发明专利ZL201410482673.5 对含有硫化氢的酸性气体进行脱硫并回收硫的方法

<正>一种对含有硫化氢的酸性气体进行脱硫并回收硫的方法,依次包括如下步骤:将酸性气体通入燃烧炉中,与从另一管道通入的空气混合进行燃烧反应,在燃烧炉中反应后的气体进入到降温器中降温至230~250℃,降温后液态硫从液体出口分离,而在燃烧炉中的混合气体进入催化剂反应器,在催化剂反应器中使硫化氢与二氧化硫之间反应生成硫与水,生成的液态硫从催化剂反应器液体出口分离;催化剂反应器中的混合气体进入至加氢反应器中,在加氢反应器中的二氧化硫与氢气反应;加氢反应器     

糠醛在Pd-Cu膜反应器中催化加氢合成糠醇

以糠醛催化加氢合成糠醇作为模型反应,采用共沉淀法制备的Cu/MgO-K₂O作为催化剂,考察了Pd-Cu膜反应器的加氢性能.膜反应器由双套管组成,采用分别进料的方式操作.即糠醛气化后由载气带入中心膜管的催化床层,而氢气则进入管壳层通过Pd-Cu合金膜渗透到反应区.在不同条件下分别进行糠醛催化加氢反应,考察了糠醛转化率、产品糠醇选择性和收率,并与传统的共进料填充床反应器进行比较.研究结果显示,膜反应器比传统的填充床反应器具有产品收率高、选择性好和副产物少的特点.此外,本文结合催化剂的组成、结构和表面形貌的表征对催化剂的催化活性和失活行为进行了讨论.     

放射性密度计在加氢反应器上的应用

0　前言从氧化装置来的粗对苯二甲酸 ,充分搅拌后 ,形成一定浓度的ＴＡ浆料 ,经过加热后达到额定的温度 ,与高压氢气一起送入加氢反应器 ,通过放置在加氢反应器中部的钯炭催化剂 ,进行充分反应 ,去除杂质 ,经过结晶 ,干燥后生产出精对苯二甲酸。进入加氢反应器的浆料浓度很重要 ,浓度的变化直接关系加氢反应器的反应状态 ,当浆料浓度太高 ,超过了催化剂的负载能力时 ,轻者引起催化剂活性降低 ,重者引起催化剂中毒失效 ;当浆料浓度太低时 ,又达不到精制反应的要求。所以 ,对浆料浓度的要求非常重要 ,而浓度和密度又有一定的关系 ,选用ＩＣＩ…     

热管式脱氢反应器研究与试验

介绍了热管式反应器在乙苯脱氢和环己醇脱氢反应中应用的试验过程和结果。单管试验和中试结果都表明,热管式反应器具有比较高的反应转化率、选择性和收率,热管等温反应器床层温度均匀,没有列管式反应器内吸热反应过程中的冷点,相同转化率时,热管式反应器床层高度低,催化剂用量少,生产能力大,能耗低。     

耦合传质的羰基化固定床反应器传热模拟分析

固定床反应器中进行强放热反应时, 反应器的热点温度对操作参数变化敏感,容易引起飞温,导致转化率下降,影响催化剂寿命。为强化羰基化固定床反应器内热质传递与化学反应的协同性,建立考虑颗粒内扩散影响的羰基化固定床反应器拟均相一维传热模型,考察操作参数对床层热点温度、反应转化率、床层温升的影响。不仅体现传热传质和反应的协同作用,而且影响关系明晰、求解方便。为保证反应转化率,本实验条件下确定催化剂颗粒直径小于等于1.5 mm。反应器入口温度/冷却剂油温既要满足床层热稳定性需求,又要使反应转化率和床层温升都在合理范围内。模拟结果表明在床层入口温度升高的同时,可通过降低冷却剂油温获得良好的反应转化率和较小的床层温升。在此基础上,考察入口环氧乙烷浓度对反应转化率和床层温升的影响。本研究可为固定床反应器满足转化率要求、床层合理温升而选择催化剂颗粒直径、床层入口温度、冷却剂油温和床层入口浓度等操作参数提供计算依据。     

径向流固定床反应器的流动特性研究及结构参数的合理选择

径向流固定床反应器的操作状态和反应效果在很大程度上取决于反应器内穿越催化剂床层径向气流沿反应器轴向分布的均匀程度，亦即床层内催化剂负荷的均布程度。本文对此类反应器内的流动特性进行了研究，对立了描述反应器内流动规律的基本运动方程。研究结果表明，径向气流的轴向分布情况与反应器的流动结构型式、反应器内分流流道与合流流道截面积的比值、催化剂床层的阻力系数以及反应器的高径比等参数有关。并提出了如何合理选择反     

2-氧代-4-苯基丁酸乙酯不对称加氢滴流床反应器模型

研究了滴流床反应器中2-氧代-4-苯基丁酸乙酯在10,11-二氢辛可尼定修饰的Pt/A l2O3作用下不对称催化加氢反应特征,实验在4个不同催化床层中进行。考虑催化剂部分润湿和静、动持液量,结合复杂的传质和反应过程,建立了不对称催化加氢滴流床反应器模型。在本征动力学研究的基础上,用模型模拟了滴流床中反应物和产物沿反应器轴向的浓度分布,并对不同操作条件下不对称加氢反应的转化率和光学收率进行了预测,与实验数据比较一致,表明此反应器模型对非均相不对称催化反应的工程化有重要的指导意义。     

利用Fluent软件对N_2O催化分解反应器数值模拟

为了设计N_2O催化分解反应器,运用Fluent软件对整体式分子筛催化剂进行数值模拟,考察孔密度和操作条件对整体式分子筛催化剂转化率的影响。结果表明,在相同温度下,N_2O的转化率随着催化剂孔密度的减小而降低。在反应器轴向距离120 mm处,气体反应最快;提高入口温度、浓度或降低空速,均有利于在较短的轴向距离内达到较高的N_2O转化率。在固定床反应器中,比较棒状催化剂和整体式催化剂中床层温度、反应转化率及轴向压降的变化规律,为整体式分子筛催化剂工业化设计提供理论基础。     

一种催化干气加氢催化剂的研制

分析了作为制氢原料的催化干气的组成性质。由于烯烃和有机硫含量较高,若将其全部通过绝热加氢反应器饱和,则加氢催化剂床层飞温可达到500℃以上,使操作无法进行。因此,开发了一种用于等温床或变温床的加氢催化剂,以便与后序绝热加氢催化剂联合使用。T202B催化干气加氢催化剂在中温250℃时,烯烃转化率为85%,有机硫噻吩的转化率为54%,对于烯烃及有机硫具有较高的转化率。     

乙烯直接水合粗乙醇加氢精制试验

试验方法试验方法计量泵把计量管中的粗乙醇打入反应器;氢气从高压钢瓶经钴催化剂罐脱除氢气中的CO、CO_2后进入反应器。反应产物加氢乙醇流     

Selective hydrogenation of styrene: Poisoning effect of thiophene

The poisoning effect of thiophene on a commercial selective hydrogenation Pd/Al₂O₃ catalyst, using the styrene hydrogenation to ethylbenzene as a test reaction, has been studied. It was found that the addition of thiophene to the reactants modifies the electronic properties of Pd and also prevents (within certain limits) the catalyst from a subsequent poisoning when a second amount of thiophene is added. These modifications on Pd electronic state have been followed by X-ray photoelectron spectroscopy, and the poison addition has been studied by IR spectroscopy.     

Catalyst poisoning and fixed bed reactor dynamics

The poisoning kinetics of thiophene on Ni-kieselguhr catalysts and the deactivation behavior of nonisothermal fixed bed reactors have been studied experimentally using benzene hydrogenation as a model exothermic reaction. The time dependent axial temperature profiles in the reactors were measured and compared with values evaluated from a dispersion model, the parameters of which have been determined in separate experimentation.Poisoning kinetics were measured in a series of differential reactor experiments at atmospheric total pressure, thiophene partial pressures of 0·037-0·19 torr, hydrogen to benzene molar ratios >$\text{8}\text{1}$ and temperatures from 60–180°C. Excellent agreement was found with a power law equation for the rate of change of activity with time, first order in catalyst activity and in thiophene concentration, with an experimental activation energy of 1080 kcal/kmole.This correlation of poisoning kinetics, however, was not able to predict the propagation of the zone of activity (hot-spot) on poisoning of an integral fixed bed reactor. Initial (steady state) temperature profiles were modeled satisfactorally, but the rate of migration of the hot spot was found experimentally to be more rapid than that predicted from the correlation of poisoning kinetics. A semi-empirical two site deactivation model is shown to resolve the discrepancy.     

Poisoning of Pd–carbon catalysts by sulphur,chloro and heavy metal compounds in liquid phase hydrogenation of o-nitrophenol to o-aminophenol

The poisoning of Pd–carbon (4·1% Pd) catalysts by thiophene, dichloroethane, mercuric chloride and lead, zinc and mercuric acetates at different concentrations (0–5000 g m⁻³) in the liquid phase hydrogenation of o-nitrophenol to o-aminophenol (at 308 K and H₂ pressure of 1508 kPa) in a three-phase stirred slurry reactor has been investigated. The hydrogenation activity of the catalyst is drastically reduced due to the presence of these poisons in the reaction mixture, even at a very low concentration of poison (20 g m⁻³). Among the poisons, mercuric acetate was found to be the most potent. © 1998 Society of Chemical Industry     

Selective hydrogenation of styrene. II. Poisoning of Pd/Al2O3 by thiophene and pyridine

The poisoning of a commercial Pd/Al₂O₃ catalyst by pyridine and thiophene during the selective hydrogenation of styrene to ethylbenzene was studied. It was found that the Pd electronic state is the main factor controlling the interaction between the metal and the poisons. Pyridine added to the non-poisoned feed in a pulse produces a modification in the Pd electronic state and a decrease in conversion, but, within certain limits, inhibits the adsorption of more pyridine or thiophene molecules.     

Simulation of an Industrial Pyrolysis Gasoline Hydrogenation Unit

A model is developed based on a two‐stage hydrogenation of pyrolysis gasoline to obtain a C₆–C₈ cut suitable for extraction of aromatics. In order to model the hydrogenation reactors, suitable hydrodynamic and reaction submodels should be solved simultaneously. The first stage hydrogenation takes place in a trickle bed reactor. The reaction rates of different di‐olefines as well as hydrodynamic parameters of the trickle bed (i.e., catalyst wetting efficiency, pressure drop, mass transfer coefficient and liquid hold‐up) have been combined to derive the equations to model this reactor. The second stage hydrogenation takes place in a two compartment fixed bed reactor. Hydrogenation of olefines takes place in the first compartment while sulfur is eliminated from the flow in the second compartment. These reactions occur at relatively higher temperature and pressure compared to the first stage. The key component in this stage is considered to be cyclohexene, of which the hydrogenation was found to be the most difficult of the olefines present in the feed. The Langmuir‐Hinshelwood kinetic expression was adopted for the hydrogenation of cyclohexene and its kinetic parameters were determined experimentally in a micro‐reactor in the presence of the industrial catalyst. The model was solved for the whole process of hydrogenation, including hydro‐desulfurization. The predictions of the model were compared with actual plant data from an industrial scale pyrolysis gasoline hydrogenation unit and satisfactory agreement was found between the model and plant data.     

Polyborane-derived metal borides. 1. Hydrodesulphurization catalysts with potential for coal liquefaction

A new class of metal borides prepared at elevated temperatures and under hydrogen pressure from borane anions and cobalt or nickel salts catalyse the hydrodesulphurization of thiophene at 400 °C to butane and H₂S. The most active catalysts are prepared from the anions NaB₅H₈ and NaB₁₀H₁₃. These borides have unusually high boron levels (12–17%) and exhibit high sulphidation resistances. Using these catalysts, 88–99% conversion of thiophene is observed. With less active catalyst systems or at lower temperatures, butene and tetrahydrothiophene are also produced. Under similar reaction conditions, the nickel-pentaborane derived catalyst promotes 93% hydrogenolysis of furan. The boride catalysts do not promote hydrogenation of non-heterocyclic aromatics such as toluene and ethylbenzene. The potential of these new boride systems in processes related to coal liquefaction is discussed.     

苯甲酸甲酯气相原位加氢制苯甲醛

提出了苯甲酸甲酯气相原位加氢制苯甲醛的路线。在常压固定床反应器上研究了浸渍法制备的Cu-MnO/γ-Al₂O₃双功能催化剂催化苯甲酸甲酯气相原位加氢制苯甲醛的反应性能,考察了催化剂的组成、反应温度、进样速率、酯/醇/水摩尔比等因素对苯甲酸甲酯转化率和苯甲醛选择性的影响。在优化的反应条件（苯甲酸甲酯/甲醇/水摩尔比为0.5/40/40、反应温度为420℃、进样速率为0.1 ml&#8226;min^-1）下,苯甲醛选择性可达到88.5%,苯甲酸甲酯的转化率为79.6%,且Cu-MnO/γ-Al₂O₃催化剂具有较好的稳定性。根据产物分布提出了苯甲酸甲酯原位加氢的反应机理。该反应体系不需要外部供应氢气,避免了氢气的生产和运输,简化了反应工艺。     

苯与乙烯在ZSM－5上的烷基化反应（Ⅲ）固定床反应器行为的化较

给出了低浓度乙烯和苯在ＺＳＭ－５型分子筛催化剂上的宏观动力学方程。建立了中试固定床反应器模型。模型值与中试结果相一致。化较了单段绝热床、等温床和多段绝热床反应器行为。结果表明：在达到乙烯９５％转化率时，苯生成乙苯和乙烯生成乙苯的选择性为等温床要化单段绝热床好；四段绝热床可达到与等温床相当的指标。考虑到绝热床投资少，操作简单，可变性强，四段绝热床反应器应该是首选的反应装置。     

大型乙苯脱氢轴径向反应器的研究与开发(Ⅰ) 流体力学特性

乙苯脱氢轴径向反应器是一种催化床上部采用催化剂自封结构的新颖径向反应器 ,其催化床中的流体流动是复杂的二维流动 .在催化床的表征体积元上应用连续性方程和Ergen方程描述了其流动 ,应用有限差分法通过数学模拟得出了轴径向反应器流场 ,其结果在Φ30 0 0× 10 0 0 0的冷模装置得到了验证 .以大型乙苯脱氢轴径向反应器为背景 ,讨论了流向和触媒封高对流场的影响 ,得出径向段主要以径向流动为主 ,在催化剂封区以轴向、径向二维流动为主 ;催化剂封高是影响流场的主要因素 ,对于向心流动δ在 0 .7附近是Q_a/Q与Q_r/Q相同的等比流量点 ,对于离心流动在δ为 1.1处 ,是Q_a/Q和Q_r/Q相同的等比流量点 .δ小于此值 ,是以轴向流动为主径向流动为次的二维流动区 ;δ大于此值 ,是轴向流动为次径向流动为主的二维流动区 ;与离心流动型相比 ,向心流动型轴径向床有明显的限流作用     

沸腾床催化剂活性的工业评价方法及失活应对措施

结合煤直接液化加氢稳定装置实际运行经验,介绍沸腾床催化剂在工业应用中活性评价方法,建立操作中可实时监控催化剂活性的方案;对催化剂因颗粒破碎、金属中毒及表面积炭等原因引起的催化剂失活,采取从催化剂强度、磨耗指标控制、加强原料油管控、优化操作以及根据催化剂活性调整置换速率等一系列应对措施,延长催化剂在反应器中的运行周期,降本增效。