锆基双金属氧化物催化剂硫中毒的研究

在工业二氧化碳加氢制甲醇过程中,硫化氢气体的引入将对该过程中使用的催化剂活性及稳定性带来负面的影响。基于此,采用微反应合成法成功制备了InZrO_x和ZnZrO_x锆基催化剂,并研究了在二氧化碳加氢反应中,硫化氢气体对锆基催化剂的结构性质及其催化性能的影响规律。结果表明,在T=573 K、p=3.0 MPa和GHSV=18 000 mL/(g_cat·h)条件下,仅通入二氧化碳/氢气反应气时,InZrO_x和ZnZrO_x催化剂的二氧化碳转化率和甲醇选择性分别为7.2%、9.3%和93%、92%。在二氧化碳/氢气原料气中通入体积分数为5×10^-3硫化氢气体时,InZrO_x和ZnZrO_x催化剂的二氧化碳转化率和甲醇选择性都降为0,这主要是因为硫化氢气体占据了氧空位,导致锆基双金属氧化物催化剂硫中毒失活。当停止通硫化氢气体时,InZrO_x和ZnZrO_x催化剂的二氧化碳转化率和甲醇选择...     

EFFECT OF THE DISTRIBUTION OF PYRIDINE 1-OXIDE ON ITS CATALYZED TWO-PHASE REACTION OF BENZOYL CHLORIDE AND CARBOXYLATE ION

Benzoyl chloride (PhCOCl) exhibits a peculiar inhibitve effect on its reaction with some sodium carboxylates (RCOONa) catalyzed by pyridine I-oxide (PNO) in a CH₂Cl₂/H₂O medium. However, the reaction follows well the rate law -d[PhCOCl]_org/dt = K_obs[PhCOCl]_org = (k_h + k_c [PNO]_i.aq )[PhCOCl]_org. Where k_h is the uncatalyzed rate coefficient, k_c is the catalyzed rate coefficient, and [PNO]_i,aq is the initial concentration of PNO in aqueous phase. When the concentration of RCOONa is the sufficiently high, k_obs, can be expressed as k_obs, = k_h + kPNO[P-NO]_i,aq/(l + k_PNO) Where is k_PNO the intrinsic rate coefficient of the reaction between PhCOCl and PNO in CH₂Cl₂ and k_PNO is the distribution constant of PNO between H₂O/CH₂Cl₂ phases and is defined as k_PNO = [PNO]_aq/[PNO]_org. In order to account for this peculiar phenomenon, the effects of organic compounds, including CCl₄, alcohol, ester, and carboxylic acid, were investigated. The presence of organic additive affects the distribution of PNO between H₂O and CH₂Cl₂ phases, the reaction rate, and the yield of product. In general, the value of k_PNO correlated well with the effective concentration of free PNO in the CH₂Cl₂ phase. For the PNO-catalyzed reaction of PhCOCl and CH₃COONa in H₂O/CH₂Cl₂ medium, the main conclusions are:

(1)The presence of ROH additive in CH₂Cl₂ increases the distribution of PNO is CH₂Cl₂ and the value of k_PNO due to the hydrogen bonding between ROH and PNO.

(2)The presence of nonpolar CC1₄ and RCOOR' in CH₂Cl₂ decreases distribution of PNO and the values of k_PNO.

(3)The presence of RCOOH in CH₂Cl₂ enchances the distribution of PNO in CH₂Cl₂ and the value of k_PNO. However, the main product is PhCOOCOR instead of PhCOOCOCH₃ in contrast to the cases of adding ROH, CCl₄, and RCOOR'.     

负载型Mn基低温NH3-SCR脱硝催化剂研究综述

MnO_x以其良好的低温催化活性成为当前低温NH₃-SCR脱硝催化剂研究的热点,负载型Mn基低温脱硝催化剂较好地解决了非负载型低温N₂选择性差、易中毒等难题,具有良好的工业应用前景.本文综述了负载型Mn基低温脱硝催化剂的研究现状,从活性组分、载体、制备方法、机理和动力学以及抗H₂O、SO₂性能5个方面介绍了负载型Mn基低温脱硝催化剂的研究现状,着重阐述了金属氧化物、分子筛、炭基等人工和天然载体负载MnO_x在制备方法和脱硝活性方面的最新研究成果,简述了Mn基低温脱硝催化剂的催化机理以及动力学研究进展,分析了Mn基低温脱硝催化剂的H₂O和SO₂中毒机理.指出提高负载型Mn基低温脱硝催化剂的抗中毒性能和再生是今后研究的重点.     

ESTIMATION OF EFFECTIVE SHEAR RATE FOR AERATED NON-NEWTONIAN LIQUIDS IN AIRLIFT BIOREACTOR”“

Effective shear rate is one of the indispensable parameters for the design of aerobic fermentors using a viscous non-Newtonian system. The estimation of effective shear rate in airlift loop bioreactors has been investigated with liquid circulation velocity. An empirical correlation of effective shear rate in airlift loop reactors is proposed.

γ_eπ= 3.26-3.51 ; 10²U_G + 1.48 10⁴U²_G

It is found that the effective shear rate is lower in airlift reactors than in bubble columns. This equation can be used for the cultivation of cells sensitive to shear stress.     

Catalytic desulphurization of benzothiophene in an emulsion via in situ generated H2

Catalytic desulphurization of benzothiophene (BTH) in a water/toluene emulsion, a model system for heavy oil emulsions, was achieved at 340°C using a water-soluble phosphomolybdic acid (PMA), a precursor for dispersed Mo catalyst. This process is based on the activation of H₂O to generate H₂ in situ via the water gas shift reaction (WGSR) for hydrodesulphurization (HDS). At 340°C with an initial CO loading of 4.14 MPa, essentially complete sulphur removal was obtained. Kinetic expressions for the WGSR and HDS of BTH with in situ generated H₂ and externally supplied H₂ were developed and verified experimentally. The kinetic analysis indicates that WGSR is rate-determining and desulphurization with in situ generated H₂ is a relatively fast step. Apparently, in situ H₂ is about seven times more active than externally supplied H₂ for the hydrogenation of BTH. A mechanism for desulphurization involving initial hydrogenation of BTH to dihydrobenzothiophene (DHBTH) followed by hydrogenolysis to give ethylbenzene (EB) and H₂S is proposed.     

Hydrodenitrogenation of pyridine over alumina-supported iridium catalysts

The catalytic properties of alumina-supported Ir catalysts (≈1 wt% Ir) were studied in the hydrodenitrogenation (HDN) of pyridine at 320°C and 20 bar of pressure in the absence as well as presence of parallel hydrodesulfurization (HDS) of thiophene. The effects of Ir precursor (Ir(AcAc)₃, Ir₄(CO)₁₂, H₂IrCl₆, (NH₄)₂IrCl₆), metal dispersion and sulfur addition were investigated. Ir₄(CO)₁₂ gave the most active catalyst which was ascribed to a lower amount of contaminants originated from the starting Ir compounds rather than to a better Ir dispersion. The decrease of Ir dispersion by sintering in air led to much higher decrease of the rate of C–N bond hydrogenolysis than that of pyridine hydrogenation. The Ir dispersion determined partly the HDN selectivity; a better dispersed Ir phase gave a lower amount of intermediate piperidine. Presulfidation of the reduced catalyst led to 20% decline of the rates of both consecutive HDN steps. An additional and much larger activity decline was caused by the simultaneous execution of HDS. The competitive adsorption of thiophene (or H₂S) was selectively affecting C–N bond hydrogenolysis more than pyridine hydrogenation. The alumina-supported Ir catalysts possessed much higher HDN activity and HDN/HDS selectivity than a conventional NiMo system.     

Accelerated deactivation of hydrotreating catalysts: comparison to long-term deactivation in a commercial plant

Accelerated deactivation tests of a laboratory prepared Co–Mo/Al₂O₃ catalyst were performed using three kinds of petroleum feedstocks. A high reaction temperature employed in the accelerated aging resulted in large amounts of carbonaceous deposition with high aromaticity, which were found to be the major deactivation cause. However, the effect of carbonaceous deposition during accelerated deactivation tests might have been overestimated compared with that during practical hydrotreating. When the catalysts were aged in a H₂S/H₂ stream without petroleum under the same reaction conditions, the crystal growth of MoS₂ layered structures was significant, but this rather resulted in an increase of both k (HDS) and k (HY). It was also suggested that the crystal growth during a commercial hydrotreating run was unlikely to be the major cause of catalyst deactivation.     

CO and CO2 hydrogenation study on supported cobalt Fischer–Tropsch synthesis catalysts

The conversion of CO/H₂, CO₂/H₂ and (CO+CO₂)/H₂ mixtures using cobalt catalysts under typical Fischer–Tropsch synthesis conditions has been carried out. The results show that in the presence of CO, CO₂ hydrogenation is slow. For the cases of only CO or only CO₂ hydrogenation, similar catalytic activities were obtained but the selectivities were very different. For CO hydrogenation, normal Fischer–Tropsch synthesis product distributions were observed with an of about 0.80; in contrast, the CO₂ hydrogenation products contained about 70% or more of methane. Thus, CO₂ and CO hydrogenation appears to follow different reaction pathways. The catalyst deactivates more rapidly for the conversion of CO than for CO₂ even though the H₂O/H₂ ratio is at least two times larger for the conversion of CO₂. Since the catalyst ages more slowly in the presence of the higher H₂O/H₂ conditions, it is concluded that water alone does not account for the deactivation and that there is a deactivation pathway that involves the assistance of CO.     

THE KINETICS OF H2S DECOMPOSITION OVER PRECIPITATED COBALT SULPHIDE CATALYST

Cobalt sulphide catalyst prepared via a new method involving the precipitation reaction between cobaltous acetate and ammonium sulphide solutions has been shown to be favourably active for the catalytic decomposition of H₂S when compared with data for other transition metal sulphides.

The BET surface area of this unsupported catalyst is about an order of magnitude higher than cobalt sulphide formed by direct sulphidation of cobalt oxide with H₂S gas. XRD, SEM and TEM analyses were used to obtain bulk composition and morphological characteristics. Catalyst specimen calcined at 823 K showed the best activity.

The kinetics of the decomposition reaction has been studied over this new preparation. Experiments conducted at atmospheric pressure between 933-983 K using about 11 feed compositions showed that below 40% H₂S/Ar the reaction was essentially 1st order with respect to H₂S partial pressure. Beyond this point, rate remained invariant with feed composition. A mechanism involving catalysis via co-ordinative unsaturation sites on the CoS was proposed and kinetic model based on the cleavage of the surface H-S bond as the rate-determining step appeared to be the most adequate representation of the rate data. Hydrogen production rates at all temperatures also paralleled the behaviour seen for H₂S decomposition. Activation energy for H₂S decomposition and H₂ production rates were estimated as 111 kJ mol^-1 and 88 kJ mol^-1 respectively     

ACETIC ACID AS AN OXYGEN CARRIER BETWEEN TWO PHASES FOR EPOXIDATION OF OLEIC ACID

Acetic acid was found to be an effective oxygen carrier for epoxidation of oleic acid. The reaction model of oleic acid epoxidation in the two-phase reaction system was systematically analyzed and the rate determining step was experimentally identified.

The results indicated that the rate of oxidation of the unsaturated acid was independent of the concentration of oleic acid and depended on the mixing rate and the rate of formation peracetic acid which in turn depended on the concentration of acetic acid, strength of acid catalyst and the oxygen source, hydrogen peroxide. In the region of reaction control, the rate equation of epoxidation was found to be

$

where k = 2.98 × 10^-2 M^-2 min^-1 at temperature of 35^°C.     

H2在Mo x S y 团簇上吸附解离的尺寸效应研究

浆态床加氢工艺可以处理不同来源的劣质重油、渣油,氢气的活化是重油加氢处理过程中发生的主要反应之一。钼基催化剂的分散性是影响重油加氢活性的关键因素。构建了Mo₇S₁₅、Mo₁₂S₂₆、Mo₁₈S₃₉、Mo₂₅S₅₄和Mo₃₃S₇₁团簇,利用密度泛函理论研究了团簇自身的稳定性、活性以及H₂在不同尺寸团簇上的吸附与解离过程。结果发现,在目前所建立的团簇中,其尺寸越小,结合能越低,最高占据分子轨道-最低未占分子轨道(HOMO-LUMO)能隙值越小,团簇稳定性越弱,活性越强。H₂在簇上的稳定吸附位点为边缘位点。随团簇尺寸增大,吸附能分别为-64.25、-34.60、-34.14、-7.20、-6.82 kJ/mol,吸附能绝对值减小,氢气分子与团簇的相互作用减弱,并且解离能逐渐增大,分别为13.76、33.14、53.64、60.75、64.47 kJ/mol。目前的结果表明,团簇尺寸越小,氢气的吸附解离越容易,显示出更高的活性。     

H2在MoxSy团簇上吸附解离的尺寸效应研究

浆态床加氢工艺可以处理不同来源的劣质重油、渣油,氢气的活化是重油加氢处理过程中发生的主要反应之一。钼基催化剂的分散性是影响重油加氢活性的关键因素。构建了Mo₇S₁₅、Mo₁₂S₂₆、Mo₁₈S₃₉、Mo₂₅S₅₄和Mo₃₃S₇₁团簇,利用密度泛函理论研究了团簇自身的稳定性、活性以及H₂在不同尺寸团簇上的吸附与解离过程。结果发现,在目前所建立的团簇中,其尺寸越小,结合能越低,最高占据分子轨道-最低未占分子轨道(HOMO-LUMO)能隙值越小,团簇稳定性越弱,活性越强。H₂在簇上的稳定吸附位点为边缘位点。随团簇尺寸增大,吸附能分别为-64.25、-34.60、-34.14、-7.20、-6.82 kJ/mol,吸附能绝对值减小,氢气分子与团簇的相互作用减弱,并且解离能逐渐增大,分别为13.76、33.14、53.64、60.75、64.47 kJ/mol。目前的结果表明,团簇尺寸越小,氢气的吸附解离越容易,显示出更高的活性。     

STABILIZATION OF ZEOLITIC HYDROCRACKING CATALYST

The stability of a palladium-containing hydrocracking catalyst is improved by the ion exchange addition of zinc. The zinc appears to be uniformly distributed near the cracking sites where it effectively hydrogenates the coke precursors to minimize coking and maintain catalyst activity.

To be effective, the zinc ion exchange should be conducted at low pH to prevent zinc precipitation, and the catalyst should be reduced with H₂ prior to use. Incorporation of zinc has no effect on the initial activity of the hydrocracking catalyst     

HEAT TRANSFER IN TRICKLE-BED REACTORS

The mechanism of radial heat transfer in two-phase flow through packed beds is examined. A model with 2 parameters: an effective radial thermal conductivity in the bed, k_e, and a heat transfer coefficient, h_w, at the wall, give a satisfactory interpretation of the radial temperature profile.

k_e was expressed in terms of a stagnant contribution, due to the heat conduction through the solid and the fluid in the void space, and a radial mixing contribution of the gas and liquid phases, due to the radial component of the velocity of both fluids. The radial mixing contribution of the liquid ( k_e)_L was compared with radial mass dispersion data, and a satisfactory agreement was obtained.

Moreover, ( k_e)was much higher than the gas mixing and the stagnant contributions.

Correlations for hw and k_e)_L have been proposed in accordance with the hydrodynamic regimes of the two-phase flow.     

氨分解制氢棒状LaxCe1-xOy负载Ru催化剂

氨分解得到的H₂不含CO _x 、SO _x 、NO _x 等有害物质,是其他所有含碳资源为原料制氢所不能比拟的。本文采用无模板水热法制备了一系列棒状载体,并采用沉积沉淀法制备了Ru/La _x Ce_1-x O _y 催化剂,考察了制备方法、催化剂组成对性能的影响,并通过扫描电镜（SEM）、X射线衍射（XRD）、BET、H₂-程序升温还原（TPR）和CO₂-程序升温脱附（TPD）进行了表征。结果表明,La₂O₃掺杂量为40%的Ru/La_0.4Ce_0.6O_1.8催化剂在常压、7800h^-1、450℃下氨分解转化率为98%。该催化剂活性高归因于部分还原的CeO_2-x 对Ru的供电子性能和Ru/La_0.4Ce_0.6O_1.8催化剂表面的强碱性增加了对Ru活性位的给电子能力。同时考察了K₂O含量的影响,最优的催化剂为Ru-2%K/La_0.4Ce_0.6O_1.8,在400℃、7800h^-1氨气转化率可以达到93%。结果表明Ru-2%K/La_0.4Ce_0.6O_1.8可以作为一种新型高效氨分解催化剂,为工业化应用提供了可能,具有良好的发展前景。     

CO在成型催化剂上脱除NOx的反应动力学模型

采用实验和模拟相结合的方法研究了NO_x在固定床反应器中的吸附还原过程。选取商业常用的堇青石和TiO₂为主要的成型催化剂基体材料，以铜铁铈复合型金属氧化物为活性成分，制备了蜂窝成型催化剂，对蜂窝催化剂的吸附性能和脱硝还原活性进行测定。建立了固定床反应器中CO脱除NO_x的反应动力学模型，由于CO法脱硝反应的解耦分解，脱硝反应模型也由吸附模型和还原模型组成。吸附模型由固相和气相的微分质量平衡方程建立，还原模型由一组微分方程组成。通过固定床NO_x吸附曲线和不同温度下NO_x的转化率对模型中的关键参数进行了拟合，得到了CO在成型催化剂上脱除NO_x的反应动力学模型，该模型与实验数据吻合较好。在此基础上，模拟了其他条件下吸附过程的穿透曲线和还原反应的转化率。此模型能较好地揭示CO在蜂窝催化剂上还原NO_x的反应动力学，为CO法成型催化剂脱除NO_x的实验或者工程提供理论指导。     

The Strength of Liquid Bridges Between Dissimilar Materials

The strength of the liquid bridge between a sphere and a plate of dissimilar materials was studied. An equation was derived using the surface energy approach. For small amounts of liquid, the force of adhesion f was f=2πRy(cosθ₁ + cosθ₂ where R is the sphere radius, y is the surface tension, and θ₂, θ₂ the contact angles. In the derivationn, major simplications about the meniscus shape were possible.

The equation was experimentally tested with water, ethyl alcohol, aniline and iodobenzene using factorial combinations with different solids. Force of adhesion measurements were carried out using a tensile testing machine at controlled loading rates. Excellent agreement was obtained in the experimental and predicted adhesion values. The McFarlane-Tabor equation was identified as correct only for small amounts of liquids and similarly wet solids.     

Effect of water on HDS of DBT over a dispersed Mo catalyst using in situ generated hydrogen

A novel process was developed for the bitumen emulsion upgrading, wherein emulsion breaking and upgrading occurred in the same reactor using H₂ generated in situ from the water in the emulsion via the water gas shift reaction (WGSR). In this study, dibenzothiophene (DBT) was chosen as a model compound to investigate the effect of water and in situ H₂ on hydrodesulfurization (HDS). All the experiments were performed in a 1-L autoclave reactor at temperatures between 300 and 380 °C using in situ H₂ and ex situ H₂ (externally supplied H₂) over a dispersed Mo catalyst formed from phosphomolybdic acid (PMA). At very low water content, water was found to promote the HDS reaction in the ex situ H₂ run probably because it facilitates the formation of more active dispersed MoS_x species. At higher water content, however, water inhibits every individual reaction in the reaction network in the HDS of DBT, blocking the hydrogenation pathway more than the hydrogenolysis pathway. The relative reactivity of the in situ and ex situ H₂ depends on the water content present in the reaction system. At an optimized mole ratio of H₂O:CO (1.35), higher HDS activity was observed in the in situ H₂ run compared to ex situ H₂ run, and particularly, the hydrogenation pathway was promoted in the in situ H₂ run.