Carbon Monoxide Hydrogenation on Cobalt/Zeolite Catalysts

The synthesis of hydrocarbons from catalytic hydrogenation of CO/H₂ was investigated over Co/zeolite catalysts at 1 atm, 493–553 K, H₂/CO = 2, and GHSV = 1200. Various zeolites, such as NaA, NaX, NaY, KL and NaMordenite, were used as the supports. The catalysts were prepared by impregnation and were characterized by H₂/CO chemisorption and temperature-programmed reduction (TPR). Based on TPD measurements, the CO/H₂ adsorption ratio can be used as an index for the extent of metal-zeolite interaction. The stronger the metal-zeolite interaction is, the higher the Co/H₂ adsorption ratio on metal is. The activity and selectivity of cobalt supported in zeolites were affected by complex factors such as framework structure, Si/Al ratio, and the complementary cations. The activity of the catalyst is in the order: Co/KL > Co/NaX > Co/NaY > Co/NaMordenite > Co/NaA. All of the Co/zeolite catalysts had a very high selectivity to C₂–C₄ olefins, which would decrease with increasing reaction temperature. Cobalt oxide supported in zeolite was difficult to reduce. Increasing the reduction temperature could increase the reducibility of cobalt and resulted in the increase of activity.     

Preparation of egg-shell nanonickel catalyst for CO hydrogenation

Egg-shell like Ni-based catalyst was prepared on a porous hollow silica (PHS) support to synthesize methanol from CO hydrogenation. It was found from Transmission Electron Microscope (TEM) that Ni particles with a size of 9–11 nm were loaded on PHS to obtain the egg-shell catalysts. X-ray Diffraction (XRD) and X-ray Photoelectron Spectroscopy (XPS) analyses indicated that the active site of the catalysts was metallic Ni, which would not be oxidized during the reaction. When the as-prepared Ni/SiO₂ egg-shell catalyst was used for CO hydrogenation at 220 °C and 2.0 MPa, the conversion of CO and selectivity to methanol were about 69.5 mol% and 92 mol%, respectively, showing higher activity and selectivity than conventional catalysts. The thermodynamic analysis of CO hydrogenation for methanol synthesis indicated that the conversion of CO is 69.5 mol% under these conditions.     

Core–shell structured Cu@m-SiO2 and Cu/ZnO@m-SiO2 catalysts for methanol synthesis from CO2 hydrogenation

The core–shell catalysts with Cu and Cu/ZnO nanoparticles coated by mesoporous silica shells are prepared for CO₂ hydrogenation to methanol. With the confined effect of silica shell, the size of Cu nanoparticles is only about 5.0 nm, which results in high activity for CO₂ conversion. The CH₃OH selectivity is enhanced significantly with the introduction of ZnO. The core–shell structured catalysts endow the Cu nanoparticles trapped inside with excellent anti-aggregation and no deactivation is observed with time-on-stream. Therefore, the core–shell Cu/ZnO@m-SiO₂ catalyst exhibits the maximum CH₃OH yield with high stability.     

n-Octane aromatization on Pt-containing non-acidic large pore zeolite catalysts

Platinum catalysts supported on the potassium-form of different large-pore zeolites (i.e. K-LTL, K-BEA, K-MAZ, and K-FAU) have been tested for n-octane aromatization at 500 °C. All catalysts were prepared by the vapor phase impregnation (VPI) method. It was found that the Pt/K-LTL catalyst exhibit a better aromatization performance than the other zeolite catalysts. However, due to secondary hydrogenolysis, the C8 aromatics produced inside the zeolite are converted to benzene and toluene. By contrast, a non-microporous Pt/SiO₂ catalyst did not present the secondary hydrogenolysis. Therefore, despite a lower initial aromatization activity, Pt/SiO₂ results in higher selectivity to C8 aromatics than any of the other zeolite catalysts. All fresh catalysts were characterized by hydrogen chemisorption and FT-IR of adsorbed CO. In addition, the residual acidity of the supports was analyzed by temperature programmed desorption (TPD) of ammonia. In agreement with previous studies, it was found that after reduction at either 350 or 500 °C, the Pt/K-LTL showed much higher Pt dispersion than other catalysts. It is known that the structure of L zeolite can stabilize the small Pt clusters inside the zeolite channel. By contrast, FT-IR indicated that a large fraction of platinum clusters were located outside the zeolite channels in the case of Pt/K-BEA and Pt/K-MAZ catalysts.     

Highly selective hydrogenation of phenol and derivatives over Pd catalysts supported on SiO2 and γ-Al2O3 in aqueous media

Pd/Al₂O₃ and Pd/SiO₂ catalysts containing Pd nanoparticles in the size range of 3–13 nm were prepared and investigated in direct selective hydrogenation of phenol to cyclohexanone. Catalysts with 3 nm Pd nanoparticles present highly active and promoted the selective formation of cyclohexanone under atmospheric pressure of hydrogen in aqueous media without additives. Conversion of 99% and a selectivity higher than 99% were achieved within 3 h at 333 K. The generality of Pd/Al₂O₃ catalyst with 3 nm Pd nanoparticles for this reaction was demonstrated by selective hydrogenation of other hydroxylated aromatic compounds with similar performance.     

Confined Iron Nanoparticles on Mesoporous Ordered Silica for Fischer–Tropsch Synthesis

Iron oxide particles were deposited in an ordered mesoporous material (SBA-15) with the aim of studying its behavior in the catalytic hydrogenation of CO (Fischer–Tropsch Synthesis). Bulk iron oxide, and iron supported on porous silica with different textural properties (Aerosil^®-200) were used for comparison. The characterization of the materials showed that in the Fe@SBA-15 material, iron nanoparticles were confined inside the mesopores of the SBA-15 support (pore diameter ~?8 nm), and Fe@Aerosil^®-200 material also presented iron oxide nanoparticles highly dispersed on the material. In situ Synchrotron radiation XRD studies were performed in order to study the evolution of iron phases in the Fe@SBA-15 and the bulk iron oxide under hydrogen and hydrogen/carbon monoxide conditions. DFT calculations were performed on bare Fe(100) and a Fe₁₆ cluster in CO activation and C_xH_y hydrogenation. Catalytic microactivity tests, performed at conversions of ~?6–8%, showed important differences in the selectivity of the materials. Higher selectivity to methane and light hydrocarbons were observed in the supported catalysts (Fe@SBA-15 and Fe@Aerosil^®-200) than in bulk Fe catalyst. Moreover, the supported catalysts showed selectivity to ethylene (Fe@SBA-15) and propylene (Fe@Aerosil^®-200), products that were not observed in the bulk iron catalyst. On the other hand, bulk iron showed a major selectivity to higher hydrocarbons (C₅–C₉) and oxygenates.

     

Hydrogenation of CO2 to formic acid on supported ruthenium catalysts

We report on the preparation and application of novel heterogeneous supported ruthenium catalysts. The catalysts are active in the synthesis of formic acid from the hydrogenation of carbon dioxide and are characterized by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, X-ray powder diffraction analysis and transmission electron microscopy. Abundant hydroxyl groups, which interact with the ruthenium components, play an important role in the catalytic reactions. Highly dispersed ruthenium hydroxide species enhance the hydrogenation of CO₂, while crystalline RuO₂ species, which are formed from the relatively high ruthenium content or the pH of the solution during preparation of the catalyst, restrict the production of formic acid. Optimal activity of ruthenium hydroxide as a catalyst for the hydrogenation of CO₂ to formic acid is achieved over a γ-Al₂O₃ supported 2.0 wt% ruthenium catalyst, which is prepared in a solution of pH 12.8 with NH₃·H₂O as a titration solvent. A possible hydrogenation mechanism for the hydroxide ruthenium catalyst is proposed.     

Solvothermal One-Step Synthesis and Effect of Carbon on Properties of Ruthenium Sulfide Catalysts

Abstract  

Solvothermal one-step synthesis method was used for the preparation of ruthenium sulfide catalysts supported on the carbon black by the reaction of Ru₃(CO)₁₂ and sulfur powder with the carbon black in i-propanol. The carbon black acted as not only a supporting substrate but also a dispersing agent for ruthenium sulfide nanoparticles in the solvothermal one-step synthesis. The oxygen reduction properties of the products prepared by the solvothermal one-step synthesis were improved in comparison with those of the catalysts prepared by physically mixing the carbon black with the solvothermally prepared ruthenium sulfide powder.     

Changes in the selective hydrogenation of citral induced by copper addition to Ru/KL catalysts

Bimetallic Ru–Cu catalysts supported on KL zeolite have been prepared by coimpregnation with ionic precursors and characterized by several methods, such as temperature-programmed reduction, CO and hydrogen chemisorption, nitrogen adsorption, infrared spectroscopy of chemisorbed CO and microcalorimetry of CO adsorption. The catalytic behavior of the samples was analyzed in the selective hydrogenation of citral in the liquid phase, at 323 K and 5 MPa. The presence of bimetallic entities as well as of segregated copper species was recognized by the TPR measurements. The CO-FTIR and microcalorimetry results evidence that the higher the Cu/Ru atomic ratio the larger the surface heterogeneity, with formation of Cu^δ+ species. Bimetallic catalysts are more active than the monometallic ruthenium catalyst in the hydrogenation of citral, but this activity decreases with the increasing of copper concentration. In addition, selectivity towards citronellal decreases as the copper content increases, in opposite trend to the selectivity toward geraniol and nerol. For low copper loading (Cu/Ru ≈ 0.4) formation of a surface alloy is discussed. This surface structure is particularly active for hydrogenation of the conjugated CC double bond of citral. For Cu/Ru = 0.8 and Cu/Ru = 1.2 samples, three-dimensional islands of segregated copper seem to cover, in part, the surface alloy. This latter surface structure is less active than the preceding one for hydrogenation of the CC double bond, but more selective for hydrogenation of the CO group of citral.     

Porous carbon as support for iron and ruthenium catalysts

Iron and ruthenium catalysts have been supported on a porous carbon prepared by pyrolysis and activation of the copolymer Saran. For comparison, a graphitized carbon black (V3G) has also been used as support for both metals. The catalysts have been characterized by chemisorption of H₂ and CO₂ at 298 K (373 K in some cases) and by X-ray line broadening. The hydrogen chemisorption on iron catalysts was very low and increased with adsorption temperature, whereas the CO chemisorption results indicate the formation of subcarbonyl species. However, H₂ and CO uptakes led to similar dispersion values for the ruthenium catalysts. The X-ray results were in good agreement with the chemisorption results except in the case of highly dispersed Fe catalysts. The results obtained in the hydrogenation of CO indicate that in the case of Fe catalysts the highest selectivity toward hydrocarbons was given by the catalyst supported on V3G, with large metal particle size which, at the same time, exhibited a lower decrease in activity with reaction time than the other Fe catalysts with smaller average particle size. The olefin/paraffin ratio is very large for the catalyst prepared from Fe(CO)₅.The Ru catalysts are essentially of the methanation type.     

Hydrogenation of vegetable oil using highly dispersed Pt/γ-Al2O3 catalyst: Effects of key operating parameters and deactivation study

In the present work, Pt/γ-Al₂O₃ catalysts with high metal dispersion were prepared and characterized using chloroplatinic acid and platinum acetylacetonate as metal precursors. The activity and selectivity of the catalysts were evaluated in the hydrogenation of sunflower oil. A comprehensive analysis of the effects of key operational parameters on catalytic performance was carried out. The experimental variables were hydrogen pressure (275.8–551.6 kPa), temperature (160–200°C), and catalyst loading (0.005–0.015 kg Pt_exp/m³_oil). Platinum catalysts were active, with a double bond conversion of 28% at 2 h. The metal precursor affected catalyst selectivity. The catalyst prepared with chloroplatinic acid exhibited a lower formation of trans-isomers compared with Pt acetylacetonate. The γ-Al₂O₃ supported platinum catalyst with a metal loading of 0.51 wt.% and a metal dispersion of 98% maintained its initial catalyst activity and selectivity after 10 consecutive uses (1200 min accumulate operation time), without changes in its catalytic properties. The obtained results suggested that Pt catalysts are an attractive alternative to conventional nickel catalysts for the hydrogenation of vegetable oil.     

Catalysts with noble metals based on super-cross-linked polystyrene for the hydrogenation of aromatic hydrocarbons

A series of catalysts containing noble metals on a super-cross-linked polystyrene (SCP) support with a developed specific surface area (>1000 m²/g) and high thermal stability are prepared and studied to develop an effective catalyst for the low-temperature hydrogenation of aromatic hydrocarbons. A study of Pt- and Pd-containing catalysts based on SCP, carbon supports, and alumina in the hydrogenation of simple (benzene, toluene), branched (n-butylbenzene) and polycyclic (terphenyl) aromatic compounds is conducted. In the hydrogenation of aromatic hydrocarbons, the activity of the catalysts on SCP is comparable to or surpasses analogous catalysts based on Al₂O₃ and Sibunit in the content of noble metals; it is established that catalysts on SCP have greater selectivity in the hydrogenation of benzene in a benzene-toluene mixture. The electronic state of metals in the Pt(Pd)/SCP catalysts is studied by the IR spectroscopy of adsorbed CO. In testing the catalysts in the hydrogenation of terphenyl, it is found that Pt-containing catalyst on the SCP can operate in reversible hydrogenation-dehydrogenation cycles (terphenyl-tercyclohexane); this is promising for the use of such catalyst systems in creating composite materials for hydrogen storage.     

Hydrogenation of carbon dioxide by hybrid catalysts,direct synthesis of aromatics from carbon dioxide and hydrogen

Direct synthesis of aromatics from carbon dioxide hydrogenation was investigated in a single stage reactor using hybrid catalysts composed of iron catalysts and HZSM-5 zeolite. Carbon dioxide was first converted to CO by the reverse water gas shift reaction, followed by the hydrogenation of CO to hydrocarbons on iron catalyst, and finally the hydrocarbons were converted to aromatics in HZSM-5. Under the operating conditions of 350°C, 2100 kPa, and CO₂/H₅ = 1/2, the maximum aromatic selectivity obtained was 22% with a CO₂ conversion of 38% using fused iron catalyst combined with the zeolite. Together with the kinetic studies, thermodynamic analysis of the CO₂ hydrogenation was also conducted. It was found that unlike Fischer Tropsch synthesis, the formation of hydrocarbons from CO₂ may not be thermodynamically favored at higher temperatures.     

Synthesis of a nano-nickel catalyst modified by ruthenium for hydrogenation and hydrodechlorination

A nano-nickel catalyst was prepared by chemical reduction with N₂H₄·H₂O, and was modified with ruthenium by chemical replacement. The nano-Ni and NiRu catalysts were characterized by X-ray diffraction, transmission electron microscope, and X-ray photoelectron spectroscopy. The catalysts were evaluated in the liquid phase hydrogenation of cinnamaldehyde and hydrodechlorination of chlorobenzene. The NiRu catalyst exhibited a much higher selectivity to the hydrocinnamaldehyde and a better hydrodechlorination activity and stability than those of the Ni catalyst.     

Rhodium nanoparticles intercalated into montmorillonite for hydrogenation of aromatic compounds in the presence of thiophene

Rhodium metal nanoparticles intercalated into montmorillonite (Rh-MMT) have been prepared and used for the hydrogenation of benzene and other aromatic compounds. Rh-MMT was characterized by PXRD, TEM and ICP-AES. The crystallite size of the rhodium particles was 6.9 nm using PXRD and the particle size by TEM was 25.6 ± 2.5 nm. Benzene hydrogenation was carried out at different substrate/catalyst mass ratios, temperature and pressure to optimize the reaction conditions. The benzene is completely hydrogenated with 100% selectivity to cyclohexane at 453 K and 6.2 MPa. The catalyst was poisoned by thiophene, and benzene hydrogenation decreased with increasing thiophene concentration. Hydrogenation of toluene, o,m,p-xylenes, naphthalene and anthracene were also carried out at the optimized reaction conditions.     

Rh<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Pd<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> Nanoparticle Composition Dependence in CO Oxidation by NO

Abstract  

Bimetallic 15 nm Pd-core Rh-shell Rh_1−x Pd _x nanoparticle catalysts have been synthesized and studied in CO oxidation by NO. The catalysts exhibited composition-dependent activity enhancement (synergy) in CO oxidation in high NO pressures. The observed synergetic effect is attributed to the favorable adsorption of CO on Pd in NO-rich conditions. The Pd-rich bimetallic catalysts deactivated after many hours of oxidation of CO by NO. After catalyst deactivation, product formation was proportional to the Rh molar fraction within the bimetallic nanoparticles. The deactivated catalysts were regenerated by heating the sample in UHV. This regeneration suggests that the deactivation was caused by the adsorption of nitrogen atoms on Pd sites.     

Influences of preparation methods of ZrO2 support and treatment conditions of Cu/ZrO2 catalysts on synthesis of methanol via CO hydrogenation

ZrO₂ supports were prepared by different methods (conventional precipitation method, shortened as “CP”, and alcogel/thermal treated with nitrogen method, shortened as “AN”), and Cu/ZrO₂ catalysts were prepared by impregnation method. The supports and catalysts were characterized by BET, XRD, TEM and TPR. The effects of the preparation methods of ZrO₂ supports and the treatment conditions (calcination and reduction temperatures) of the catalyst precursors on the texture structures of the supports and catalysts as well as on the catalytic performances of Cu/ZrO₂ in CO hydrogenation were investigated. The results showed that the support ZrO₂-AN had larger BET specific surface area, cumulative pore volume and average pore size than the support ZrO₂-CP. Cu/ZrO₂-AN catalysts showed higher CO hydrogenation activity and selectivity of oxygenates (C₁–C₄ alcohols and dimethyl ether) than Cu/ZrO₂-CP catalysts. Calcination and reduction temperatures of supports and catalyst precursors affected the catalytic performance of Cu/ZrO₂. The conversion of CO and the STY of oxygenates were 12.7% and 229 g/kg h, respectively, over Cu/ZrO₂-AN-550 at the conditions of 300 °C, 6 MPa.     

Deep desulphurization of diesel fuels on bifunctional monolithic nanostructured Pt-zeolite catalysts

The preparation of Pt-zeolite catalysts, including choice of the noble metal precursor and loading (1.0–1.8 wt.%), was optimized for maximizing the catalytic activity in thiophene hydrodesulphurization (HDS) and benzene hydrogenation (HYD). According to data obtained by HRTEM, XPS, EXAFS and FTIR spectroscopy of adsorbed CO, the catalysts contained finely dispersed Pt nanoparticles (2–5 nm) located on montmorillonite and zeolite surfaces as: Pt⁰ (main, ν_CO = 2070–2095 cm⁻¹), Pt^δ+ (ν_CO = 2128 cm⁻¹) and Pt²⁺ (ν_CO = 2149–2155 cm⁻¹). It was shown that the state of Pt depended on the Si/Al zeolite ratio, montmorillonite presence and Pt precursor. The use of H₂PtCl₆ as the precursor (impregnation) promoted stabilization of an oxidized Pt state, most likely Pt(OH)_xCl_y. When Pt(NH₃)₄Cl₂ (ion-exchange) was used, the Pt⁰ and hydroxo- or oxy-complexes Pt(OH)₆²⁻ or PtO₂ were formed. The addition of the Ca-montmorillonite favoured stabilization of Pt^+δ. The Cl⁻ ions inhibit reduction of oxidized Pt state to Pt particles. The Pt-zeolite catalyst demonstrated high efficiency in ultra-deep desulphurization of DLCO. The good catalyst performance in hydrogenation activity and sulphur resistance can be explained by the favourable pore space architecture and the location and the state of the Pt clusters. The bimodal texture of the developed zeolite substrates allows realizing a concept for design of sulphur-resistant noble metal hydrotreating catalyst proposed by Song [C. Song, Shape-Selective Catalysis, Chemicals Synthesis and Hydrocarbon Processing (ACS Symposium Series 738), Washington, 1999, p. 381; Chemtech 29(3) (1999) 26].     

Effect of impregnation sequence on performance of SiO2 supported Cu-Fe catalysts for higher alcohols synthesis from syngas

The effects of different impregnation sequences of copper and iron on the performance of Cu-Fe/SiO₂ catalysts for higher alcohols synthesis from syngas were investigated by N₂ adsorption, XRD, H₂-TPR, CO-IR, XPS, and CO hydrogenation reaction. The results indicate that the catalyst prepared by impregnation of support first with Fe and then with Cu exhibits the highest selectivity (36.1%) and space time yield (153.3 g·kg_cat^− 1·h^− 1) of alcohols. The CO conversion and alcohol selectivity of the catalysts was closely related to the content of surface Cu, and the ratio of surface contents of Cu to Fe, respectively.     

Hydrogenation of quinoline by ruthenium nanoparticles immobilized on poly(4-vinylpyridine)

A series of catalysts composed of ruthenium nanoparticles immobilized on poly(4-vinylpyridine) was prepared by NaBH₄ reduction of RuCl₃ · 3H₂O in methanol in the presence of the polymer; TEM measurements of a 10 wt% Ru/P4VPy material indicate that ruthenium particles of 1–2 nm predominate. This catalyst is efficient for the selective hydrogenation of quinoline to 1,2,3,4-tetrahydroquinoline at 100–120 °C and 30–40 bar H₂. The activity increases with hydrogen pressure up to 40 bar but is essentially independent of quinoline concentration. Polar solvents, triethylamine, and acetic acid enhance catalytic performance, suggesting an ionic mechanism involving heterolytic hydrogen activation.