Tamás Kasza

Production of Bio Gas Oil from Bioparaffins over Pt/sapo-11

In this paper a new field of the application of Pt/SAPO-11 catalyst is introduced. The isomerization of C12-C20 paraffin mixtures produced from rapeseed oil was investigated over different platinum containing (0.2; 0.3; 0.4; 0.5; 0.7; 1.0 %) SAPO-11 catalysts at 300-400°C, 30-80 bar; 0.5-4.0 h -1 LHSV and 200-800 Nm 3 /m 3 H2/HC ratio. It was concluded that economically the most favourable results (high isomer content at high yield) could be obtained using SAPO-11 catalyst with 0.4 % platinum content. At the favourable operational parameters (determined in compromise by the product yield, the ratio of monoand multibarched paraffins, the place of branchings) (T= 360 °C; p=5060 bar; LHSV 1.0-1.5 h -1 , H2/HC = 350 Nm 3 /m 3 ) high isoparaffin containing mixtures were produced with high liquid yield (>90%) and high i-C12 i-C20 selectivity. The cetane numbers of these products were 75-85 units (EU Standard value is ≥51), and the cold filter plugging points were between -2 and -11 °C.

ISOMERIZATION OF PARAFFIN MIXTURES PRODUCED FROM SUNFLOWER OIL

The importance of biofuels becomes more acute, especially in the European Union. Beside them, the bio gas oil is a promising product that is a fuel with high isoparaffin content in the gas oil boiling range, which can be produced by the catalytic hydrogenation of different triglycerides. In this paper the isomerization of different intermediate products obtained over different hydrogenation catalysts and having high n-paraffin content was studied on SAPO-11 catalyst at 300–380 °C temperature, 20–80 bar pressure, 0.5–3.0 h-1 of liquid space velocity and 400 Nm3/m3 of H2/feed ratio. It was found that the oxygen containing intermediate products significantly changed the degree ofisomerization, but the hydrocarbon composition and the aromatic content of the n-paraffin mixtures had no noticeable effect on the conversion. During the experiments excellent quality diesel gas oil blending components were produced with high i-paraffin content and they were practically free of heteroatom content.

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.

APPLICATION OF IMPROVED BIO-PARAFFINS IN DIESEL FUELS

Bio-paraffin containing mixtures produced from different natural triglycerides (conventional and improved vegetable oils, used cooking oils and fats, etc.) have high cetane number (95-105 units), but their freezing points are high (between +15 and +32°C). This property can be improved by catalytic hydroisomerization. Products obtained over 0.5% Pt/SAPO-11 catalysts (T = 280–380°C; P = 20–80 bar; LHSV = 0.25–4.0 h-1; apparent contact time: between 1/3 and 4.0 h (at LHSV = 3.0 h-1; H2/feedstock = 400 Nm3/m3) had CFPP values of +5°C; -20°C and -32°C. At the same time, there was decreased cetane number of the isomerates (87, 70 and 65 unit, respectively) relative to the feedstock. These biogasoils are suitable for bio-components of premium quality diesel fuel or for the improvement of cetane number. They can also reduce the density of low grade components providing some economic savings and some flexibility to refineries.

Investigation of the Heterogeneous Catalytic Transformation of Vegetable Oil/Gas Oil Blends

The applicability of vegetable oils (tryglycerides) and their derivates is well-known for a long time. The main goal (to produce fuels from non-fossil based energy source) has been extended with the global aims of reducing the environmental pollution. Therefore the main objective now is to produce, store, transport and use fuels with lower emission levels. Until the last couple of years the vegetable oils were mostly transesterified catalytically to biodiesel to produce fuels. Because of the numerous disadvantages of biodiesel production and application the alternative chemical transformations of triglycerides were started to be studied intensively. One of the best alternative is to convert the vegetable oils (or other materials containing triglycerides) and/or their blends with gas oil to hydrocarbons rich in paraffins. These compounds can be applied in Diesel-engines directly or blended with petroleum-based gas oil. In our experimental work we examined the heterogeneous catalytic conversion of light gas oil fraction containing 10% sunflower oil on transition metal/Al2O3 catalyst. Our objective was to study the effect of the operating parameters to the yield of liquid organic products, to the yield of the fraction of gas oil boiling point range and to the product properties. Based on our results it can be concluded that with the catalytic hydrogenation of the feedstock containing 10% sunflower oil products with excellent properties can be produced with high yield. The product gas oil had ³10 mg/kg sulphur and nitrogen content, lower than 10% total aromatic content and ³-5 °C cold filter plugging point. The cetane number of the products was significantly higher than the limit (51) of the EN 590:2004 standard.

Production of Bio-Isoparaffins by Hydroisomerisation of Bioparaffins

The importance of biofuels becomes more acute, especially in the European Union. Beside them, those second generation products are spreading increasingly which have better product and performance properties relative to the first generation biofuels. The bio gas oil is a promising product that is a fuel with high isoparaffin content in the gas oil boiling range, which can be produced by the catalytic hydrogenation of different triglycerides. In this paper the isomerisation of an intermediate product with high n-paraffin content was studied on SAPO-11 catalyst at 300–360 °C temperature, 20–40 bar pressure, 1.0–3.0 liquid space velocity and 400 Nm3/m3 H2/feed ratio. During the experiments we succeeded to produce an excellent quality diesel gas oil blending component with high i-paraffin content which is practically free of heteroatom content. This product satisfies with some addition all the requirements of the European diesel fuel standard.