乙炔加氢制乙烯浆态床反应器的CFD模拟

对浆态床反应器中乙炔加氢制乙烯过程进行了模拟研究，采用TFM-PBM耦合方法描述浆态床内气相与浆态相的流动，并耦合乙炔加氢反应动力学建立流动-反应综合模型。通过小试实验对该模型进行验证，并将验证后的模型应用于浆态床中试装置中内构件作用机制与操作条件影响的模拟分析。结果表明，在浆态床反应器放大时，可通过设置竖管内构件，以破碎气泡，抑制气相径向运动，使乙炔加氢过程均匀、充分地进行。乙炔加氢制乙烯过程与气相停留时间和反应温度密切相关，在反应器放大中需严格控制温度，并可通过改变反应器内液位高度实现对气相停留时间的调控，从而可在保证乙炔充分转化的同时获得更高的乙烯选择性。     

Inlet effect on the coal pyrolysis to acetylene in a hydrogen plasma downer reactor

Coal pyrolysis to acetylene in hydrogen plasma is a clean process for the coal utilization. A gas–solid downer reactor was employed to facilitate the high temperature reactions of coal pyrolysis in milliseconds. The effect of the inlet design on the coal injection was studied using CFD simulations, which were qualitatively compared with the cold model experiments in the prototype of a 2 MW hydrogen plasma reactor. The results revealed that the distribution of the coal particles near the inlet nozzles was significantly influenced by the layout of the flat‐shaped nozzles and the operating conditions. Accordingly the heating efficiency of the particles by the hot gas showed strong dependence on the inlet design. The hot model tests demonstrated that the reactor performance characterized by the concentration of acetylene in the product gas increased from ～7.6 to 9.6% by optimizing the nozzle design, which indicated the critical role of the nozzle design in the coal pyrolysis process.     

The pyrolysis of natural gas: A study of carbon deposition and the suitability of reactor materials

This study of methane pyrolysis was designed to look at carbon deposition on the internal reactor and wafer surface during CH₄ pyrolysis. The rate of carbon deposition on the internal reactor surfaces could be reduced with: lower methane/oxygen ratios, shorter residence times, and lower temperatures. The type of carbon formed appeared to have a significant effect on the pyrolysis process. Pyrolytic carbon with a lower order structure produces a higher selectivity for carbon formation compared to carbon with a higher order structure. Form a process perspective, there are two obvious means of addressing this: deposited carbon could be regularly removed; and/or pyrolysis conditions are selected that produce carbon with a higher order structure. From the results, it is very clear that any development of a commercial process for natural gas pyrolysis in ceramic reactor systems would have to carefully address the selection of reactor material. © 2018 American Institute of Chemical Engineers AIChE J, 65: 1035–1046, 2019     

压力反应釜中低温热裂解废旧LLDPE塑料制备PE蜡

以废旧线性低密度聚乙烯（LLDPE）为原料,采用压力反应釜在封闭条件下通过热裂解方法制备聚乙烯蜡（PE蜡）,研究了裂解时间、温度和压力对产物的产率、分子量和滴熔点的影响,并通过红外光谱对产物的官能团进行了分析。实验结果表明,在裂解时间为15~60 min,裂解温度约为260℃的条件下,LLDPE裂解所得到的PE蜡性能较佳,其主要成分为直链烷烃和烯烃,滴熔点大于100℃,黏均分子量处于1400~4700;由动力学分析可知,由于封闭反应体系增加了反应压力,降低了裂解温度和活化能,促进了LLDPE裂解反应进行,同时抑制了气体分子的产生,有利于获得PE蜡。     

CFD simulations of quenching process for partial oxidation of methane:Comparison of jet-in-cross-flow and impinging flow configurations

A new quenching process using the cold pyrolysis gas has been proposed for the partial oxidation (POX) of methane to recover the heat.The mixing of hot product gas and cold pyrolysis gas in milliseconds is critical to this new approach.Two most widely-used rapid mixing configurations,i.e.the jet-in-cross-flow (JICF) and impinging flow configurations,are compared in terms of mixing and quenching performances using computational fluid dynamics (CFD) coupled with detailed reaction mechanism Leeds 1.5.The mixedness,residence time distribution,temperature decreasing rate and loss ratio of acetylene during the quenching are systematically studied.The results show that the impinging flow has a more uniform mixing and narrower residence time distribution than the JICF.However,the temperature decreasing rate of the mainstream is faster in the JICF than in the impinging flow.The loss ratio of acetylene in the quenching process is 2.89％ for the JICF and 1.45％ for the impinging flow,showing that the impinging flow configuration is better and feasible for the quenching of POX of methane.     

Pyrolysis oil upgrading by high pressure thermal treatment

High pressure thermal treatment (HPTT) is a new process developed by BTG and University of Twente with the potential to economically reduce the oxygen and water content of oil obtained by fast pyrolysis (pyrolysis oil), properties that currently complicate its co-processing in standard refineries. During the HPTT process, pyrolysis oil undergoes a phase split yielding a gas phase, an aqueous phase and an oil phase. In this study, HPTT experiments were carried out at different operating conditions in a continuous tubular reactor. Experimental results showed that, with increasing temperature and residence time, the release of gases (mainly CO₂) and the production of water increased, reducing the oxygen content of the oil phase and hence increasing the energy content (from 14.1 to 28.4 MJ/kg) having the temperature a larger effect when compared to the residence time. Using gel permeation chromatography (GPC), an increase of the molecular weight of the oil phase, probably due to polymerisation of the sugars present in pyrolysis oil, was observed. When water was added as solvent to dilute the feed oil, a decrease of the molecular weight of the resulting oil phase was observed. This indicated that the concentration of organic components had a direct effect on the formation of high molecular weight components. In conclusion, during HPTT an oil with lower oxygen and water content with higher energy value was produced, but adverse formation of high molecular weight components was also detected.     

超短接触反应器气固快分装置的数值模拟

A gas-solids fast separator was studied for its potential application in the process of coal pyrolysis to acetylene in plasma. The CFD method was employed to simulate the flow behavior in the gas-solids fast separator based on the realizable k-ε turbulence model and the discrete particle model（DPM）.The separation efficiency and residence time of gas phase in the gas-solids fast separator could be calculated. The numerical simulations were validated by the experimental results at a low velocity of the inlet gas（e. g. ,4 m·s^-1）.With the increase of gas velocity at the inlet,the separation efficiency was increased,and the residence time of gas phase was reduced accordingly. The separation efficiency approached 100% when particle diameter was larger than 20 μm. When inlet velocity was 100 m·s^-1,the mean residence time of gas phase was about 35 ms. To be noted,the performance of the gas-solids fast separator could be improved,for example by shortening the length of the separator,with a reduced residence time of gas phase at ～20 ms. It is expected that the gas-solids fast separator can meet the stringent demand of the coal pyrolysis to acetylene process for the milliseconds reaction,quench and separation.     

Gas and soot products formed in the pyrolysis of acetylene–ethanol blends under flow reactor conditions

The present paper reports a laboratory study on the pyrolysis of different blends containing acetylene, known as an important soot precursor, and ethanol, regarded as an appropriate additive to conventional fuels aiming to diminish the emission of pollutants coming from combustion processes. Pyrolysis experiments of acetylene–ethanol blends, for a total initial concentration of reactants of 50,000 ppm, with variable volume percentages of ethanol between 0 and 40% with respect to the total concentration of reactants, have been carried out in a quartz flow reactor working in a temperature range of 975–1475 K. The influence of both pyrolysis temperature and ethanol concentration in the blend on the gas and solid products has been evaluated. As the reaction temperature is increased, the soot production is higher and yield to carbonaceous gas products decreases. It is noticed that the presence of ethanol inhibits the production of soot and the diminution of soot formation does not present a linear dependency with the ethanol concentration; the influence is comparatively stronger when adding small amounts of ethanol. The analysis of the gas products reveals that increasing the ethanol percentage in the blend causes an increase of the concentration of some intermediates such as ethylene, ethane, methane or benzene, pointing to a variation of the reacting species which could prevent soot formation. A literature detailed gas phase kinetic mechanism including reaction subsets for acetylene and ethanol conversion has been used to simulate the experimental results. This theoretical study has been carried out with the purpose of analyzing the trends of the evolution of gas products and getting a better understanding of the gas phase processes involved in the pyrolysis of the different blends, although soot formation is not included.     

管式反应器液相循环反应制备二甘醇乙烯基醚

以乙炔和二甘醇为原料,二甘醇钾为催化剂,采用管式反应器液相循环反应制备二甘醇乙烯基醚。研究了催化剂用量、反应温度、反应压力和停留时间等因素对乙炔转化率的影响,得到较为适宜的反应条件为：催化剂二甘醇钾用量为二甘醇质量的4%、反应温度175℃、反应压力6MPa、停留时间175s。在该条件下进行了液相连续循环反应,反应达到稳态时,二甘醇的转化率为76.03%,二甘醇单乙烯基醚收率为59.03%,二甘醇双乙烯基醚的收率为15.10%,合计二甘醇乙烯基醚总收率为74.13%。单位反应体积二甘醇乙烯基醚的产率为143.2g/（h·mL）。二甘醇与乙炔反应符合一级反应动力学方程,反应的指前因子k₀=1.20×10⁸s^–1,反应的活化能E=86.86kJ/mol。管式反应器中无气相乙炔,克服了高温高压下气相乙炔易燃易爆的危险。     

Simulation Study of a Novel Process Co‐Producing Synthesis Gas and Light Olefins

There are abundant resources of heavy hydrocarbons worldwide, and their utilization is becoming more widespread as time progresses. The present paper proposes a process that combines coke gasification and heavy hydrocarbon pyrolysis, producing synthesis gas and light olefins. Simulation studies on the process are carried out by using Aspen Plus. The results show that the temperature of the gasification‐pyrolysis can be controlled by changing the feed rate of O₂ and steam. In addition, the coke jam problem can be solved by increasing the gasification‐pyrolysis temperature or residence time. The maximum amount of light olefins can be acquired by controlling the gasification‐pyrolysis residence time. More than 37 wt % heavy hydrocarbons are changed to synthesis gas with more than 15 wt % changed to light olefins in the case studied.     

催化裂解反应条件对产物收率的影响

增产低碳烯烃、轻质芳烃等产物是催化裂解技术发展的趋势,反应条件是影响催化裂解产物分布的关键因素。介绍催化裂解过程涉及的反应机理,概述反应温度、剂油质量比、停留时间(空速)、水油质量比等反应条件,裂解装置和原料油性质对产物收率的影响,结合工业实例分析反应条件对产物收率的影响。     

Thermodynamic analysis of coal pyrolysis to acetylene in hydrogen plasma reactor

A systematic re-examination of the thermodynamic study on the process of coal pyrolysis to acetylene in a hydrogen plasma reactor was performed with referenced pilot-plant data at the scale of 2-MW plasma. At the ultra-high temperature conditions, the gas phase composition may reach thermodynamic equilibrium immediately no matter whether the solid carbon exists or not. The mass ratio of C/H in the gaseous phase plays a significant role in the acetylene concentration at the thermodynamic equilibrium states. It is demonstrated either in thermodynamics calculation or in hot tests that a mass ratio of C/H near or above 2 is essential to gain an acceptable concentration of acetylene in the mixed gases, which indicates that the mixing efficiency between gas and coal particles near the coal injection point becomes pivotal to the yield of acetylene for its direct influence on the devolatilization of coal, i.e., the gaseous C/H ratio. Being consistent with the hot test experience, the extra amount of water added into the system may inhibit the production of acetylene. However, the addition of methane might impose a positive effect on the yield of acetylene and therefore on the overall reactor performance.     

热等离子体煤制乙炔裂解气烃类循环过程分析

针对等离子体煤裂解制乙炔过程, 提出了将过程裂解气中副产的烃类分离, 循环输入等离子体反应器的新型工艺流程。基于新疆天业2 MW示范平台装置的典型运行参数, 采用热力学分析手段, 理论上分析了该工艺流程对于体系乙炔产量、单位质量乙炔煤耗和裂解电耗等的影响。结果表明, 裂解气烃类循环可以有效提高裂解气中乙炔浓度和产率, 同时减少煤粉输送气等流程气体的使用。典型操作条件下, 采用裂解气烃类循环工艺可以增加35.6%的乙炔收率和13.4%的氢气收率, 降低30%的单位乙炔煤耗和裂解电耗, 是高效可行的优化方案。     

煤等离子体热解制乙炔工艺的工程探讨

与传统的煤 炼焦 电石 乙炔的工艺路线相比 ,等离子体裂解煤制取乙炔工艺是一项具有广阔工业前景的新技术 ,它的工业化将推动煤的优化利用。分析了煤和等离子体射流的混合情况、反应时间及急冷方式对乙炔收率的影响 ;探讨了等离子发生器的热效率、成流气的初始温度、反应器的热损失、反应生成物余热回收率、残渣分离、反应气的分离和精制以及成流气的循环能耗等 7因素对等离子体热解煤制乙炔能耗的影响以及长周期生产的影响因素 ;提出了煤间接等离子体热解制乙炔工艺的思路 ,可以克服煤直接等离子体热解制乙炔工艺中的部分缺陷 ,消除煤种对裂解原料的限制。     

Effect of governing parameters on pyrolysis of liquefied petroleum gases in the high-temperature heat carrier

Detailed measurements of temperature and product distributions are carried out during the pyrolysis of liquefied petroleum gases in a model reactor where the inlet conditions of the feedstock/heat carrier fast mixing are realized. The developed theoretical process model involves the detailed kinetic scheme that is tested by the reference data and our experiments. The yield of the most valuable product of petrochemistry, ethylene, substantially increased as compared to the conventional furnace-pyrolysis method is the specific feature of the performed experiments results. By the results of the numerical simulation, the effect of temperature, pressure, and residence time in the reactor on the pyrolysis product composition is determined. The calculation results enable to optimize operation conditions for the fast-mixing reactor.     

热等离子体热解煤焦油制乙炔

利用热等离子高温、高焓等特性热解煤焦油制乙炔是一条清洁高效的乙炔生产技术。在实验室对热等离子体热解煤焦油反应中的原料进样温度、反应气氛、输入比焓等关键因素展开了研究。结果表明,热等离子体可将煤焦油直接转化为乙炔及其他小分子气态产品,预热煤焦油可改善其流动性从而提高煤焦油和等离子体射流的初始混合效率;氢等离子体的加入可显著提高煤焦油转化率和乙炔收率并减少结焦;随着输入比焓的增加,煤焦油转化率、乙炔收率和气态产品总收率均得到提高。在实验中得到的煤焦油转化率最高为86.3%,乙炔收率最高为24.6%,气态产品总收率最高为51.7%。煤焦油在热等离子体的热解过程中副产乙烯,乙烯收率达到7.9%。乙炔收率和乙烯收率的比值可用于预测气相体系温度。     

A novel biomass air gasification process for producing tar-free higher heating value fuel gas

Biomass is a promising sustainable energy source. A tar-free fuel gas can be obtained in a properly designed biomass gasification process. In the current study, a tar-free biomass gasification process by air was proposed. This concept was demonstrated on a lab-scale fluidized bed using sawdust under autothermic conditions. This lab-scale model gasifier combined two individual regions of pyrolysis, gasification, and combustion of biomass in one reactor, in which the primary air stream and the biomass feedstock were introduced into the gasifier from the bottom and the top of the gasifier respectively to prevent the biomass pyrolysis product from burning out. The biomass was initially pyrolyzed and the produced char was partially gasified in the upper reduction region of the reactor, and further, char residue was combusted at the bottom region of the reactor in an oxidization atmosphere. An assisting fuel gas and second air were injected into the upper region of the reactor to maintain elevated temperature. The tar in the flue gas entered the upper region of the reactor and was decomposed under the elevated temperature and certain residence time. This study indicated that under the optimum operating conditions, a fuel gas could be produced with a production rate of about 3.0 Nm³/kg biomass and heating value of about 5000 kJ/Nm³. The concentration of hydrogen, carbon monoxide and methane in the fuel gas produced were 9.27%, 9.25% and 4.21%, respectively. The tar formation could be efficiently controlled below 10 mg/Nm³. The system carbon conversion and cold gasification efficiency reached above 87.1% and 56.9%, respectively. In addition, the investigation of energy balance for the scale-up of the proposed biomass gasification process showed that the heat loss could be recovered by approximately 23% of total energy input. Thus, partial fuel gas that was produced could be re-circulated and used to meet need of energy input to maintain the elevated temperature at the upper region of reactor for tar decomposition. It was predicted the heating value of product fuel gas would be 8000 kJ/Nm³ if the system was scaled up.     

页岩灰和FCC催化剂调控油页岩热解产物二次反应特性

采用两段反应器对油页岩热解初级挥发分进行二次催化反应特性研究,考察了第2段反应器内不同的催化载体、反应气氛与停留时间对油气收率及品质的影响。结果表明,在考察的停留时间范围内页岩灰具有相对适中的催化活性来调控热解挥发分产物的二次反应,水蒸气气氛能够进一步提高热解油收率约5%,并能够在一定程度上抑制裂解气体中C₂~C₃组分的生成。页岩灰作为催化载体能够转化热解油中VGO（馏程>350℃）等重质组分,随停留时间增加油品馏程向轻组分转移。油品组分GC-MS结果表明,较短停留时间内（<3 s）,水蒸气添加能够有效抑制热解油中脂肪烃类的过度裂解,与氮气相比提高汽柴油馏分含量20%以上。过长的停留时间（3~5 s）会造成VGO等馏分缩聚生成焦炭,从而大幅降低热解油收率。     

Catalytic Treatment of Vacuum Carburizing Off Gas

The aim of this investigation was to find a suitable procedure for the treatment of higher polycyclic aromatic hydrocarbons, produced during vacuum carburizing of steel. In a lab scale apparatus the carburizing gas acetylene was pyrolyzed and the generated gases converted in a downstream catalytic bed reactor. The results show that it is possible to remove the higher pyrolysis products from the off gas. A complete conversion of the off gases into carbon and hydrogen was achieved with a Ni/SiO₂/SiC‐catalyst at temperatures ? 520 °C. Coke, formed during the conversion of the hydrocarbons on the catalyst, is removed from the catalyst by burning it off. The functionality of the catalyst is investigated for both the reduced and the non‐reduced state, whereby the non‐reduced catalyst deactivates faster.     

煤制乙炔裂解气的降温工艺

介绍了煤制乙炔工艺中裂解气降温工艺流程并对关键设备的选型进行了详细计算。