Catalytic degradation of oxygenates in Fischer–Tropsch aqueous phase effluents to fuel gas via hydrodeoxygenation over Ru/AC catalyst

BACKGROUND: Aqueous phase Fischer–Tropsch (FT) effluents co‐produced with hydrocarbons in the FT process contain various water‐soluble oxygenates, e.g. carboxylic acids, alcohols. Purification of the FT aqueous phase is important from the viewpoint of effective resource utilization and environmental stewardship. In this work, an aqueous‐phase hydrodeoxygenation process was investigated for the degradation of FT aqueous phases. RESULTS: The Ru/AC catalyst was determined to be the most active catalyst. The key parameters, i.e. temperature, pressure, weight hourly space velocity and Ru loading, were comprehensively optimized. Under optimal conditions, ca 98% of the oxygenates were converted to C₁～C₆ alkanes. The degraded water had no odour, a neutral pH, and as low as 1000 mg L^?1 chemical oxygen demand. The Ru/AC catalyst exhibited long‐term stability (1300 h) and no ruthenium leaching. A reaction pathway is proposed for this process in which the carboxylic acids are hydrogenated to alcohols via the formation of aldehydes. Alcohols and aldehydes are then converted to methane and alkanes of one carbon atom less than the substrate through C? C bond cleavage. CONCLUSIONS: This process is effective for treating FT aqueous phase effluent, and holds great promise for industrial applications due to its high efficiency, simplicity and stability. Copyright © 2011 Society of Chemical Industry     

Catalytic decomposition of ammonia over fly ash supported Ru catalysts

Fly ash (FA), an industrial waste material, has been treated by physical and chemical methods. These materials were then employed as supports for preparation of Ru-based catalysts for H₂ generation from ammonia decomposition. The physicochemical properties of the supports and Ru-based catalysts were characterised using several techniques. The results revealed that the surface area of FA could be enhanced and thus improved the dispersion of Ru particles, resulting in higher catalytic activity. Ru/FA-800 exhibits the highest conversion due to higher surface loading of Ru, stronger NH₃ adsorption and least acid sites.     

Fischer–Tropsch synthesis. Conversion of alcohols over iron oxide and iron carbide catalysts

Both iron oxide (Fe₂O₃) and iron carbide catalysts are active for the dehydration of tertiary alcohols; the oxide catalyst is not reduced nor is the bulk carbide oxidized by the steam generated during the dehydration reaction. Secondary alcohols are selectively converted to ketones plus hydrogen by both the iron oxide and carbide catalyst. Fe₂O₃ is reduced to Fe₃O₄ during the conversion of secondary alcohols. Both iron carbide and oxide catalysts dehydrogenate a primary alcohol (C_n) to an aldehyde which undergoes a secondary ketonization reaction to produce a symmetrical ketone with 2n−1 carbons. These results plus those of our earlier ¹⁴C-tracer studies suggest that dehydration of alcohols to produce olefins makes a minor, if any, contribution during Fischer–Tropsch synthesis with an iron catalyst at low and intermediate pressure conditions.     

Effect of Ru addition to Co/SiO2/HZSM-5 catalysts on Fischer–Tropsch synthesis of gasoline-range hydrocarbons

Microporous HZSM-5 zeolite and mesoporous SiO₂ supported Ru–Co catalysts of various Ru adding amounts were prepared and evaluated for Fischer–Tropsch synthesis (FTS) of gasoline-range hydrocarbons (C₅–C₁₂). The tailor-made Ru–Co/SiO₂/HZSM-5 catalysts possessed both micro- and mesopores, which accelerated hydrocracking/hydroisomerization of long-chain products and provided quick mass transfer channels respectively during FTS. In the same time, Ru increased Co reduction degree by hydrogen spillover, thus CO conversion of 62.8% and gasoline-range hydrocarbon selectivity of 47%, including more than 14% isoparaffins, were achieved simultaneously when Ru content was optimized at 1 wt% in Ru–Co/SiO₂/HZSM-5 catalyst.     

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.     

Morphology and deactivation behaviour of Co–Ru/γ‐Al2O3 Fischer–Tropsch synthesis catalyst

Deactivation of Co–Ru/γ‐Al₂O₃ Fischer–Tropsch (FT) synthesis catalyst along the catalytic bed over 850 h of time‐on‐stream (TOS) was investigated. Catalytic bed was divided into four parts and structural changes of the spent catalysts collected from each catalytic bed after FT synthesis were studied using BET, ICP, XRD, TPR, carbon determination, H₂ chemisorption and oxygen titration techniques. Rapid deactivation was observed during first 200 h of FT synthesis. In this case, the deactivation rate was not dependent on the number of the catalyst active sites. It was zero order to CO conversion and independent of the size of active sites. Beyond the TOS of 200 h, the deactivation could be simulated with a power law expression: . The physical properties of the catalyst charged in 1st half of the reactor did not change significantly. Interaction of cobalt with alumina and formation of mixed oxides of the form xCoO·yAl₂O₃ and CoAl₂O₄ was increased along the catalytic bed. Percentage reducibility and dispersion decreased by 2.4–25.5% and 0.5–8.8% for the catalyst in the beds 1 and 4, respectively. Particle diameter increased by 0.8–6.1% for the catalyst in the beds 1 and 4 respectively suggesting higher rate of sintering at last catalytic bed. The amount of coke formation in the 4th catalytic bed was 6 times more than that of in bed 1.     

Catalytic combustion of methane over supported bimetallic Pd catalysts: Effects of Ru or Rh addition

A series of Pd/γ-Al₂O₃ catalysts with various amounts of Ru or Rh with, and/or without, BaO were prepared by successive incipient wetness impregnation. The catalysts were investigated for the catalytic methane combustion before, and after, H₂S poisoning in an oxygen-rich atmosphere. The addition of ruthenium enhanced the catalytic activity for methane oxidation even after H₂S poisoning while maintaining the initial catalytic activity of the fresh catalyst. These results are explained in terms of dispersion of palladium by ruthenium and poisoning resistance of ruthenium. The addition of rhodium did not improve the overall activity in methane oxidation.     

Study on products distribution of iron and iron–zeolite catalysts in Fischer–Tropsch synthesis

The dependencies of hydrocarbon product distributions of iron and physical mixture of iron–zeolite catalyzed Fischer–Tropsch synthesis on reaction conditions include: reaction temperature, reaction pressure, H₂/CO feed ratios; space velocity and effect of zeolite presence have been investigated. The concept of two superimposed Anderson–Schulz–Flory distributions has been applied for the representation of the product distribution for both iron and iron–zeolite catalysts. Zeolite presence increased secondary reactions that include cracking of heavier products and light olefins oligomerization. Product distribution of iron–zeolite catalyst was comparable with iron catalyst at high space velocity, because the role of the zeolite on overall reaction declined.The results of the product distribution dependency on the reaction conditions over both iron and iron–zeolite catalysts showed that the average number of carbon decreases with H₂/CO ratio increasing and the reaction temperature in product.     

The application of Mössbauer emission spectroscopy to industrial cobalt based Fischer–Tropsch catalysts

⁵⁷Co-Mössbauer emission spectroscopy (MES) has been used to study the oxidation of cobalt as a deactivation mechanism of high loading cobalt based Fischer–Tropsch catalysts for the gas-to-liquids process. It was reported previously [Catal. Today 58 (2000) 321; Proceedings of the International Symposium on the Industrial Applications of the Mössbauer Effect, 13–18 August, 2000, Virginia Beach, VA] that oxidation was observed at atmospheric pressure under conditions that were in contradiction with the bulk cobalt phase thermodynamics. A high-pressure MES cell was designed and constructed, which created the opportunity to study the oxidation of cobalt based Fischer–Tropsch catalysts under realistic synthesis conditions. The cobalt catalyst preparation procedure was investigated by means of ⁵⁷Fe-Mössbauer absorption spectroscopy, applying ⁵⁷Fe as a probe atom. Initial results indicate, although not yet conclusive, that a ⁵⁷Co-MES catalyst can be prepared from the industrial prepared standard Co catalyst by an additional simple incipient wetness impregnation procedure.     

负载型NiO和CoO催化剂上N2O分解研究

本研究在对多种金属氧化物催化剂进行初步筛选的基础上，研制出以莫来石为载体的负载型NiO、CoO催化剂，考察了分解温度、催化剂组成和负载量对N2O分解率的影响，并对其分解反应动力学进行了研究。结果表明莫来石负载NiO、CoO催化剂对N2O分解有良好的催化性能；其反应速度对N2O均为一级反应；同样负载量下NiO有更好的催化分解活性；这一研究为开发阻力低、催化性能好的工业用蜂窝型规整填料奠定了基础。     

Catalytic hydrothermal liquefaction of D. tertiolecta for the production of bio‐oil over different acid/base catalysts

In this article, two acid catalysts (ZrO₂/SO₄^2? and HZSM‐5) and two base catalysts (MgO/MCM‐41 and KtB) were used in catalytic hydrothermal liquefaction (HTL) of Dunaliella tertiolecta (D. tertiolecta) for the production of bio‐oil. The results indicated that the acid/base property of the catalyst plays a crucial role in the catalytic HTL process, and the base catalyst is conducive to the improvement of conversion and bio‐oil yield. When KtB was used as the catalyst, the maximum conversion and bio‐oil yield was 94.84 and 49.09 wt %, respectively. The detailed compositional analysis of the bio‐oil was performed using thermogravimetric analysis, elemental analysis, FT‐IR, and GC‐MS. The compositional analysis results showed that the introduction of catalyst is beneficial for reducing the fixed carbon content in the bio‐oil, and the structure of catalyst influences on the bio‐oil composition and boiling point distribution. Based on our results and previous studies, the probable catalytic HTL microalgae model over various catalysts can be described that the main chemical reactions include ketonization, decarboxylic, dehydration, ammonolysis, and so forth. with HZSM‐5 and MgO/MCM‐41 as the catalyst; the cyclodimerization, decomposition, Maillard reaction, and ketonization are the main reactions with ZrO₂/SO₄^2? as the catalyst; the dehydration, ammonolysis, Maillard reaction, and ketonization can occur with KtB as the catalyst. Therefore, a plausible reaction mechanism of the main chemical component in D. tertiolecta is proposed. © 2015 American Institute of Chemical Engineers AIChE J, 61: 1118–1128, 2015     

Performance and characterization of Ru/Al2O3 and Ru/SiO2 catalysts modified with Mn for Fischer–Tropsch synthesis

Mn effect and characterization on γ-Al₂O₃-, -Al₂O₃- and SiO₂-supported Ru catalysts were investigated for Fischer–Tropsch synthesis under pressurized conditions. In the slurry phase Fischer–Tropsch reaction, γ-Al₂O₃ catalysts showed higher performance on CO conversion and C₅⁺ selectivity than -Al₂O₃ and SiO₂ catalysts. Moreover, Ru/Mn/γ-Al₂O₃ exhibited high resistance to catalyst deactivation and other catalysts were deactivated during the reaction. From characterization results on XRD, TPR, TEM, XPS and pore distribution, Ru particles were clearly observed over the catalysts, and γ-Al₂O₃ catalysts showed a moderate pore and particle size such as 8 nm, where -Al₂O₃ and SiO₂ showed highly dispersed ruthenium particles. The addition of Mn to γ-Al₂O₃ enhanced the removal of chloride from RuCl₃, which can lead to the formation of metallic Ru with moderate particle size, which would be an active site for Fischer–Tropsch reaction. Concomitantly, manganese chloride is formed. These schemes can be assigned to the stable nature of Ru/Mn/γ-Al₂O₃ catalyst.     

Selective hydrogenation of benzene to cyclohexene catalyzed by Ru supported catalysts: Influence of the alkali promoters on kinetics, selectivity and yield

The selective hydrogenation of benzene to cyclohexene in the presence of Ru supported catalysts has been investigated in a tetraphase slurry reactor at 423 K, at 5 MPa of pressure, in the presence of two liquid phases: benzene and an aqueous solution of ZnSO₄ (0.6 mol l⁻¹). A study of the influence of the transport phenomena on the reactivity of the catalyst has been carried out. But no correlation between Carberry and Wheeler–Weisz numbers and the selectivity of the catalysts has been found. The main features of the catalysts are the strong dependence between the catalysts preparation procedure and their activity and selectivity. The best results have been observed with Ru/ZrO₂ catalysts. The influence of the bases employed in the precipitation of the catalysts precursor has also been investigated. KOH is the most effective, yield of 41% and initial selectivity of 80% of cyclohexene has been observed.     

基于MCM-41的镍基甲烷化催化剂活性与稳定性

采用浸渍法分别以MCM-41,Al₂O₃和SiO₂ 为载体制备了不同镍负载量的甲烷化催化剂,并在连续流动固定床反应装置上对其甲烷化催化活性进行了评价。研究结果表明,与Ni/Al₂O₃和Ni/SiO₂相比,相同镍负载量的Ni/MCM-41催化剂具有更好的催化活性。同时研究了Ni含量对于Ni/MCM-41催化剂催化活性的影响,发现随着Ni含量的增加,CO转化率和CH₄收率逐渐升高,并且在Ni含量大于10%（质量分数）以后趋于稳定。在n（H₂）：n（CO）=3：1、反应压力1.5 MPa、反应温度350℃及质量空速12000 ml·h^-1·g^-1的反应条件下,10%Ni/MCM-41催化剂CH₄选择性达到94.9%,CO转化率接近100%。在100 h催化活性稳定性试验中,10%Ni/MCM-41催化活性无明显下降,表现出良好的催化活性稳定性。采用X射线衍射（XRD）、氮气物理吸附（BET）、热重分析（TG）及氢气程序升温还原（H₂-TPR）等技术手段对催化剂进行了表征,结果表明Ni颗粒大小是影响Ni/MCM-41催化剂催化活性的主要因素。     

Intrinsic kinetics of Fischer–Tropsch reactions over an industrial Co–Ru/γ-Al2O3 catalyst in slurry phase reactor

The rate of Fischer–Tropsch synthesis over an industrial well-characterized Co–Ru/γ-Al₂O₃ catalyst was studied in a laboratory well mixed, continuous flow, slurry reactor under the conditions relevant to industrial operations as follows: temperature of 200–240 °C, pressure of 20–35 bar, H₂/CO feed ratio of 1.0–2.5, gas hourly space velocity of 500–1500 N cm³ g_cat^− 1 h^− 1 and conversions of 10–84% of carbon monoxide and 13–89% of hydrogen. The ranges of partial pressures of CO and H₂ have been chosen as 5–15 and 10–25 bar respectively. Five kinetic models are considered: one empirical power law model and four variations of the Langmuir–Hinshelwood–Hougen–Watson representation. All models considered incorporate a strong inhibition due to CO adsorption. The data of this study are fitted fairly well by a simple LHHW form − R_H2 + CO = ap_H2^0.988p_CO^0.508 / (1 + bp_CO^0.508)² in comparison to fits of the same data by several other representative LHHW rate forms proposed in other works. The apparent activation energy was 94–103 kJ/mol. Kinetic parameters are determined using the genetic algorithm approach (GA), followed by the Levenberg–Marquardt (LM) method to make refined optimization, and are validated by means of statistical analysis. Also, the performance of the catalyst for Fischer–Tropsch synthesis and the hydrocarbon product distributions were investigated under different reaction conditions.     

Catalytic oxidization of SO2 from incineration flue gas over bimetallic Cu–Ce catalysts supported on pre-oxidized activated carbon

To improve the deep sulfation of alumina support, the inertness material activated carbon was used as an alternative support for copper/cerium catalysts to remove SO₂ from incineration flue gas which contained other air pollutants such as NO_X, CO, CO₂, HCl, carbon particulates, and heavy metal vapor. During the 473–820 K, the AC support showed no retention of SO₂. However, the metal Pb composed in the flue gas exhibited the toxic characterization to M/AC catalysts, which was due to the outer orbitals of d subshell all paired.     

Supercritical water gasification of aqueous fraction of pyrolysis oil in the presence of a Ni‐Ru catalyst

This study demonstrated that aqueous fraction of pyrolysis oil can be efficiently gasified into fuel gases methane and hydrogen via supercritical water gasification (SCWG) at moderate temperatures (500–700°C) over Ni_20%Ru_2%/γ‐Al₂O₃ catalyst. All experiments were performed in a bench‐scale continuous down‐flow tubular reactor packed with the catalyst. Carbon gasification efficiency of 0.91 mol/mol‐C (converted into CH₄ and CO₂) was achieved in SCWG of the aqueous fraction of pyrolysis oil (containing 2.98 wt % C) at 700°C in the presence of the catalyst. A similar carbon gasification efficiency (approx. 0.89 mol/mol‐C) was obtained at a lower temperature (600°C) with a diluted feedstock (0.7 wt %C). Scanning Electron Microscopy coupled with Energy Dispersive x‐ray and inductively coupled plasma analysis results confirmed that this catalyst was stable during SCWG of aqueous fraction of pyrolysis oil after 6 h on‐stream. © 2016 American Institute of Chemical Engineers AIChE J, 62: 2786–2793, 2016