Conversion of Triglycerides to Hydrocarbons Over Supported Metal Catalysts

The deoxygenation of triglycerides (tristearin, triolein and soybean oil) under nitrogen atmosphere was investigated over 20 wt% Ni/C, 5 wt% Pd/C and 1 wt% Pt/C catalysts. Use of the Ni catalyst resulted in near quantitative conversion of the triglyceride in each case, high yields of linear C5 to C17 alkanes and alkenes being obtained. Oxygen was rejected as CO and CO₂, while small amounts of light alkanes (C1–C4) and H₂ were also formed. ¹³C NMR spectroscopic analysis of the liquid product from soybean oil deoxygenation at intermediate reaction times suggested that one pathway for triglyceride deoxygenation involves liberation of fatty acids via C–O bond scission and concomitant H transfer, followed by elimination of CO₂ from the acids in a later step. Compared to Ni, catalysts containing Pd or Pt supported on activated carbon showed lower activity for both triglyceride deoxygenation and for cracking of the fatty acid chains.     

Stepwise Conversion of Methane over Supported Metal-Boron Amorphous Alloy Catalysts

The stepwise conversion of CH₄ to higher hydrocarbons over HMCM-22 zeolite supported metal-boron amorphous alloy catalysts has been investigated, including: (1) the influence of metals (Co, Ni, Pt, Rh and Ru) of the catalysts on the reaction; (2) the promotional effect of V on the catalytic behavior of the catalysts; (3) the influence of hydrogenation pressure and CH₄ decomposition temperature; and (4) the nature of carbon species. It is found that the yield of C⁺ ₂ hydrocarbons is strongly dependent on the metals. Good yields of C⁺ ₂ hydrocarbon are reached only on the supported NiB and CoB catalysts. The probability of C--C chain growth is increased by V promotion without seriously affecting the activities of CH₄ decomposition and hydrogenation. The ease of carbon removal via hydrogenation is strongly affected by the CH₄ decomposition temperature. Increasing hydrogenation temperature has a negative effect on the yield of C⁺ ₂ hydrocarbons. XPS measurements show that a carbide(-like) carbon species is active and selective for hydrogenation to produce higher hydrocarbons. Its activity/selectivity is greatly reduced at high CH₄ decomposition temperatures, mainly due to transition of the reactive carbidic to unreactive graphitic form. Graphite/filamental carbons were found to be formed at high CH₄ decomposition temperature.     

Sorbitol Hydrogenolysis Over Ni, Pt and Ru Supported on NaY

The hydrogenolysis of sorbitol into 1,2-propanediol (PD), ethylene glycol (EG) and glycerol (G) was investigated over Ni, Pt and Ru supported on NaY at 220 °C and 60 bar in a batch reactor. Ni(6 %)–NaY was investigated in detail at different process conditions, including its recyclability. Attempts have been made to rationalize the experimentally observed conversion and product selectivity obtained over the different catalysts with results of Density Functional Theory calculations of adsorption energy and bond length changes in sorbitol adsorbed over various planes of Ni, Pt and Ru.     

Tunability of Propane Conversion over Alumina Supported Pt and Rh Catalysts

Propane conversion over alumina supported Pt and Rh (1 wt% metals loading) was examined under fuel rich conditions (C₃H₈:O₂:He = 1:2.25:9) over the temperature range 450–650 °C. Morphological characteristics of the catalyst materials were varied by calcining at selected temperatures between 500 and 1,200 °C. X-ray diffraction and BET analysis showed the treatment generated catalyts metals with particle sizes in the range of <10 to >500 nm, and support surface areas in the range of 20–240 m²/g. Remarkably, both Rh and Pt yielded product compositions close to equilibrium values (with high H₂ and CO selectivity, complete oxygen conversion and almost complete propane conversion) so long as the metal particle size was sufficiently low, ≲10–15 nm. In cases where the particle size was large, primarily complete oxidation rather than partial oxidation products were observed, along with unreacted C₃H₈, indicative of a direct oxidation pathway in which gas-phase CO and H₂ are not present as intermediate species. It is proposed that the high resistance of Rh to coarsening is largely responsible for the observation of a higher selectivity of this material for syngas products when prepared by procedures similar to those for Pt. Overall, the tunability of the product composition obtained over Rh and Pt via processing steps has direct significance for the incorporation of such catalyts into the anodes of solid oxide fuel cells.     

Comparison of n-Dodecane Hydroisomerization Performance Over Pt Supported ZSM-48 and ZSM-22

ZSM-48 and ZSM-22 zeolites with similar Si/Al ratio were synthesized and modified by alkali treatment. Moreover, n-dodecane hydroisomerization performance of Pt supported ZSM-22 and ZSM-48 were investigated. The catalytic results showed that the activity and the isomers selectivity of n-dodecane hydroisomerization could be improved by alkali treatment. The isomers distributions were distinct for Pt/ZSM-48 and Pt/ZSM-22. Mono-branched isomers near the end of the chains were more prone to be generated on Pt/ZSM-22 catalyst, which suggested “pore-mouth” catalysis model dominating the hydroisomerization catalysis. However, di-branched isomers and mono-branched isomers with methyl near the middle of the carbon chains were favorable to be formed over Pt/ZSM-48 catalyst according to the “key-lock” catalysis model. Moreover, more central-branched isomers were formed at high reaction temperature (>?320 °C) especially for Pt/ HZSM-22.

Graphic Abstract

     

Complete Oxidation of Methane at Low Temperature over Pt Catalysts Supported on High Surface Area SnO2

The catalytic activity of Pt catalysts supported on high surface area tin(IV) oxide in the complete oxidation of CH₄ traces under lean conditions at low temperature was studied in the absence and in the presence of water (10 vol.%) or H₂S (100 vol.ppm). Their catalytic properties were compared to those of Pd/Al₂O₃ and Pt/Al₂O₃. In the absence of H₂S in the feed, Pt/SnO₂appears as a very promising catalyst for CH₄ oxidation, being even significantly more active under wet conditions than the best reference catalyst, Pd/Al₂O₃. Catalysts steamed-aged at 873 K were also studied in order to simulate long term ageing in real lean-burn NGV exhaust conditions. To this respect, Pt/SnO₂ is slightly less resistant than Pd/Al₂O₃. In the presence of H₂S, Pt/SnO₂catalysts are rapidly and almost completely poisoned, comparably to Pd/Al₂O₃and the catalytic activity is hardly restored upon oxidising treatment below 773 K. A synergetic effect between Pt and specific surface SnO₂sites active in CH₄oxidation is proposed to explain the superior catalytic behaviour of Pt/SnO₂.     

Pure H2 Production by Decomposition of Methane Over Ni Supported on Hydroxyapatite Catalysts

The catalytic decomposition of CH₄ for the production of pure H₂ is carried out over Ni supported on hydroxyapatite [Ca₅(PO₄)₃(OH)] catalysts at 650 °C and atmospheric pressure. CH₄ decomposition activity is decreased with time on stream and finally deactivated completely. The physicochemical properties of the fresh catalysts are characterized by XRD, DTA/TG, TPR and SEM techniques along with CHNS analyses of the used samples. It is found that the 30 wt% Ni/HAp displayed higher H₂ production rates over the other Ni loadings, which is correlated with Ni metal surface area measured by O₂ pulse chemisorption. IICT communication number: 051211.     

MnO2 Supported Pt Nanoparticels with High Electrocatalytic Activity for Oxygen Reduction Reaction

We report the hydrothermal synthesis of manganese dioxide (MnO₂) and its application as platinum nanoparticles (PtNPs) support for oxygen reduction reaction (ORR). The prepared MnO₂ samples with different hydrothermal reaction time were systematically investigated by X‐ray diffraction (XRD) and scanning electronic microscopy (SEM), conforming that the crystalline structure of samples was transferred from γ phase to β phase, and the morphology was changed from microspheres to nanorods, respectively. The ORR activity of the samples was evaluated by rotating ring‐disk electrode (RRDE) method and the optimized sample was further utilized as PtNPs support to form a new nanocomposite used as ORR catalyst. We show that the 1 wt.%Pt@MnO₂ has a promising performance toward the electrochemical catalytical reduction of oxygen, which an overall quasi 4‐electron transfer in ORR, as well as a limiting reduction current of 0.71 mA was achieved. In comparison with commercialized Pt@C and other Pt‐based catalysts, the MnO₂ supported PtNP exhibited remarkable mass activity (per unit mass of Pt), as high as 7.07 mA μg^–1, in alkaline solution. We demonstrate that the hydrothermal synthesized MnO₂ may offer useful applications as reliable, cost‐effective and morphology controllable support for PtNP as efficient ORR catalysts.     

Morphologic Control of Pt Supported Titanate Nanotubes and Their Photocatalytic Property

Morphologic control of Pt supported titanate nanotubes was attempted by the hydrothermal hot-pressing (HHP) technique in order to improve the handleability as a photocatalyst. The bulk of Pt-nanocrystal supported titanate nanotubes was successfully fabricated without the H₂ reduction process by applying the HHP technique. The bulky Pt-nanocrystal supported titanate nanotubes possessed dense microstructures, significantly sharp distributions of mesopores, and high Brunauer–Emmett–Teller (BET) surface area. Furthermore, the bulky Pt-nanocrystal supported titanate nanotubes showed the photocatalytic degradation activities of 2-propanol aqueous solution under UV-light irradiation.     

Direct Conversion of Levulinic Acid into Valeric Biofuels Using Pd Supported Over Zeolites as Catalysts

Topics in Catalysis - A series of Pd-based catalysts was prepared by incipient wetness impregnation over different acidic supports: amorphous SiO2-Al2O3, ZSM5 and beta zeolites. In addition to the...     

甲烷化炉超温原因分析及对策

大型合成氨装置设置甲烷化炉的主要目的是把进入合成工序的氢氮气中的CO、CO2除去,以防造成合成塔催化剂中毒,导致催化剂活性下降无法满足合成工序生产要求。甲烷化炉运行状况直接关系到后续系统的安全稳定运行。     

Direct Hydrogenolysis of Highly Concentrated Glycerol Solutions Over Supported Ru,Pd and Pt Catalyst Systems

Abstract  

The evaluation of supported precious metal catalysts, in combination with and without solid acids, for the hydrogenolysis of highly concentrated glycerol solutions, with the aim to produce lower alcohols, in particular 1-propanol was studied. GCMS analysis of the product mixtures obtained has shed some light on the possible mechanism leading to unwanted condensation products, as well as the composition of these compounds.     

Flame-made Alumina Supported Pd–Pt Nanoparticles: Structural Properties and Catalytic Behavior in Methane Combustion

Bimetallic palladium–platinum nanoparticles supported on alumina were prepared by flame spray pyrolysis. The as-prepared materials were characterized by scanning transmission electron microscopy (STEM), CO chemisorption, nitrogen adsorption (BET), X-ray diffraction (XRD), temperature programmed reduction (TPR), thermogravimetric analysis (TGA) and extended X-ray absorption fine structure (EXAFS) spectroscopy. The materials were tested for the catalytic combustion of methane with a focus on the thermal stability of the noble metal particles. After flame synthesis the noble metal components of the materials were predominantly in oxidized state and finely dispersed on the alumina matrix. Reduction afforded small bimetallic Pd–Pt alloy particles (< 5 nm) supported on Al₂O₃ ceramic nanoparticles. The addition of small amounts of platinum made the palladium particles more resistant against sintering at high temperatures and further lowered the deactivation observed during methane combustion.     

Methane Conversion to Synthesis Gas by Partial Oxidation and CO2 Reforming over Supported Platinum Catalysts

Partial oxidation of methane and reforming of methane with CO₂ were carried out with Pt/Al₂O₃, PtZrO₂ and Pt/CeO₂ catalysts, in the temperature range of 350–900 °C. For partial oxidation, the catalysts showed similar stabilities, with the PtZr slightly more active. The reaction occurs in two simultaneous stages: total combustion of methane and reforming of the unconverted methane with steam and CO₂, with the O₂ conversion of 100% over the whole temperature range. For reforming with CO₂, the catalysts presented similar activities, but with distinct deactivation rates: while the PtAl deactivates very fast at 800 °C, due to deposition of inactive carbon, the PtZr and PtCe catalysts offer higher resistance to coke formation, due to the metal-support interactions and the higher mobility of oxygen in the oxide lattice.     

甲烷催化燃烧用介孔ZrO2担载CuO催化剂

以介孔ZrO2为载体,采用湿式浸渍法制备了担载型铜基催化剂,以甲烷催化燃烧为模型反应考察了不同铜含量对催化剂结构和性能的影响,并采用N2吸附-脱附、程序升温还原 (TPR) 和X射线衍射 (XRD)等技术对催化剂进行了表征.结果显示CuO/ZrO2催化剂具有优良的甲烷催化燃烧性能;铜含量为5%质量分率的催化剂表现出最好的低温催化活性和优良的稳定性,甲烷转化率达到90 %时对应的反应温度 (T90) 低至358 ℃;若铜含量继续增加,活性组分CuO会发生聚集,导致催化剂的低温活性降低.