高速固定床F-T法合成液体燃料

本文在一般性介绍F-T合成各种床型的同时,将着重叙述高气速固定床反应器和过程参数对反应结果的影响,通过各种反应器床型特性的比较,说明高气速固定床采用尾气循环增加气速有利传热,提高了催化剂负荷,而相对冷却面仅是其余反应器的5～7％,在F-T合成液体燃料反应器中高气速固定床是成熟,可靠的反应器。     

一氧化碳等温变换技术进展

对现代合成氨CO变换技术中发展起来的不同种类的固定床等温反应器进行了比较 ,从转化率、操作稳定性、结构复杂程度及发展前景等方面进行了论述。特别分析了另一类等温反应器———流化床反应器的特点 ,并结合其在传热、传质、处理量及操作等方面的优势和流态化技术的发展。流化床反应器在CO变换过程中的工业化应用很有前景     

费托合成反应器应用研究进展及展望

费托合成反应是强放热的气液固三相反应,为有效移热及提高目标产物产率,应加强费托合成反应器的研发,系统介绍了工业上几种费托合成反应器的特点、应用规模等,论述了近几年已经或有望进行工业化应用的几种费托合成反应器,如固定床反应器、流化床反应器、浆态床反应器等,并比较了各类反应器的优劣,最后对费托合成反应器的选型和发展提出了建议和展望。固定床反应器技术成熟,产品容易分离,催化剂损失少,但是移热效果较差;浆态床反应器,反应物混合均匀,移热效果好,但产品固液分离较为困难;流化床反应器可以在高温下运行,生产高价值的轻烃产物,但催化剂消耗较大。研究认为,如果目标产品是以分子质量较大的柴油和石蜡为主,建议选择浆态床反应器;如果目标产品是生产烯烃等化学品,建议选择固定流化床反应器。     

F—T合成技术进展

Ｆ－Ｔ合成技术分高温与低温技术两类。高温技术包括早期的疏相流化床反应器技术和后开发的密相流化床反应器技术,低温技术则包括早期的Ａｒｇｅ管式固定床反应器技术和新开发的浆态床反应器技术。本文分别介绍了上述技术的最新进展。     

乙炔法合成氯乙烯固定床反应器的数学模拟和工况分析

根据对乙炔，氯化氢在ＨｇＣｌ_２－活性碳催化剂上合成氯乙烯反应动力学、失活动力学及固定床反应器的分析，建立拟均相二维有效扩散模型以描述氯乙烯合成固定床反应器的特性，用此模型对现有生产中的工况进行定量分析，并提出改进操作的方案。     

脂肪酸甲酯的喷射磺化工艺研究

利用新开发的高气液比喷射磺化反应器，对脂肪酸甲酯进行了连续的SO3气相磺化试验，考察了老化条件、摩尔比、喉管气速、夹套介质温度以及气液比等因素对产品脂肪酸甲酯磺酸质量(活性物、无机酸、游离油)的影响，井与玻璃管膜式磺化反应器进行了对比。结果表明，喷射磺化时脂肪酸甲酯转化率为90％～95％，SO3利用率达99％，与膜式反应器相近。且喷射磺化反应器结构简单、紧凑，制造、维修成本低，生产操作弹性大，具有较好的应用前景。     

列管式固定床F-T合成反应器的模拟及优化

针对列管式固定床F-T合成反应器的特点建立了一维拟均相数学模型。通过对模型计算与试验结果进行对比分析,表明该模型可以较好的描述反应过程。并从固定床反应器的操作热稳定性出发,对列管式固定床F-T合成反应器的最大允许管径和最大传热温差进行了计算。结合模型计算结果得出了合适的反应管直径与冷却介质温度范围,可以优化列管式固定床F-T合成反应器的设计。     

流化床与固定床中甲烷裂解制氢过程的比较

本文对流化床与固定床操作模式下的甲烷催化裂解制氢进行了比较研究。以纯甲烷为原料,分别考察了75Ni10Cu15Al和2Co1Al（原子比）催化剂上流化床与固定床操作模式下甲烷裂解制氢反应,结果表明流化床中的甲烷裂解反应速率较高。流化床操作的高表观速率主要是因为此模式下有效消除了外扩散,同时极大减少了内扩散阻力。同时不同温度下催化剂上生长的碳的TEM表征发现,金属颗粒尺寸随反应温度增加而增加,表明催化剂烧结是失活原因之一。但相同温度下固定床中催化剂金属颗粒尺寸明显大于流化床中的金属颗粒尺寸,且金属颗粒尺寸分布变宽,这说明流化床反应器有利于阻止金属颗粒的烧结。通过对甲烷裂解催化剂失活原因的分析发现流化床中催化剂颗粒的流态化有利于延长催化剂活性寿命。     

乙炔法气相合成醋酸乙烯工业固定床反应器的优化操作的…

在前面乙炔法气相合成醋酸乙烯的宏观动力与失活动力学研究的基础上，建立了工业固定床反应器的数学模型，同时为优化操作计算机模拟提供了一系列计算机软件。依据工厂试生产数据用该模型进行了计算机模拟，得到了工业固定床反应器的反应动力学和失活动力学模型参数。     

乙炔法气相合成醋酸乙烯工业固定床反应器的优化操作的研究Ⅲ工业固定床的数学模型与操作优化的计算机模拟

在前面乙炔法气相合成醋酸乙烯的宏观动力学与失活动力学研究的基础上，建立了工业固定床反应器的数学模型，同时为优化操作计算机模拟提供了一系列计算机软件。依据工厂试生产数据用该模型进行了计算机模拟，得到了工业固定床反应器的反应动力学和失活动力学模型参数。基于该模型对工业操作进行优化模拟计算［１～４］，生产试验的结果表明，按照计算机所选择的适当的操作条件和升温制度，可在保证日产率的前提下延长催化剂使用周期     

SOME ASPECTS OF THEORETICAL COMPARISON OF FISCHER-TROPSCH REACTORS

The reactor systems used for the Fischer-Tropsch synthesis, fixed bed, fluidized bed and slurry bed, are compared on the basis of space time yield (STY) and level of conversion obtainable under the same set of feed and operating conditions. The slurry bed and fluidized bed reactor were compared on the basis of a first order reaction model. The performance of these two reactors was found to be comparable at low values of WHSV, but at higher values of WHSV, the fluidized bed reactor gave higher conversions and STY. A power law kinetic expression was used to compare the performance of the slurry bed and fixed bed reactors. Higher conversions and STY were obtained from the fixed bed with varying WHSV. This may be due to the omission of the intra and inter phase mass transfer resistances in the modelling of the fixed bed reactor.     

MoO3/MgO as a catalyst in the oxidative dehydrogenation of n-butane in a two-zone fluidized bed reactor

Butadiene has been produced from butane by oxidative dehydrogenation on a MoO₃/MgO catalyst using a two-zone fluidized bed reactor (TZFBR). The effect of the main TZFBR operating variables was studied, and its performance was compared with that of conventional fluidized beds and fixed bed reactors loaded with the same catalyst. These results have been compared with those obtained on a selective V₂O₅/MgO catalyst.     

流化床在甲烷临氧CO2重整反应中的作用研究

在流化床反应器中进行甲烷临氧CO₂重整制合成气反应。通过计算分析了催化剂颗粒在床层内的流化特性。对比实验表明,流化床反应器在催化剂活性、稳定性、自热过程以及催化剂积炭等方面均体现出比固定床反应器的优越性。在流化床反应器中进行的甲烷自热重整反应,甲烷的转化率接近热力学平衡值,床层温度梯度小于10 ℃, 反应20 h后,催化剂表面无积炭。     

流化床与沸腾床内部微生物群落演变与分析

用流化床反应器和沸腾床反应器处理焦化废水,对两种反应器运行效能及微生物群落变化进行对比研究。结果表明,提高污泥负荷后流化床COD去除率优于沸腾床反应器。提高进水污泥负荷对沸腾床内微生物的冲击更大,致使其种群丰富程度下降明显。研究结果证明,流化床在宏观去除率、维持菌种丰富度方面具有较大优势。     

Performance of catalytic reactors for the hydrogenation of CO2 to hydrocarbons

Fluidized bed and slurry reactors were employed to increase the CO₂ conversion and desirable product selectivity in the direct hydrogenation of CO₂ to hydrocarbons over K-promoted iron catalysts, as it is beneficial for the removal of heat generated due to highly exothermic nature of the reaction. The iron catalysts (Fe-K/Al₂O₃ and Fe-Cu-Al-K) were characterized by BET surface area, CO₂ and H₂ chemisorption, temperature-programmed reduction (TPR), X-ray diffraction (XRD) and temperature-programmed hydrogenation (TPH). The results of TPR and TPH study clearly indicated that co-precipitated Fe-Cu-Al-K catalyst has much higher reducibility and catalytic activity of CO₂ hydrogenation at low temperature than Fe-K/Al₂O₃. The performance of fluidized bed or slurry reactors was superior to that of fixed bed reactor for the CO₂ hydrogenation over Fe-Cu-Al-K catalyst in terms of CO₂ conversion and hydrocarbon productivity. Moreover, light olefins and heavy hydrocarbons were selectively synthesized in fluidized bed and slurry reactors, respectively. The optimum operation conditions and the effects of operating variables on the CO₂ conversion and its product distribution in these catalytic reactors were also discussed.     

Syngas production from methane reforming with CO2/H2O and O2 over NiO–MgO solid solution catalyst in fluidized bed reactors

Catalyst performance of NiO–MgO solid solution catalysts for methane reforming with CO₂ and H₂O in the presence of oxygen using fluidized and fixed bed reactors under atmospheric and pressurized conditions was investigated. Especially, methane and CO₂ conversion in the fluidized bed reactor in methane reforming with CO₂ and O₂ was higher than those in the fixed bed reactor over Ni_0.15Mg_0.85O catalyst under 1.0 MPa. In contrast, conversion levels in the fluidized and fixed bed reactor were almost the same over MgO-supported Ni and Pt catalysts. It is suggested that the promoting effect of catalyst fluidization on the activity is related to the catalyst reducibility. On a catalyst with suitable reducibility, the oxidized and deactivated catalyst can be reduced with the produced syngas and the reforming activity regenerates in the fluidized bed reactor during the catalyst fluidization. In addition, the catalyst fluidization inhibited the carbon deposition.     

流化床冷凝模式操作与乙烯聚合过程的研究Ⅱ露点提高组分对流化床反应器运行状态的影响

以Ｕｎｉｐｏｌ气相法乙烯聚合工艺作为流化床反应器冷凝模式操作的一个实例,通过模拟计算考察了在不同的操作负荷下,进反应器的循环物流的露点、组成和温度对反应器运行状态的影响,并对反应器运行的稳定性作了初步探讨。     

Experience with a new type of reactor for Fischer-Tropsch synthesis

Circulating fluidised bed (CFB) reactors have traditionally been used for the high temperature Fischer-Tropsch synthesis-Synthol process. A development program undertaken by Sasol with the assistance of The Badger Company recently led to the successful commissioning of a commercial scale conventional, fixed fluidised bed (FFB) reactor as an alternative to the CFB reactor.Work was done in a small pilot plant which was followed by work in a 1 m diameter semi-works pilot plant operated in parallel with one of the commercial CFB reactors. Based on the positive results obtained, it was decided to build a commercial scale FFB reactor with a capacity similar to existing commercial reactors at Sasol One. This reactor was successfully commissioned and has been in operation since May 1989.The reactor is easy to operate and can withstand major plant instabilities. A techno-economic analysis and comparison between the Synthol-CFB and Synthol-FFB reactors indicates significant advantages for the Synthol-FFB reactor, both with respect to capital and operating costs. The results of this analysis and comparison are presented and the significance of the findings discussed in terms of future plants for the conversion of synthesis gas to liquid fuels.     

Development of a CH4 dehydroaromatization–catalyst regeneration fluidized bed system

A pilot-scale methane dehydroaromatization–H₂ regeneration fluidized bed system (MDARS) was developed. In the MDARS, the catalyst circulation between a fluidized bed reactor and a fluidized bed regenerator with the help of a catalyst feeder allowed methane dehydroaromatization (MDA) and H₂ regeneration to be carried out simultaneously, which is good for maintaining a stable MDA catalytic activity. A fixed bed reactor (FB) and a single fluidized bed reactor (SFB) were also used for a comparative study. The experimental results showed that the catalytic activity in the MDARS was more stable than that in the FB and SFB reactors. The effects of some parameters of MDARS on the CH₄ conversion and product selectivity were investigated. To verify the feasibility and reliability of the MDARS, an eight-hour long-term test was carried out, which demonstrated that the operation of the MDARS was stable and that the catalytic activity remained stable throughout the entire experimental period.