Search results for: oxygenates

Authors: Ahmed Aboforn

Abstract:

Butene-1 product is consider effectively raw material in Polyethylene production, however Oxygenates impurities existing will be effected ethylene/butene-1 copolymers synthesized through titanium-magnesium-supported Ziegler-Natta catalysts. Laterally, Petrochemical industries are challenge against poor quality of Butene-1 and other C4 mix – feedstock that reflected on business impact and production losing. In addition, propylene product suffering from contamination by oxygenates components and causing for lose production and plant upset of Polypropylene process plants. However, Multidimensional gas chromatography (MDGC) innovative analytical methodology is a chromatography technique used to separate complex samples, as mixing different functional group as Hydrocarbon and oxygenates compounds and have similar retention factors, by running the eluent through two or more columns instead of the customary single column. This analytical study striving to enhance the quality of Oxygenates analytical method, as monitoring the concentration of oxygenates with accurate and precise analytical method by utilizing multidimensional GC supported by Backflush technique and Flame Ionization Detector, which have high performance separation of hydrocarbon and Oxygenates; also improving the minimum detection limits (MDL) to detect the concentration <1.0 ppm. However different types of oxygenates as (Alcohols, Aldehyde, Ketones, Ester and Ether) may be determined in other Hydrocarbon streams asC3, C4-mix, until C12 mixture, supported by liquid injection auto-sampler.

Keywords: analytical chemistry, gas chromatography, petrochemicals, oxygenates

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Authors: Jianli Chang, Yusheng Zhang, Yali Yao, Diane Hildebrandt, Xinying Liu

Abstract:

The influence of feed-gas ratio on the ethene hydroformylation over an Rh-Co bimetallic catalyst supported by reduced graphene oxide (RGO) has been investigated in a tubular fixed bed reactor. Argon was used as balance gas when the feed-gas ratio was changed, which can keep the partial pressure of the other two kinds of gas constant while the ratio of one component in feed-gas was changed. First, the effect of single-component gas ratio on the performance of ethene hydroformylation was studied one by one (H₂, C₂H₄ and CO). Then an optimized ratio was found to obtain a high selectivity to C₃ oxygenates. The results showed that: (1) 0.5%Rh-20%Co/RGO is a promising heterogeneous catalyst for ethene hydroformylation. (2) H₂ and CO have a more significant influence than C₂H₄ on selectivity to oxygenates. (3) A lower H₂ ratio and a higher CO ratio in feed-gas can lead to a higher selectivity to oxygenates. (4) The highest selectivity to oxygenates, 61.70%, was obtained at the feed-gas ratio CO: C₂H₄: H₂ = 4: 2: 1.

Keywords: ethene hydroformylation, reduced graphene oxide, rhodium cobalt bimetallic catalyst, the effect of feed-gas ratio

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Authors: Ala’a H. Al-Muhtaseb, Farrukh Jamil, Sandeep K. Saxena

Abstract:

The fast growth rate of energy consumption along with world population expected to demand 50% more energy by 2030 than nowadays. At present, the energy demand is mostly provided by limited fossil fuel sources such as oil, natural gas, and coal that are resulting in dramatic increase in CO2 emissions from combustion of fossil fuels. The growth of the biodiesel industry over the last decade has resulted in a price drop because glycerol is obtained as a by-product during transesterification of vegetable oil or animal fats, which accounts for one tenth of every gallon of biodiesel produced. The production of oxygenates from glycerol gains much importance due to the excellent diesel-blending property of the oxygenates that not only improve the quality of the fuel but also increases the overall yield of the biodiesel in helping to meet the target for energy production from renewable sources for transport in the energy utilization directives. The reaction of bio-glycerol with bio-acetone was carried out in a magnetically stirred two necked round bottom flaskS. Condensation of bio-glycerol with acetone in the presence of various modified forms of beta zeolite has been done for synthesizing solketal (AB-2 modified with nitric acid, AB-3 modified with oxalic acid). Among all modified forms of beta zeolite, AB-2 showed the best performance for maximum glycerol conversion 94.26 % with 94.21 % solketal selectivity and minimum acetal formation 0.05 %. The physiochemical properties of parent beta zeolite and all its modified forms were analyzed by XRD, SEM, TEM, BET, FTIR and TPD. It has been revealed that AB-2 catalysts with high pore volume and surface area gave high glycerol conversion with maximum solketal selectivity. Despite this, the crystallinity of AB-3 was lower than AB-2 which helps to provide the shorter path length for reactants and product but due high pore volume AB-2 was preferred which gave maximum bio-glycerol conversion. Temperature does matter the glycerol conversion and selectivity of solketal, as it increases from 40 ºC to 60 ºC the conversion of glycerol rises from 80.04 % to 94.26 % and selectivity of solketal from 80.0 % to 94.21 % but further increase in temperature to 100 ºC glycerol conversion reduced to 93.06 % and solketal selectivity to 92.08 %. AB-2 was found to be highly stable as up to 4 repeated experimental runs there was less than 10% decrease in its activity. This process offers an attractive route for converting bio-glycerol, the main by-product of biodiesel to solketal with bio-acetone; a value-added green product with potential industrial applications as a valuable green fuel additive or combustion promoter for gasoline/diesel engines.

Keywords: beta-zeolite, bio-glycerol, catalyst, solketal

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Authors: Sanjay P. Gandhi, Sanjay S. Patel

Abstract:

Dry (CO2) reforming of methane (DRM) is both scientific and industrial importance. In recent decades, CO2 utilization has become increasingly important in view of the escalating global warming phenomenon. This reaction produces syngas that can be used to produce a wide range of products, such as higher alkanes and oxygenates by means of Fischer–Tropsch synthesis. DRM is inevitably accompanied by deactivation due to carbon deposition. DRM is also a highly endothermic reaction and requires operating temperatures of 800–1000 °C to attain high equilibrium conversion of CH4 and CO2 to H2 and CO and to minimize the thermodynamic driving force for carbon deposition. The catalysts used are often composed of transition Methods like Nickel, supported on metallic and non-metallic oxides such as alumina and silica. However, many of these catalysts undergo severe deactivation due to carbon deposition. Noble metals have also been studied and are typically found to be much more resistant to carbon deposition than Ni catalysts, but are generally uneconomical. Noble metals can also be used to promote the Ni catalysts in order to increase their resistance to deactivation. In order to design catalysts that minimize deactivation, it is necessary to understand the elementary steps involved in the activation and conversion of CH4 and CO2. CO2 reforming methane over promoted catalyst was studied. The influence of ZrO2, CeO2 and the behavior of Ni-Al2O3 Catalyst, prepare by wet-impregnation and Co-precipitated method was studied. XRD, BET Analysis for different promoted and unprompted Catalyst was studied.

Keywords: CO2 reforming of methane, Ni catalyst, promoted and unprompted catalyst, effect of catalyst preparation

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Authors: Saidulu Gadari, Manoj Kumar Yadav, V. K. Satheesh, Debasis Bhattacharyya, S. S. V. Ramakumar, Subhajit Sarkar

Abstract:

Most Fluid Catalytic Cracking Units (FCCUs) are big profit makers and hence, always operated with several constraints. It is the primary source for production of gasoline, light olefins as petrochemical feedstocks, feedstock for alkylate & oxygenates, LPG, etc. in a refinery. Increasing unit capacity and improving product yields as well as qualities such as gasoline RON have dramatic impact on the refinery economics. FCCUs are often debottlenecked significantly beyond their original design capacities. Depending upon the unit configuration, operating conditions, and feedstock quality, the FCC unit can have a variety of bottlenecks. While some of these are aimed to increase the feed rate, improve the conversion, etc., the others are aimed to improve the reliability of the equipment or overall unit. Apart from investment cost, the other factors considered generally while evaluating the debottlenecking options are shutdown days, faster payback, risk on investment, etc. A low-cost solution such as replacement of feed injectors, air distributor, steam distributors, spent catalyst distributor, efficient cyclone system, etc. are the preferred way of upgrading FCCU. It also has lower lead time from idea inception to implementation. This paper discusses various bottlenecks generally encountered in FCCU and presents a case study on improvement of performance of one of the FCCUs in IndianOil through implementation of cost-effective technical solution including use of improved internals in Reactor-Regeneration (R-R) section. After implementation reduction in regenerator air, gas superficial velocity in regenerator and cyclone velocities by about 10% and improvement of CLO yield from 10 to 6 wt% have been achieved. By ensuring proper pressure balance and optimum immersion of cyclone dipleg in the standpipe, frequent formation of perforations in regenerator cyclones could be addressed which in turn improved the unit on-stream factor.

Keywords: FCC, low-cost, revamp, debottleneck, internals, distributors, cyclone, dipleg

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Authors: Lotanna Ezeonu, Jason P. Robbins, Ziyu Tang, Xiaofang Yang, Bruce E. Koel, Simon G. Podkolzin

Abstract:

The interaction of organic molecules with metal surfaces is of interest in numerous technological applications, such as catalysis, bone replacement, and biosensors. Acetic acid is one of the main products of bio-oils produced from the pyrolysis of hemicellulosic feedstocks. However, their high oxygen content makes them unsuitable for use as fuels. Hydrodeoxygenation is a proven technique for catalytic deoxygenation of bio-oils. An understanding of the energetics and control of the bond-breaking sequences of biomass-derived oxygenates on metal surfaces will enable a guided optimization of existing catalysts and the development of more active/selective processes for biomass transformations to fuels. Such investigations have been carried out with the aid of ultrahigh vacuum and its concomitant techniques. The high catalytic activity of platinum in biomass-derived oxygenate transformations has sparked a lot of interest. We herein exploit infrared reflection absorption spectroscopy(IRAS), temperature-programmed desorption(TPD), and density functional theory(DFT) to study the adsorption and decomposition of acetic acid on a Pt(111) surface, which was then compared with Ni(111), a model non-noble metal. We found that acetic acid adsorbs molecularly on the Pt(111) surface, interacting through the lone pair of electrons of one oxygen atomat 90 K. At 140 K, the molecular form is still predominant, with some dissociative adsorption (in the form of acetate and hydrogen). Annealing to 193 K led to complete dehydrogenation of molecular acetic acid species leaving adsorbed acetate. At 440 K, decomposition of the acetate species occurs via decarbonylation and decarboxylation as evidenced by desorption peaks for H₂,CO, CO₂ and CHX fragments (x=1, 2) in theTPD.The assignments for the experimental IR peaks were made using visualization of the DFT-calculated vibrational modes. The results showed that acetate adsorbs in a bridged bidentate (μ²η²(O,O)) configuration. The coexistence of linear and bridge bonded CO was also predicted by the DFT results. Similar molecular acid adsorption energy was predicted in the case of Ni(111) whereas a significant difference was found for acetate adsorption.

Keywords: acetic acid, platinum, nickel, infared-absorption spectrocopy, temperature programmed desorption, density functional theory

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