裂解热模拟实验中碳同位素变化特征及其地球化学意义

采用高温模拟技术,对原油、氯仿沥青“A”、烃源岩、干酪根和原油族组分样品进行热模拟实验,分析不同样品在裂解过程中产物碳同位素组成的变化特征,研究其地球化学意义。原油、氯仿沥青“A”、干酪根、烃源岩和饱和原油族组分随热演化温度的增加,热模拟气态烃碳同位素演化规律是由重变轻再变重的演化趋势,700℃以前碳同位素分布呈正碳同位素系列分布,750℃以后出现丙烷碳同位素倒转,芳烃馏分和沥青质馏分的碳同位素值和正碳同位素系列分布出现差异;各样品随热模拟温度的增加,Δδ¹³C_2-1值都呈增大的趋势;Δδ¹³C_3-1、Δδ¹³C_3-2对原油、氯仿沥青“A”、饱和烃馏分与芳烃馏分和沥青质馏分随模拟温度的变化有差异;δ¹³C₂ -δ¹³C₃ 值和LN（C₂/C₃）值随模拟温度的增加呈正相关性。     

An optimized process for fabrication of high-aspect-ratio photoresist-derived carbon microelectrode array on silicon substrate

An optimized process was developed for fabrication of high-aspect-ratio photoresist-derived carbon microelectrode array on silicon substrate. This process consisted of conventional photolithography, three-step linear pyrolyzing process and micromechanical interlocking. Comparing with previous two-step pyrolysis, three-step linear pyrolysis process can better preserve the geometry of microstructure during pyrolysis, and micromechanical interlocking was introduced to improve bonding strength between carbon microstructure and substrate. As a result, it can be achieved that high-aspect-ratio carbon microelectrode array remained upright and robustly with substrate. The experimental results confirmed that the optimized process is very effective, and the technology will be helpful for integration of 3-dimensional carbon-based devices in the fields of bioMEMS and electrochemical analysis.     

Oil shale pyrolysis kinetics and variable activation energy principle

A modified first order kinetic equation with variable activation energy is employed to model the total weight loss of Ellajjun oil shale samples. Fixed bed retort with 400 g of oil shale sample size is used in this study in 350–550 °C temperature range. Variable heating rate, h, in the range 2.6–5 °C min⁻¹ are tested.     

Study on co-cracking performance of different hydrocarbon mixture in a steam pyrolysis furnace

Co-cracking is a process where the mixtures of different hydrocarbon feed stocks are cracked in a steam pyrolysis furnace, and widely adopted in chemical industries. In this work, the simulations of the co-cracking of ethane and propane, and LPG and naphtha mixtures have been conducted, and the software packages of COILSIM1D and SimCO are used to account for the cracking process in a tube reactor. The effects of the mixing ratio, coil outlet temperature, and pressure on cracking performance have been discussed in detail. The co-cracking of ethane and propane mixture leads to a lower profitability than the cracking of single ethane or single propane. For naphtha, cracking with LPG leads to a higher profitability than single cracking of naphtha, and more LPG can produce a higher profitability.     

Pyrolysis of waste-derived fuel mixtures containing PVC

This paper describes an experimental analysis of the pyrolysis of PVC and mixtures of PVC with wood (Finnish pine) and LDPE (low density polyethene) in nitrogen at 250-400 °C. The aim is to optimise the temperature range for producing low-chlorine or chlorine-free fuel in a dehydrochlorination reactor without pyrolysing any of the other combustible fractions. Results are presented for various process temperatures for PVC, PVC/wood and PVC/LDPE mixtures. It was found that the PVC tested is dehydrochlorinated at approximately 350 °C, and that secondary pyrolysis is suppressed when LDPE is present.     

Study on the structure and pyrolysis characteristics of Chinese western coals

The structure and pyrolysis characteristics of three inertinite-rich Chinese western coals were researched and compared with one relative vitrinite-rich Chinese middle coal by means of XRD, TG-DTG and fixed-bed reactor. The results show that the atomic ratio O/C, aromaticity factor, even ring condensation number and ring condensation index increase and atomic ratio H/C decreases with increasing inertinite content in coal; inertinite contains more aromatic ring structure than that of vitrinite; the crystallite structure order of coal char increases slightly with increasing heat treatment temperature. The higher inertinite content in coal is, the lower pyrolysis reactivity of coal is at lower temperature, and yet they have obvious second pyrolysis reactivity in higher temperature. The pyrolysis reaction in primarily devolatilisation phase that comes mainly from the decomposition of containing hydrogen function groups and the secondary devolatilisation at high temperature is mainly the decomposition of stable containing oxygen function groups in coal matrix with higher inertinite.     

Microwave heating processes involving carbon materials

Carbon materials are, in general, very good absorbents of microwaves, i.e., they are easily heated by microwave radiation. This characteristic allows them to be transformed by microwave heating, giving rise to new carbons with tailored properties, to be used as microwave receptors, in order to heat other materials indirectly, or to act as a catalyst and microwave receptor in different heterogeneous reactions. In recent years, the number of processes that combine the use of carbons and microwave heating instead of other methods based on conventional heating has increased. In this paper some of the microwave-assisted processes in which carbon materials are produced, transformed or used in thermal treatments (generally, as microwave absorbers and catalysts) are reviewed and the main achievements of this technique are compared with those obtained by means of conventional (non microwave-assisted) methods in similar conditions.     

Steam gasification reactivity of char from rapid pyrolysis of bio-oil/char slurry

A slurry of bio-oil and char originating from wood pyrolysis is a promising gasifier feed-stock because of its high energy density. When such a slurry is injected into a high temperature gasifier it undergoes a rapid pyrolysis yielding a char which then reacts with steam. The char produced by pyrolysis of an 80 wt% bio-oil/20 wt% char mixture at heating rates of 100-10,000 °C/s was subjected to steam gasification in a thermogravimetric analyzer. The original wood char from the bio-oil production was also tested. Gasification was conducted with 10-50 mol% steam at temperatures from 800 to 1200 °C. Reactivity of the slurry chars increased with pyrolysis heating rate, but was lower than that of the original chars. Kinetic parameters were established for a power-law rate model of the steam-char reaction, and compared to values from the literature. At temperatures over 1000 °C, the gasification rates appeared to be affected by diffusional resistance.     

裂解反应动力学模型研究概况

裂解反应动力学模型是裂解炉模拟的核心,其准确性直接影响裂解产物预测的准确性以及裂解炉先进控制水平,最终影响乙烯生产的成本.裂解反应动力学模型分为经验模型、分子反应模型和机理模型.分别介绍了三种模型的主要方法和优缺点,指出各类模型的应用方向.同时介绍了裂解反应模型未来研究方向.把裂解反应动力学模型和CFD模型结合进行模拟,计算结果的准确度将得到较大的提高,将为乙烯裂解炉的精确控制提供强有力的参考.     

Biodiesel production from waste animal fats using pyrolysis method

It is necessary to utilize waste cooking oil as a raw material of biodiesel because the land area available for cultivation in Japan is limited. Waste cooking oil also includes long-chain saturated compounds and free fatty acids derived from animal fats. The former has a high freezing point and the latter forms a soap with the alkali catalyst typically used in biodiesel production, reducing the yield. To make waste cooking oil available for biodiesel production, pyrolysis of the waste oil was attempted. The resulting triacylglycerols were found to decompose at 360 to 390 °C, fatty acids were generated by cleavage of the ester bond, and short-chain hydrocarbons and short-chain fatty acids were generated by cleavage of the unsaturated bonds in the hydrocarbon chain. When the retention time was extended with a reaction temperature of 420 °C, light-oil hydrocarbons were generated by decarboxylation of the fatty acids. By adding palladium supported by activated carbon (Pd/C) as a catalyst, decarboxylation was promoted, and hydrocarbons comparable to light oil were selectively obtained in high yield at 85 wt.%. Compared to the biodiesel obtained by transesterification, the biodiesel obtained by pyrolysis showed improvement of about − 5 °C in the pseudo-cold filter plugging point.