但解决了氢源问题，而且还便于调节产物中氢气、CO和烯烃的比例，为天然气和重质原料的共同加工提供结合点。
Light alkenes play a significant role in the petrochemical industry. They are commercially prepared by the traditional pyrolysis with the characteristics of high-energy consumption and high CO2 emission. Due to its strong endothermic nature, the further development in the pyrolysis is inhibited.
The oxidative cracking of model compounds, such as hexane, cyclohexane, isooctane and decane, were investigated in this paper. Emphases were put on the co-production of light alkenes and CO by the gas phase oxidative cracking (GOC) of above hydrocarbons and the oxidative cracking of hexane with the addition of hydrogen over platinum based catalysts. The aim of this paper is to decrease the energy consumption, reduce CO2 emission and realize the high efficient utilization of carbon resource during the process for the production of light alkenes by the introduction of oxygen, hydrogen (or syngas) and to find out if there exists a relationship between the utilization of natural gas and the processing of heavy feed.
It had been demonstrated by our experiments that higher conversion of hydrocarbons and yield of light alkenes could be obtained in the GOC of various hydrocarbons than those in the pyrolysis. The GOC process was also fit for the cycloalkanes, the ring cleavage of which was known to be hard in the pyrolysis process. Therefore, the GOC process could process naphthenes rich heavy feed. Apart from light alkenes, CO prevailed in the produced COX while the selectivity to CO2 was always below 1 %, so the efficient utilization of carbon resources in the GOC process is high. Based on the thermodynamic calculations, the GOC process
could proceed in an autothermic way, which would reduce greatly the discharging of
CO2 from the external burning of fuel. Due to the considerable CO in the products, the GOC process would be fit for offering raw materials to such process as hydroformylation, which demands for a mixture of light alkenes and CO instead of pure light alkenes.
In the catalytic oxidative cracking of hexane with three typical catalysts, the selectivity to COX could not be low enough and the conversion of hexane and yield of light alkenes could not compete with those in the GOC process. With the platinum based catalysts, the selectivity to COX could be significantly depressed and the selectivity to light alkenes could be correspondingly enhanced in the oxidative cracking of hexane with the addition of hydrogen. However, the hydrogen produced in the reactions could not compensate for that added in the feed. Syngas (H2 / CO) could replace the pure hydrogen in the oxidative cracking of hexane with the addition of hydrogen, which not only acted as a hydrogen resource but also adjusted the ratio of light alkenes / H2 / CO in the products. The usage of syngas in the oxidative cracking of hexane enlightens a way to co-process natural gas and heavy feed.
引文
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