Jenő Hancsók

Fuel purpose hydrotreating of sunflower oil on CoMo/Al2O3 catalyst

The importance of the economical production and usage of new generation biofuels, the so-called bio gas oil (paraffins from triglycerides) and the results of the investigation for their productability on the CoMo/Al(2)O(3) catalyst, which was activated by reduction, are presented. The conversion of triglycerides, the yield of total organic fractions and the target product, furthermore the type and ratio of deoxygenation reactions were determined as a function of process parameters. The advantageous process parameters were found (380 degrees C, 40-60 bar, 500-600 Nm(3)/m(3) H(2)/sunflower oil ratio, 1.0 h(-1)), where the conversion of triglycerides was 100% and the yield of the target fraction [high paraffin containing (>99%) gas oil boiling range product] was relatively high (73.7-73.9%). The deoxygenation of triglycerides the reduction as well as the decarboxylation/decarbonylation reactions took place. The yield of the target fractions did not achieve the theoretical values (81.4-86.5%). That is why it is necessary to separate the target fraction and recirculate the heavy fraction.

Oligomerisation of isobutene with silica supported ionic liquid catalysts

Bronsted acidic ionic liquids, supported on silica gel, have been used effectively in oligomerisation of isobutene. The supported catalysts could be used several times without loss of activity or change in selectivity. The ratio of the products could be influenced by the proper choice of the ionic liquid component of the catalyst and the reaction temperature.

Bio gas oil production from waste lard

Besides the second generations bio fuels, one of the most promising products is the bio gas oil, which is a high iso-paraffin containing fuel, which could be produced by the catalytic hydrogenation of different triglycerides. To broaden the feedstock of the bio gas oil the catalytic hydrogenation of waste lard over sulphided NiMo/Al2O3 catalyst, and as the second step, the isomerization of the produced normal paraffin rich mixture (intermediate product) over Pt/SAPO-11 catalyst was investigated. It was found that both the hydrogenation and the decarboxylation/decarbonylation oxygen removing reactions took place but their ratio depended on the process parameters (T = 280–380°C, P = 20–80 bar, LHSV = 0.75–3.0 h−1 and H2/lard ratio: 600 Nm3/m3). In case of the isomerization at the favourable process parameters (T = 360–370°C, P = 40 –50 bar, LHSV = 1.0 h−1 and H2/hydrocarbon ratio: 400 Nm3/m3) mainly mono-branching isoparaffins were obtained. The obtained products are excellent Diesel fuel blending components, which are practically free of heteroatoms.

Investigation of the Oligomerization of Light Olefins on Ion Exchange Resin Catalyst

The requirements against the quality of motor fuels were rendered more rigorous in the past decade; the most important ones were the major reductions of the sulphur and aromatic content. Besides the changing of the regulation of the motor fuels, the harmful material emission of the Otto- and Diesel-engine built vehicles was also limited significantly. These effects make necessary the greater use of the environmentally friendly, relatively “clean burning”, technically heteroatom- and aromatic free, great n- and i-paraffinic containing blending components in the case of gasoline and diesel gas oils. During our experimental work we studied the possibilities of producing motor fuel blending components like these blending components with the oligomerization of the olefin content of light FCC-naphtha – assuming later industrial application – on Amberlyst-15 acidic ion exchange resin type catalyst. This topic is very important in a modern oil refinery, because different isoparaffin-rich motor fuel blending components can be produced (depending on the catalyst and the process parameters), and this technology can grow considerably the gasoline- and diesel gas oil flexibility of the oil refinery, too. The aim of our experiments was to produce motor fuel blending components with the oligomerization of C4-C6 olefins in light FCC-naphtha matrix. Working on the acidic ion exchange resin catalyst under different process parameters (T: 80–130 °C, P: 15–30 bar, LHSV: 0.5–3.0 h-1) we determined that in the studied process parameter range in preferable case (T: 100–110 °C, P: 25–30 bar, LHSV 0.5–1.0 h-1) the liquid product yield was: greater than 95%, the conversion of olefins: 90–92%, the selectivity of C8-C11: 70–76%, while the selectivity of C12+: 24–30%.

Benzene saturating isomerization

A new field of catalytic application of H-mordenite is shown for manufacturing gasoline blending components of high octane number and free of benzene in order to satisfy environmental and human health regulations. Experiments were carried out with catalysts containing 0.3–0.5 % platinum on the zeolite and alumina. Light gasoline fractions containing 0–4.9 % benzene, 9.6–10.3 % C6-cycloalkanes, in excess C6-paraffins (that is the precursors of benzene in naphtha reforming process) were converted at 220–280 °C, 30–40 bar, 0.8–3 1/h liquid hourly space velocity with hydrogen/hydrocarbon mole ratio 1:1–2:1. On the investigated catalysts beside significant skeletal isomerization of n-hexane practically the total amount of benzene was hydrogenated under favourable conditions determined by the kinetics and thermodynamic equilibrium of transformations. Most of the products are excellent gasoline blending components free of benzene.

PROPERTIES OF DIESEL-ALCOHOL BLENDS

Fuels from renewable sources such as biodiesel or bioalchohols are getting more attention also as blending components to fossil fuels and because of their less environmental impact. Stability and physico-chemical properties of different diesel-alcohol blends were investigated by different composition. The solubility properties of the alcohols are mainly dependent on the carbon chain length of the alcohol, their water content, additives, temperature and also on the hydrocarbon composition of the diesel fuel. Bio-butanol has better physic-chemical properties than bio-ethanol and its blends with diesel fuel have proper parameters, like Cold Filter Plugging Point and High Frequency Reciprocating Rig lubricity are close to those of the base diesel fuel.

Hydrotreating of gasoils on bimetallic catalysts: effect of the composition of the feeds

Hydrodearomatizing (HDA) and hydrodesulfurizing (HDS) activities as well as sulfur tolerance of Pt(0.3%)-Pd(0.6%) bimetallic catalyst supported on USY, SiO 2 -Al 2 O 3 and Al 2 O 3 were investigated. Gasoils containing 29.7% aromatics/5ppm sulfur, 31.8% aromatics/158 ppm sulfur and 32.5% aromatics/283 ppm sulfur were used as feeds. The results of experiments obtained under various conditions showed that introducing practically sulfur-free feed every investigated catalyst provided relatively high HDA activities. Applying gasoils of higher sulfur content resulted in decrease of HDA activities depending on the type of catalyst. Pd-Pt/USY provides the highest sulfur tolerance because it preserved the activity, even for gasoil having 283 ppm sulfur content. Additionally, Pd-Pt/USY provided higher HDS activity than the Pt-Pd/SiO 2 -Al 2 O 3 under every process condition applied.

INVESTIGATION OF CATALYTIC CONVERSION OF FISCHER-TROPSCH WAX ON Pt/AlSBA-15 AND Pt/BETA ZEOLITE CATALYSTS

Because of the more serious problems with the environment (e.g. greenhouse effect) and the crude oil supply (e.g. import dependence) the use of fuels and lubricants produced from renewable feedstocks have come to the front nowadays. The Fischer-Tropsch wax (60–80% of the Fischer-Tropsch products) which is produced on synthesis gas from different sources (biological or waste), is a mixture of high molecular weight (C20-C60) n-paraffins, which are in solid state (high pour point) at normal conditions. The products (fuels and base oils) which can be produced from this paraffin mixture have high quality and have fewer negative effects on the environment (practically zero sulphur- and nitrogen content, low aromatic content, excellent application properties) thus theydo not demand changes in the fuel supply infrastructure and in the engine constructions. The isomerization of high molecular weight n-paraffins can be effectively carried out on bifunctional catalysts. There are only a few indications about the application of metal catalysts on mesoporous carrier in the literature. Consequently our objective was to investigate some Pt/AlSBA-15 (SBA: Santa Barbara Amorphous) catalysts which have not been investigated in detail in this reaction system yet, and compare its properties with a Pt/beta zeolite catalyst which has been recommended for this reaction earlier. The applicability and catalytic activity of Pt/AlSBA-15 and Pt/beta zeolite catalysts of 0.5% platinum content for the selective isomerization of Fischer-Tropsch wax was investigated in the present experiment. The experiments werecarried out in a high-pressure microreactor system in continuous operation and on a catalyst with steady-state activity. The main properties of the feedstock which was a mixture of paraffin produced by Fischer-Tropsch synthesis (the synthesis gas was produced from biomass) were: n-paraffin content (C18-C57): 97.4%, sulphur content: 5 mg/kg, pour point: 72 °C. In the experiment the following process parameters were applied: T=275–375 °C, P=40–80 bar, LHSV=1.0–3.0 h-1, H2/hydrocarbon ratio: 400–800 Nm3/m3. The composition of the products was determined by gas chromatography. From the catalysts with different support the best results were gained on the catalysts with AlSBA-15 support, and with increasing temperature the yield of liquid products (C5+) decreased, but until 325 °C this value was above 93% in every case. Incase of the beta zeolite high amount of cracking took place. Increasing the pressure shifted back the hydrocracking reactions(with the increasing number of moles) so it had a decreasing effect on the volume of the gas products and the lower contact time (higher liquid hour space velocity) had the same effect. In the gas products mainly branched isobutane was identified, which indicated that the cracking enacted partly after the isomerization reactions. The isoparaffin contents of the liquid products in the function of process parameters increased with increasing temperature and decreased with increasing pressure and LHSV in every case while other parameters were kept constant. Based on the isoparaffin contents of the different fractions it can be concluded that on Pt/AlSBA-15 catalyst at advantageous process parameter combinations (T=300–325 °C (C11-C20)/ 275–300 °C (C21-C30), P=40–80 bar, LHSV=1.0–2.0 h-1) the catalyst was applicable to produce C11-C20 and C21-C30 fractions with high isoparaffin content (63.5–85.6% and 34.1–58.7%) with adequate yields (29.9–36.6% and 46.2–58.8%). We experienced that the gas oil fractions having the lowest pour point were obtained in the case of high concentrations of 5-methyl isomers. The C21-C30 fraction is a high viscosity index (VI ≥125) base oil. The selectivity of the target product fractions was high, and based on these facts the selective isomerization of the Fischer-Tropsch wax can be a new application area of the Pt/AlSBA-15 catalyst.

Investigation of the Hydroconversion of Lard and Lard-Gas Oil Mixture on PtPd/USY Catalyst

The necessity to maintain mobility and the increasing energy- and environmentally sound demands necessitated the research, development and utilization of engine fuels from renewable resources. Because of the negative features of the already and generally applied bio-derived Diesel fuel, the biodiesel, it was necessary to research and develop other chemical processes that convert triglycerides through different reaction ways. These second generation bio-fuels are the bio gas oils, which are mixtures of n- and i-paraffins. Otherwise these hydrocarbons are the choice components of the fossil derived Diesel fuels. During the experimental work our aim was to investigate the heterogeneous catalytic hydrogenation of waste lard – as a renewable agro-derived feedstock – and by mixing it to deep desulphurized gas oil stream, respectively on PtPd/USY catalyst. In the course of it, we studied the effects of the process parameters (temperature: 300–380 °C, pressure 40-60-80 bar, LHSV: 0.75–1.25 h-1, H2/feedstock rate: 600 Nm3/m3) on the quality and quantity of the products. We determined that during the co-processing of lard and desulphurized gas oil, the saturation of the aromatic content and the deoxygenation of the triglyceride part of the feedstock -isoparaffins formed - took place, respectively and at process temperatures (360–380 °C) found to be favourable by us, excellent, bio-component containing and significantly dearomatized diesel fuel blending components could be obtained. These products meet the valid diesel gas oil standard EN 590:2009+A1:2010, except for their cold flow properties.

Simultaneous desulphurization, isomerization and benzene saturation of n-hexane fraction on Pt-H/MOR

A new field of the catalytic application of Pt/H-MOR catalysts is presented for simultaneous HDS, isomerization and benzene saturation of n -hexane fractions. The ctalysts containing 0.3–0.75 wt% Pt were prepared from dealuminated H-MOR (Si/Al=20.5–22.4; Pt-dispersion 81–95%; acidity 0.74–0.9 meq NH 3 /g) by ion exchange with [Pt(NH 3 ) 4 ]Cl 2 . n-C 6 fractions containing 6 isomers, up to 85 ppm sulphur (mainly C 2 H 5 SH and C 3 H 7 SH) and 0–4.9% benzene were converted at temperatures 220–280°C, pressures 25–40 bar, H 2 /hydrocarbon ratios 1:1-2:1, liquid hourly space velocities 0.75–3.0 h −1 . H-MOR catalysts of 0.4%–0.5% Pt content are the most suitable for HDS, benzene saturation and isomerization in a single step. Under optimal process conditions the products are practically free of benzene and sulphur and are excellent gasoline blending components.