反应条件对钌催化剂和铁催化剂的氨合成性能影响

Activated carbon-supported Ru-based catalyst and A301 iron catalyst were prepared,and the influences of reaction temperature,space velocity,pressure,and H2/N2 ratio on performance of iron catalyst coupled with Ru catalyst in series for ammonia synthesis were investigated.The activity tests were also performed on the single Ru and Fe catalysts as comparison.Results showed that the activity of the Ru catalyst for ammonia synthesis was higher than that of the iron catalyst by 33.5%-37.6% under the reaction conditions:375-400 °C,10 MPa,10000 h-1,H2︰N2 3,and the Ru catalyst also had better thermal stability when treated at 475 °C for 20 h.The outlet ammonia concentration using Fe-Ru catalyst was increased by 45.6%-63.5% than that of the single-iron catalyst at low tem-perature (375-400 °C),and the outlet ammonia concentration increased with increasing Ru catalyst loading.     

Ni-Na/Zr02-Mn02-Zn0催化合成甲基异丙基酮和二乙基酮（英文）

ZrO2-MnO2-ZnO supports were prepared by the co-precipitation method,and then Ni-Na/ZrO2-MnO2-ZnO catalysts were prepared by the impregnation method.In this paper,the reactions to synthesize methyl isopropyl ketone and diethyl ketone by the one-step synthesis method over this catalyst were studied,and meanwhile,the impact of the catalyst preparation conditions and the reaction conditions on catalyst performance was also investigated.It was observed that under the conditions when Ni loading was 25%,calcination temperature was 400℃ and reduction temperature was 410℃,this catalyst had good catalytic performance on the reaction.The suitable reaction conditions were achieved:reaction temperature was 400℃;reaction at atmospheric pressure;liquid hourly space velocity of raw material of 0.5 h 1 ;and the molar ratio of(methanol)/(methyl ethyl ketone)/(water) was equal to 1/1/1.Under such conditions,the conversion of methyl ethyl ketone could achieve 41.7%,and the overall selectivity of methyl isopropyl ketone and diethyl ketone could achieve 83.3%,which was comparable to the conversion of 38.1% and the selectivity of 82.2% achieved by using palladium as the active material.The good stability made this catalyst have good prospects for industrial application.     

稀土催化剂上丁二烯气相聚合的宏观动力学研究

The study of the kinetics of gas phase polymerization of butadiene with heterogeneous catalyst based on neodymium(Nd) was carried out.The effects of reaction temperature,reaction pressure,dispersing medium, and types of catalyst on kinetics of polymerization were investigated .A kinetic model with two kinds of active sites was proposed.The results show that the effects of the reaction temperature and the types of dispersing medium and catalyst on the kinetic performance of polymerization are significant,and that the combined model of first and second order decay of active site of catalyst can be used to describe the phenomena.     

Studies on Macro-kinetics of Gas Phase Polymerization of Butadiene with Rare-earth Catalyst

The study of the kinetics of gas phase polymerization of butadiene with heterogeneous catalyst based on neodymium (Nd) was carried out. The effects of reaction temperature, reaction pressure, dispersing medium, and types of catalyst on kinetics of polymerization were investigated. A kinetic model with two kinds of active sites was proposed. The results show that the effects of the reaction temperature and the types of dispersing medium and catalyst on the kinetic performance of polymerization are significant, and that the combined model of first and second order decay of active site of catalyst can be used to describe the phenomena.     

An efficient green route for hexamethylene-1,6-diisocyanate synthesis by thermal decomposition of hexamethylene-1,6-dicarbamate over Co3O4/ZSM-5 catalyst:An indirect utilization of CO2

The utilization of CO2 as rawmaterial for chemical synthesis has the potential for substantial economic and green benefits. Thermal decomposition of hexamethylene-1,6-dicarbamate (HDC) is a promising approach for indirect utilization of CO2 to produce hexamethylene-1,6-diisocyanate (HDI). In this work, a green route was developed for the synthesis of HDI by thermal decomposition of HDC over Co3O4/ZSM-5 catalyst, using chlorobenzene as lowboiling point solvent. Different metal oxide supported catalysts were prepared by incipientwetness impregnation (IWI), PEG-additive (PEG) and deposition precipitation with ammonia evaporation (DP) methods. Their catalytic performances for the thermal decomposition of HDC were tested. The catalyst screening results showed that Co3O4/ZSM-525 catalysts prepared by different methods showed different performances in the order of Co3O4/ZSM-525(PEG) N Co3O4/ZSM-525(IWI) N Co3O4/ZSM-525(DP). The physicochemical properties of Co3O4/ZSM- 525 catalyst were characterized by XRD, FTIR, N2 adsorption-desorption measurements, NH3-TPD and XPS. The superior catalytic performance of Co3O4/ZSM-525(PEG) catalyst was attributed to its relative surface content of Co3+, surface lattice oxygen content and total acidity. Under the optimized reaction conditions: 6.5% HDC concentration in chlorobenzene, 1 wt% Co3O4/ZSM-525(PEG) catalyst, 250 °C temperature, 2.5 h time, 800 ml·min?1 nitrogen flow rate and 1.0 MPa pressure, the HDC conversion and HDI yield could reach 100% and 92.8% respectively. The Co3O4/ZSM-525(PEG) catalyst could be facilely separated from the reaction mixture, and reused without degradation in catalytic performance. Furthermore, a possible reaction mechanism was proposed based on the physicochemical properties of the Co3O4/ZSM-525 catalysts.     

Zn–Ca–Al mixed oxide as efficient catalyst for synthesis of propylene carbonate from urea and 1,2-propylene glycol

A series of Zn–Ca–Al oxides with different CaO and ZnO contents have been prepared and evaluated in the synthesis of propylene carbonate(PC) from 1,2-propylene glycol(PG) and urea in a batch reactor. The effect of catalyst composition, basicity and reaction process parameters such as temperature, catalyst dose, molar ratio of PG to urea, purge gas flow and reaction time has been studied to find suitable reaction conditions for the PC synthesis. The PC selectivity and yield under the desired conditions could reach 98.4% and 90.8%, respectively. The best performing catalyst also exhibited a good reusability without appreciable loss in the PC selectivity and yield after five consecutive reaction runs. In addition, a stepwise reaction pathway involving a 2-hydroxypropyl carbamate intermediate was proposed for the urea alcoholysis to PC in the presence of Zn–Ca–Al catalysts, according to the time dependences of reaction intermediates and products.     

非均相羰基氧化一步合成碳酸二苯酯的研究(Ⅴ)筛选催化剂及优化合成条件

Pd/LaxPbyMnOz, Pd/C, Pd/molecular sieve and Pd-heteropoly acid catalysts for direct synthesis of diphenyl carbonate (DPC) by heterogeneous catalytic reaction were compared and the results of DPC synthesis indicated that the catalyst Pd/LaxPbyMnOz had higher activity. The Pd/LaxPbyMnOz catalyst and the support was characterized by XRD, SEM and TEM, the main phase was Lao.szPbo.asMnOa and the average diameter could be about 25.4nm. The optimuna conditions for synthesis of DPC with Pd/LasPbyMnOz were determined by orthogonal experiments and the experimental results showed that reaction temperature was the first factor of effect on the selectivity and yield of DPC, and the concentration of O2 in gas phase also had significant effect on selectivity of DPC. The optimum reaction conditions were catalyst/phenol mass ratio l to 50, pressure 4.5MPa, volume concentration of O2 25%, reaction temperature 60℃ and reaction time 4 h. The maximum yield and average selectivity could reach 13% and 97% respectively in the     

A safe and efficient process for the preparation of difluoromethane in continuous flow

Difluoromethane is typically produced vialiquid-phase fluorination as performed in a batch reactor. However,this process suffers from some problems, e.g., severe corrosion of the reactor, high safety risk, and the regeneration of the catalyst. In this paper, a flow process as performed in the tubular reactor was designed. The optimum conditions for continuous synthesis of difluoromethane were obtained as follows: the reaction temperature was 100℃, the molar ratio of dichloromethane to hydrogen fluoride was 1.6:1 and the reaction time was 300 s. The operation of the cyclic process was stable for 24 h with the conversion per pass of hydrogen fluoride up to 16.2%.The unreacted raw materials were easily reused. The deactivation of the common catalyst, antimony pentachloride, was investigated by catalyst concentration curve and XPS analysis. The approach proposed in this work is proven to be safe, efficient and low amount of catalyst.     

液相合成甲醇催化剂活性的研究

The effects of reduction procedure, reaction temperature and composition of feed gas on the activity of a CuO-ZnO-Al2O3 catalyst for liquid phase methanol synthesis were studied. An optimized procedure different from conventional ones was developed to obtain higher activity and better stability of the catalyst. Both CO and CO2 in the feed gas were found to be necessary to maintain the activity of catalyst in the synthesis process. Reaction temperature was limited up to 523K, otherwise the catalyst will be deactivated rapidly. Experimental results show that the catalyst deactivation is caused by sintering and fouling, and the effects of CO and CO2 on the catalyst activity are also investigated. The experimental results indicate that the formation of water in the methanol synthesis is negligible when the feed gas contains both CO and CO2. The mechanism for liquid-phase methanol synthesis was discussed and it differed slightly from that for gas-phase synthesis.     

非均相催化一步合成碳酸二苯酯的研究（VI）Sn 的添加量对Pd-Sn催化性能的影响

The compound metal oxide LaxPbyMnzO used as support was prepared by the sol-gel method, and the catalyst in which Pd was used as active component and Sn as co-active component for direct synthesis of diphenyl carbonate (DPC) with heterogeneous catalytic reaction was obtained by co-calcination and precipitation respectively.The catalyst was characterized by XRD, SEM and TEM respectively. The specific surface area of catalysts was measured by ChemBET3000 instrument, and the activity of the catalysts was tested by the synthesis of DPC in a pressured reactor. The results showed that when the co-active component Sn was added by co-calcination method A, its loading content was equal to 14.43% and active component Pd was loaded by precipitation, the yield and selectivity of DPC could reach 26.78% and 99% respectively.     

Study of the Kinetics of Ammonia Synthesis and Decomposition on Iron and Cobalt Catalysts

Activity of cobalt and iron catalysts in ammonia synthesis was determined under a pressure of 10 MPa and at the temperature range of 673–823 K, in a six-channel integral steel reactor. The catalytic ammonia decomposition was studied in a differential reactor under the atmosphere of low concentration of ammonia (<6%) in the temperature range of 673–823 K under atmospheric pressure. The determined values of the activation energy for the ammonia synthesis reaction over cobalt and iron catalysts are 268 and 180 kJ/mol, respectively, whilst for the ammonia decomposition reaction they are equal to 111 and 138 kJ/mol. The cobalt catalyst showed lower activity than a commercial iron catalyst in ammonia synthesis reaction. The cobalt catalyst turned out to be more effective in ammonia decomposition reaction than the iron one.     

Palladium catalyzed synthesis of methylamines from carbon dioxide, hydrogen and ammonia

The synthesis of methylamines from carbon dioxide, hydrogen, and ammonia has been studied over two palladium-alumina catalysts with palladium loadings of 2.8 and 7.6 wt%, respectively. Catalytic tests were performed in a fixed-bed microreactor at 0.6 MPa total pressure in the temperature range 473--573 K. The catalysts showed high activity for methylamine formation at low temperatures and produced monomethylamine with selectivities higher than 80%, besides of smaller amounts of di- and trimethylamine. Other carbon containing products observed were carbon monoxide, formed by the reverse water-gas shift reaction, and methane, which was the prevailing product above 573 K. In situ diffuse reflectance FTIR studies were performed to identify the species present on the catalyst surface under reaction conditions. Ammonia and methylamines are adsorbed on Brønsted and Lewis acid sites on the catalyst. Evidence is given that surface formate and isocyanate species are present on palladium-alumina under reaction conditions.     

超临界氨合成体系的组分偏摩尔体积的计算

结合R-K方程推导出偏摩尔体积计算公式,计算了超临界氨合成体系的组分偏摩尔体积,以期进一步了解各组分的相行为,为探索超临界相氨合成新工艺提供理论依据和指导.计算的条件为：H₂/N₂=3,合成气中NH₃浓度为2％～15％,超临界体系中介质浓度为20％～50％,温度为243～699 K,压力为0.1～187 MPa.结果表明：在合成气中加入合适的超临界介质并控制反应条件,体系可以达到超临界状态;在常温下或介质的临界温度附近或工业氨合成温度范围内,在各自相应的总压和组成条件下,使介质处于超临界状态,对超临界氨合成才是有利的.     

Sulphur poisoning of nickel-based hot gas cleaning catalysts in synthetic gasification gas: I. Effect of different process parameters

The effect of different process parameters on sulphur poisoning of nickel catalysts in tar (toluene), ammonia and methane decomposition was studied. Tests were carried out in a fixed-bed tube reactor at 800–1000°C at 5 and under 20 bar total pressure using a synthetic gasification gas mixture. In the same conditions, sulphur affected less the toluene and methane decomposing activity than the ammonia decomposing activity. Ammonia conversion was affected by the catalyst type but not by the nickel content of catalyst. When temperature was increased the effect of sulphur poisoning was decreased. At 20 bar pressure the poisoning effect of sulphur was stronger than at 5 bar pressure. To prevent sulphur poisoning of nickel catalysts in the tar and ammonia decomposition process at high pressure (20–30 bar), the catalyst process should operate at > 900°C. In addition, by decreasing the space velocity of the process the sulphur poisoning effect could be compensated in the test conditions.     

合成氨工业节能减排的分析

催化合成氨技术虽然已经比较成熟,但仍然潜在巨大的节能潜力。当今全球关注的能源问题又摆在合成氨工业的面前,CO₂排放也将受到严格限制。合成氨工业的节能减排应当引起人们的高度重视。本文分析了目前合成氨工业的能耗情况及其节能减排潜力,指出节能的方向在于减少提供动力的燃料消耗,即降低合成压力及其动力消耗;节能的重点,就装置类型来说,在于中小型合成氨装置;就工序过程来说,其重点在于转化工段,就单元过程来说,其重点在于不可逆性最大的过程,如燃烧反应,高的温差、浓差、压差的传递过程。但是进一步节能的关键在于调整原料结构和采用高效催化剂及其配套工艺技术。提出了大型合成氨装置采用国产新型高效催化剂,中小型合成氨装置进行降压节能工艺技术改造以及建立以洁净煤气化技术为核心的合成氨-能源多联产系统等相关建议。     

Direct synthesis of phenol from benzene over hydroxyapatite catalysts

The direct synthesis of phenol from benzene in the gas phase was studied over hydroxyapatite catalysts. The reaction was carried out in a fixed-bed reactor at atmospheric pressure and reaction temperature of 450°C in the presence of ammonia. A high selectivity (about 97%) of phenol formation at about 3.5% conversion of benzene was achieved over catalysts containing Ca and Cu ions in the cation part of hydroxyapatite. Besides phenol as the main reaction product, aniline is also formed. The reaction mechanism involves formation of N₂O from NH₃ in the first step of reaction. Benzene is oxidized by active oxygen species which are formed on the catalyst by decomposition of N₂O.     

氨合成铁、钌催化剂联用工艺

在实验室和工业侧线装置上考察了FA-Ru型氨合成钌催化剂与铁系A202型催化剂的性能差异,以及铁催化剂和钌催化剂联用工艺与单铁催化剂工艺对氨合成效果的影响。结果表明,FA-Ru催化剂在低温（375～425℃）、低压（10～15 MPa）、低氢氮比（R=1.5～2.3）和合成气高氨浓度（10%～16 %,体积分数）条件下,活性比A202催化剂相对提高44%～75%。铁催化剂与钌催化剂混装工艺的氨合成率随着钌催化剂装量的增加而增加,比单铁催化剂的氨合成率提高24.5%～44.8%。铁催化剂串钌催化剂工艺的氨合成率同样随着钌催化剂装量的增加而增加,比单铁催化剂的氨合成率提高27.7%～58.8%。对于铁、钌催化剂联用的氨合成工艺,在实验条件下,当钌催化剂用量达铁催化剂用量1/2以上时,催化剂的最高活性点温度降至400℃。工业侧线实验表明,FA-Ru催化剂在13.0 MPa、10000～15000 h-1条件下的氨合成率可达到铁催化剂在相同空速、26 MPa 压力下的水平。根据不同工况,铁催化剂串钌催化剂生产工艺比单铁催化剂生产工艺氨合成率可相对提高43%～56%。     

影响Ru/MO_x氨合成催化剂活性关键因素

氨合成催化剂是多相催化领域中许多基础研究的起点,低温高活性的钌系催化剂为继熔铁催化剂之后的第二代氨合成催化剂。从影响氧化物负载的Ru基催化剂性能的关键因素出发,对氧化物载体的改性、助剂的作用并将其深入到反应条件下的化学状态等方面进行了分析和探讨,为新型高活性Ru基氨合成催化剂及其他多相催化剂的设计研发提供借鉴。     

Kinetic study of carbon nanotube synthesis over Mo/Co/MgO catalysts

The kinetics of carbon nanotube (CNT) synthesis by decomposition of CH₄ over Mo/Co/MgO and Co/MgO catalysts was studied to clarify the role of catalyst component. In the absence of the Mo component, Co/MgO catalysts are active in the synthesis of thick CNT (outer diameter of 7-27 nm) at lower reaction temperatures, 823-923 K, but no CNTs of thin outer diameter are produced. Co/MgO catalysts are significantly deactivated by carbon deposition at temperatures above 923 K. For Mo-including catalysts (Mo/Co/MgO), thin CNT (2-5 walls) formation starts at above 1000 K without deactivation. The significant effects of the addition of Mo are ascribed to the reduction in catalytic activity for dissociation of CH₄, as well as to the formation of Mo₂C during CNT synthesis at high temperatures. On both Co/MgO and Mo/Co/MgO catalysts, the rate of CNT synthesis is proportional to the CH₄ pressure, indicating that the dissociation of CH₄ is the rate-determining step for a catalyst working without deactivation. The deactivation of catalysts by carbon deposition takes place kinetically when the formation rate of the graphene network is smaller than the carbon deposition rate by decomposition of CH₄.     

耐高温焦炉煤气氨分解催化剂的研究

研究了经过改进的MgO载体对NH3分解活性和反应热稳定性的影响。在容易造成催化剂烧结的高温、水蒸气等条件下,对催化剂进行活性评价;通过超高温处理,观察催化剂活性下降情况,配合XRD分析结果以及SEM照片,发现通过ZrO2修饰载体和特定方法制备的催化剂,在高温下能够较好地抑制Ni、Co活性组分的烧结,具有良好的热稳定性。