Coke formation during naphtha pyrolysis in a tubular reactor

The effect of run time, temperature, conversion and inlet steam-to-naphtha ratio on the rate of coke deposition during naphtha pyrolysis in an annular tubular reactor has been investigated. Rates of coke deposition increased with increasing temperature, conversion and inlet naphtha partial pressure. Pyrolysis and coking models available for naphtha cracking were used to calculate the total coke deposited by treating the temperature difference between the reacting fluid and the outer reactor wall as a parameter. For all the runs, the experimental and calculated coking rates were in close agreement for an assumed temperature difference of 35-45°C.     

石脑油催化裂解结构化反应器反应特性的CFD模拟

以石脑油为原料,采用催化裂解六集总动力学模型,建立描述结构化反应器内催化裂解的反应器数学模型,并利用CFD软件对结构化反应器内的石脑油催化裂解性能进行数值模拟。通过改变孔道直径、反应器长度以及反应器内温度、气体入口速率考察反应器结构尺寸和反应条件对目标产物乙烯、丙烯的收率及石脑油转化率的影响。结果表明,反应器孔道直径的增加,目标产物收率减小,反应器长度20 mm时反应完全,升高反应温度和增大入口速率均有利于目标产物的生成。在入口温度680 ℃和入口速率0.4 m·s^-1条件下,石脑油转化率92%,乙烯收率19.3%,丙烯收率23.1%。而在相同反应条件下的固定床反应器中乙烯收率10.3%,丙烯收率13.3%,石脑油转化率80.0%。     

Effect of benzene and thiophene on rate of coke formation during naphtha pyrolysis

The effect of benzene or thiophene addition to the feed on the rates of coke formation during naphtha pyrolysis has been investigated in a jet-stirred reactor at atmospheric pressure in the temperature range of 1073-1103 K. In addition, the effect of temperature, space time, weight ratio of steam to naphtha and the material of construction on the rate of coke deposition was also studied. The rate of coke formation increased as the temperature, space time and aromatic content of the feed was increased whereas it decreased with an increase in the weight ratio of steam to naphtha or the thiophene content of the feed. Addition of thiophene increased the rate of naphtha pyrolysis and significantly reduced the aromatic yields. Rates of coke formation for both thiophene-free and thiophene-containing naphtha could be modeled by power law expressions involving the aromatics.     

石脑油预加氢装置运行状况分析及防护措施

介绍了中国石化西安石化分公司300 kt/a石脑油加氢装置运行状况,针对反应器压力降升高、石脑油进料/反应产物换热器内漏导致精制油硫含量超标原因进行系统分析,通过检测、比较各换热器低硫端油样中的总硫含量判断换热器的内漏位置,指出原料油携带重质馏分油及腐蚀残渣是反应器压力降升高的重要因素,垢下腐蚀和H2S-HCl-H2O-NH3酸性腐蚀是换热器管束减薄甚至穿孔的主要原因。提出进料线设置过滤器、增设1台高温脱氯器、优化注水部位及注水量、石油脑油进料直供及材质合适材质等措施,以保证装置长周期运行。     

乙烯裂解炉石脑油裂解反应的数值模拟

以 SL-Ⅱ型乙烯裂解炉反应管为对象,结合烯烃厂裂解工艺参数,对管内石脑油裂解反应过程进行了模拟研究。裂解反应模型采用 Kumar 提出的分子反应模型,模拟得到了管内油气流速、温度、裂解产物的变化规律。结果表明,近壁层流层的存在使得管内油气径向速度、温度梯度较大,二维管内模型可以更全面地描述裂解反应过程。模拟得到的裂解产物收率与裂解炉的生产运行数据进行了比较,两者基本一致,验证了裂解反应模型的合理性。     

Pyrolysis with partial combustion of oil shale fines in a spouted bed

Pyrolysis with partial combustion of oil shale fines from the Irati Formation in Brazil has been investigated in a 30 cm diameter spouted bed reactor. Experiments were carried out at atmospheric pressure and temperatures between 450 and 600°C. The oi] shale particle size was less than 6.35 mm. Spouting gas temperatures ranged from 20 to 565°C. Three inlet gas pipe diameters and two spouted bed heights were studied. Operation of the process was found to be stable over a wide range of test conditions. Results are presented for oil and gas quality, efficiency of retorting and overall performance of the plant.     

连续换热式耐硫甲烷化反应器的模拟与分析

建立了逆流换热的耐硫甲烷化列管式反应器的拟均相二维模型。运用差分将模型降阶为一阶常微分方程组,采用Ｒｕｎｇｅ－Ｋｕｔａ法求解。模拟结果是可信的。分别考察了设备参数和操作条件对反应床层的影响,结果表明：管径对温度分布影响很大;反应温度和压力是反应器操作的控制因素;原料气组成制约反应结果     

Modelling of packed bed membrane reactors for autothermal production of ultrapure hydrogen

The conceptual feasibility of a packed bed membrane reactor for the autothermal reforming (ATR) of methane for the production of ultrapure hydrogen was investigated. By integrating H₂ permselective Pd-based membranes under autothermal conditions, a high degree of process integration and intensification can be accomplished which is particularly interesting for small scale H₂ production units. A two-dimensional pseudo-homogeneous packed bed membrane reactor model was developed that solves the continuity and momentum equations and the component mass and energy balances. In adiabatic operation, autothermal operation can be achieved; however, large axial temperature excursions were seen at the reactor inlet, which are disadvantageous for membrane life and catalyst performance. Different operation modes, such as cooling the reactor wall with sweep gas or distributive feeding of O₂ along the reactor length to moderate the temperature profile, are evaluated. The concentration polarisation because of the selective hydrogen removal along the membrane length was found to become significant with increasing membrane permeability thereby constraining the reactor design. To decrease the negative effects of mass transfer limitations to the membrane wall, a small membrane tube diameter needs to be selected. For a relatively small ratio of the membrane tube diameter to the particle diameter, the porosity profile needs to be taken into account to prevent overestimation of the H₂ removal rate. It is concluded that autothermal production of H₂ in a PBMR is feasible, provided that the membranes are positioned outside the inlet region with large temperature gradients.     

Kinetics of coke deposition in naphtha pyrolysis

The effect of run time, surface area, reaction temperature and inlet naphtha partial pressure on the rate of coke formation during naphtha pyrolysis has been investigated in a jet-stirred reactor. The pyrolysis products could be predicted by a model developed earlier for naphtha pyrolysis. Various simplified models for the coke formation involving either the reactant or products were postulated and the kinetic parameters determined by a statistical analysis. The rate of coke formation was best modelled by an approximately second order reaction involving the aromatics.     

SL-Ⅱ型工业乙烯裂解炉内燃烧传热与裂解反应的耦合模拟

采用计算流体力学(CFD)方法对SL-Ⅱ型工业乙烯裂解炉辐射段炉膛内的燃烧传热及管内石脑油裂解反应过程进行耦合模拟,建模及耦合求解在CFX中完成.计算时采用标准k-ε双方程湍流模型、旋涡耗散/有限化学速率(EDM/FRC)燃烧模型和离散传播(DT)辐射模型,其中介质辐射特性采用多灰气加权模型;石脑油裂解反应采用Kuma...     

Coupled simulation of combustion with heat transfer and cracking reaction in SL-Ⅱ industrial ethylene pyrolyzer

采用计算流体力学(CFD)方法对SL-Ⅱ型工业乙烯裂解炉辐射段炉膛内的燃烧传热及管内石脑油裂解反应过程进行耦合模拟,建模及耦合求解在CFX中完成。计算时采用标准k-ε双方程湍流模型、旋涡耗散/有限化学速率(EDM/FRC)燃烧模型和离散传播(DT)辐射模型,其中介质辐射特性采用多灰气加权模型;石脑油裂解反应采用Kumar分子反应模型,流体流动方程组由全隐式的耦合算法求解。模拟结果与工业数据吻合良好,验证了模型的可靠性。结果表明,管内裂解产物丙烯和丁烯收率先增后减,甲烷和乙烯收率一直增大;出口管外壁温度沿管长分布因侧壁烧嘴的加入而更加均匀;炉膛中部的回流区使该区温度更加均匀;裂解炉结构的非对称性引起烟气流速分布不对称,进而导致后墙上侧壁烧嘴的供热效率相对前墙侧较低,本文模拟结果为裂解炉进一步设计与改造提供理论指导。     

催化裂解石脑油加氢利用路线开发

催化裂解与传统的高温蒸汽裂解相比,通过催化剂降低催化裂解反应活化能和反应温度,除生产乙烯、丙烯和丁烯等主要化工原料外,还副产一定量的轻质芳烃。分析催化裂解石脑油,结果表明,催化裂解石脑油主要为C₅~C₉馏分,芳烃质量分数62.97%,苯、甲苯和二甲苯质量分数54.38%,与全馏分裂解汽油相当,是优质的抽提芳烃原料。提出对原料进行预处理后,经两段加氢、产品抽提芳烃的利用路线,并在试验室采用切割塔及等温床完成对原料的预处理,制取满足两段加氢要求的原料。在一段入口温度(45~55) ℃、反应压力2.8 MPa、氢油体积比100∶1、液时空速1.5 h-1和二段入口温度(250~255) ℃、反应压力2.8 MPa、氢油体积比600∶1和液时空速1.5 h^-1条件下,对一段和二段进行1 000 h的加氢评价试验,结果表明,一段加氢后产品双烯值均＜2.5 g-I·（100g油）^-1,二段加氢产品溴价＜1.0 g-Br·（100g油）^-1,硫含量＜1.0 μg·g^-1,满足芳烃抽提对原料烯烃及硫含量的要求。     

Utilizing DE optimization approach to boost hydrogen and octane number in a novel radial-flow assisted membrane naphtha reactor

Hydrogen is a valuable raw material for chemical and petrochemical industry. In this regard, the operating conditions of a radial-flow tubular membrane reactor (RF-TMR) are optimized via Differential Evolution (DE) method to boost the hydrogen and aromatic yields in catalytic naphtha reforming process. In this novel configuration, the radial-flow pattern of the naphtha feed and the sweeping gas is considered in the tube and the shell sides to solve the pressure drop problem. Furthermore, the cross-section area of the tubular reactor is divided into some subsections and the gaps' wall between subsections are coated by the Pd–Ag membrane layer. The steady state and dynamic optimizations are carried out and twenty-nine decision variables such as operating pressure, membrane thickness, sweeping gas distribution and the ratio of length to diameter (LOD) are considered during the optimization process. The optimization results show 27 and 8.3 kmol h^?1 increase in the hydrogen and aromatic yields in optimized RF-TMR compared with conventional tubular reactor (CTR). Moreover, the new configuration is capable to be used in the radial-flow moving bed reactors, which are widely installed in refineries.     

垂直上升管内超临界CO2 流动传热特性研究

在压力为7.5～21 MPa，热通量为50～413 kW·m^-2，质量流速为519～1500 kg·m^-2·s^-1的实验参数范围内，对超临界CO₂在内径为10.0 mm的垂直上升管内的流动传热特性进行了均匀加热条件实验研究。分析了热通量、压力和浮升力对圆管内传热特性的影响规律。实验结果表明：随着热通量的增加，传热出现恶化现象，并且随着热通量的增加壁温峰值点向入口段移动。传热恶化发生在流体温度小于拟临界温度而壁面温度大于拟临界温度附近。增大压力时由于物性的变化趋于平缓，传热恶化被抑制。当传热恶化发生时，浮升力对传热恶化有明显的影响。基于实验数据，综合考虑物性变化和浮升力对传热的影响，建立了新的超临界二氧化碳传热关联式，在实验工况范围内，预测值与实验值的平均偏差和标准差分别为1.2%和16.29%。     

Study on the uniformity of water film in a transpiring wall reactor for supercritical water oxidation

A three-dimensional computational fluid dynamic model of a transpiring wall reactor for supercritical water oxidation has been built to optimize the uniformity of water film. Results show that the temperature and species distributions at the nozzle outlet deviate from the reactor centre. The inner wall of the porous tube near the transpiring water injection tube displays low temperatures, while high temperatures are recorded far from the injection tube. The circumferential temperature distribution on the inner wall of the porous tube is uneven. This phenomenon is due to the uneven injection of the transpiring water, leading to the uneven protection of the water film and local overheating of the porous wall. The injection velocity of the transpiring water significantly decreases when the number of injection tubes is increased, and the circumferential velocity and temperature distributions on the porous wall gradually become even. Moreover, high pressure drops across the porous wall at low porosities are useful for the uniform injection of the transpiring water. This characteristic is also conducive to obtaining a more uniform water film protection.     

下喷式液气喷射器内流体力学的数值模拟

本文用STAR-CCM+软件研究下喷式液气喷射器内的流体力学.结果表明,混合管直径一定,随面积比的增加,混合管入口的压力先增高后减低,空气抽吸量存在一个最大值,此时对应面积比约为4.在模拟的喉径比范围内,混合管人口处的压力较低,但存在一个最大的压力降,对应喉管长度为0,空气抽吸量随喉径比而变,也存在一个最大值.喷射器结...     

管式反应器中苯乙烯连续本体热聚合过程模型化和数值模拟

建立了管式层流反应器中苯乙烯本体热聚合过程的模型。数值模拟了反应介质流速和温度沿反应器的轴向和径向的分布,考察了反应器的几何尺寸、壁温、反应介质入口温度和流量对反应器出口转化率和产物相对分子质量的影响。结果表明,反应器的几何尺寸和反应器壁温及进料质量流量对单体转化率影响较大,而入口温度影响不大。     

Combustion and Pyrolysis Reactions in a Naphtha Cracking Furnace

Numerical simulation on combustion and pyrolysis reactions in a tubular reactor is carried out on a 100,000 t/a naphtha cracking furnace. A complex arrangement of bottom burners is contained in the furnace model. The hydrodynamic and radiation models are included for calculating the flue gas flow pattern and heat transfer. A molecular reactions model is applied on the basis of a two‐dimensional tubular reactor model. The results calculated indicate that there is recirculation of the flue gas at each side of the reactor tubes due to the high inlet velocity from the bottom burners, which contributes to the uniformity of flue gas temperature in the furnace. Higher temperature profiles of the tube skin are mainly located 15–20 m along the tubular reactor. The calculated pyrolysis product yield and the tube skin temperatures are in good agreement with experimental data.     

Improved methanol yield from methane oxidation in a non-isothermal reactor

Partial oxidation of methane to methanol was carried out homogeneously in a non-isothermal reactor that contained a non-permselective membrane. A tubular reactor was used with a smaller-diameter tubular membrane of 5 nm pore diameter alumina or 0.5 μm pore diameter metal. The membrane provided a uniform flow distribution and separated the hot reactor wall from a cooling tube located in the centre of the reactor. The cold region in the reactor rapidly quenched further reaction. The selectivity for CH₃OH formation at 4.6% conversion increased from 34 to 52% when quenching was used. The highest yield (selectivity times conversion) obtained was 3.8% at 55 MPa and 800 K. Methanol selectivity increased with increasing pressure and decreased with increasing temperature, residence time and O₂ concentration. The combined selectivity to partial oxidation products (CO, CH₃OH, CH₂O) was almost constant at 86%.     

聚丙烯等离子体热解与管式炉热解对比研究

叙述了等离子体热解技术的特点及相对普通热解的优越性,并以聚丙烯为实验物料,对比了等离子体热解与管式炉热解的转化率、产物分布、成分等,实验结果显示等离子体热解转化率高,所得产物易于分离,气体产物中H2体积分数高,表明等离子热解是一种颇具发展潜力的固体废弃物处理技术。