Péter Baladincz

Co-processing of FCC Light Cycle Oil and Waste Animal Fats with Straight Run Gas Oil Fraction

In the European Union the demand for middle distillates is growing, while a decrease in gasoline demand can be observed. Even the most complex refineries are not able to produce the economic yield distribution from the processed crude oil which constantly meets the changing market demand. The growing need for gasoil can be more and more exclusively satisfied by using unconventional feedstocks, such as biooriginated resources and less valuable refinery streams. The possibilities of quality upgrade of mixtures containing straight run gasoil, light cycle oil and waste animal grease in different ratios were examined during the series of experiments. The effects of the main reaction conditions (temperature: 300 380 °C, pressure: 40 70 bar, liquid hourly space velocity (LHSV): 0.75 -3.0 h -1 H2/feed ratio: 600 Nm 3 /m 3 ) on the quality and quantity of products were studied. A favourable reaction parameter combination was chosen to reach the total conversion of triglycerides into alkanes, the saturation of significant part of the aromatic compounds and the desulphurization of straight run gas oil took place. The high cetane number of alkanes, produced during the conversion of triglycerides, compensate the low cetane number of products from the saturation of aromatic components.

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.

Production of Bio Gas Oil Containing Diesel Fuel with Upgraded Cold Flow Properties by Co-processing

The aim of our experimental work was to investigate the applicability of a catalyst bed compiled of various compositions of hydrogenation catalysts to produce bio-component containing diesel fuel by co-processing of gas oil with vegetable oil. We investigated the heterogeneous catalytic transformability of gas oil fractions with 0, 5, 15, 25 % sunflower oil content at 50-80 bar pressure, 300380°C temperature (LHSV = 0.75-3.0 h -1 and H2/HC ratio 600 Nm 3 /m 3 ) on catalyst systems containing only the main catalyst and the three catalyst layers as well. In case of both catalytic systems and under the favourable operational conditions (360 380 °C, P = 80 bar, LHSV = 0.75-1.0 h -1 , H2/HC=600 Nm 3 /m 3 ) the main properties of the high-yield products made from maximum 0-15 % vegetable oil containing feedstocks satisfy the requirements of standard EN 590:2009+A1:2010. The amount of vegetable oil higher than 15 % reduced the desulphurisation efficiency. By using the catalyst bed prepared of the three catalysts products with CFPP value reduced by 3-4 °C could be produced as in case of using only the main catalyst.

Production of diesel fuel via hydrogenation of rancid lard and gas oil mixtures

For the second generation bio-fuels the most promising product mixtures are the bio gas oils and diesel fuels containing bio gas oils. These products are in the gas oil boiling point range and made by catalytic hydrogenation of pure triglycerides or triglyceride-gas oil mixtures. The bio gas oil product is a mixture of n- and i-paraffins. During the experimental work our aim was to investigate the heterogeneous catalytic hydrogenation of rancid lard and its 50% mixtures of gas oil fraction on sulphided CoMo/Al2O3 catalyst. During a series of experiments we studied the effects of the different feedstocks (lard content of 50-100%) and the process parameters (temperature: 300-380 °C, pressure 40-80 bar, LHSV: 1.0-2.0 h -1 , H2/feedstock rate: 600 Nm 3 /m 3 ) on the yield and quality of the products. We assessed that in the course of the heterogeneous catalytic hydrogenation the deoxygenation of the triglyceride part of the feedstock occurred while the removal of the sulphur and nitrogen content and the saturation of the aromatic content took place with a high degree as well. In the course of the experiments we managed to make excellent quality products, which are suitable for the use in Diesel-engines.

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.

Expanding Feedstock Supplies of the Second Generation Bio-Fuels of Diesel-Engines

Nowadays the first generation bio-fuels are already introduced in the European Union and amongst them the one used in Diesel-engines is the triglyceride containing feedstock derived product, the so-called biodiesel. However these fatty-acid-methyl-esters have multiple disadvantages (e.g.: poor oxidation and heat stability, lower energy content than the fossil derived diesel fuels, etc.) because of their chemical structure. Therefore it has become necessary to develop new bio-derived fuels on triglyceride supply, with other chemical structure. These bio-derived fuels are the second generation bio-fuels and amongst them the most promising product is the bio gas oil. The bio gas oil is a mixture of n- and i-paraffins (these are the primal components of the fossil diesel fuels also) in the gas oil boiling point range made from triglyceride containing feedstock. To ensure the eligible quantity and quality of bio gas oils, it is necessary to examine the utilization of other feedstocks with high triglyceride content. The European Union also urges the expanding of the feedstock supplies of the bio-derived motor fuels [COM(2006)34]. During our experimental work we examined the possibilities of the catalytic hydrogenation of mixtures of gas oil and lard or vegetable oil respectively, on NiMo/Al2O3 catalyst. Besides the examination of the reaction parameters (temperature: 360 °C, pressure: 80 bar, LHSV: 1.0 h-1 , H2/feedstock ratio: 600 Nm3/m3) which were found to be congenial for the catalytic conversion of vegetable oils for the conversion of the different, respectively lard or vegetable oil containing (0–10–20–30–50–100%) gas oil feedstocks we investigated the convertibility of the triglyceride part and the effect of the feedstock on the quality and the quantity of the product, furthermore the effect of the triglyceride in the feedstock on the desulphurisation, denitrification and dearomatisation. We determined that in the case of respectively 10% vegetable oil or lard containing feedstocks, the product was already an excellent bio-constituent containing diesel fuel blending component.

Fuel Production from Triglycerides Containing Gas Oils

Lately the development and the use of energy sources which are of bio-origin are required. The engine fuels have special importance. Based on their origin they can be conventional, alternative or conventional + alternative. Biofuels which can be produced from biomass, thus from a renewable energy source, are alternative fuels. The objective of our research work was to investigate the production of diesel fuel with excellent quality and/or of diesel fuel blending component by heterogeneous catalytic conversion of gas oil fraction containing 75% sunflower oil. Furthermore, our aim was to determine the advantageous process parameters (temperature, pressure, liquid hourly space velocity, hydrogen/hydrocarbon ratio) during application of the selected NiMo/Al2O3 catalyst. Based on the results obtained we determined that the main properties of these products were significantly better compared to the feed as diesel fuel components. The products which were made under desired combination of process parameters (T=350–380 °C; p=80 bar; LHSV=1.0–1.5 h-1; H2/feed ratio: 600 Nm3/m3) had lower than 10 mg/kg sulphur and nitrogen content, and the cetane numbers were significantly higher than it is specified in the MSZ EN 590:2009 standard (minimum 51).

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.

Production of Gas Oil Components from Waste Fats

The modern-minded man has discovered that it is necessary to substitute a part of the fossil-derived energy sources with renewable energy sources to cover the energy demand of mobility, which sustains and accelerates the human society and economy. Nowadays, the transportation sector tries to achieve this through the development and utilisation of bio-derived motor fuels. In terms of Diesel-engines the biodiesel has been utilized in great volumes already, which is made from triglycerides via esterification (fatty-acid-methyl-ester, FAME). The FAME or biodiesel, due to its molecular structure, has some unfavourable properties. Therefore, it was necessary to develop a new generation of bio-derived motor fuel for Diesel-engines. The most promising product of these efforts is the bio gas oil, which is a mixture of n- and i-paraffins and obtained via hydroconversion of triglycerides. These compounds are the best components of conventional gas oils, too. Nowadays, mainly different vegetable oils are used as triglyceride source, but for the hydroconversion any feedstock with high triglyceride content can be used (e.g. brown greases of sewage works, used cooking oils, animal fats, etc.). The waste feedstocks can be especially beneficial. Hence, during the experimental work, our aim was to investigate the possibilities of the production of bio gas oil and bio gas oil containing gas oils on waste fat basis via the hydroconversion of waste rancid lard itself and as a 50% mixture with gas oils. We applied a CoMo/Al2O3 catalyst in sulphide and in nonsulphide state for our experiments. We studied the effects of the process parameters (temperature: 300–380°C, pressure: 40–80 bar, LHSV: 1.0–2.0 h-1, H2/feedstock ratio: 600 Nm3/m3) on the quality and yield of the products. The obtained main product fraction at the process parameters (360–380°C, 60–80 bar, LHSV: 1.0 h-1, H2/feedstock rate: 600 Nm3/m3) found to be favourable by us which were met the valid diesel gas oil standard EN 590:2009 + A1:2010 without additivation, except for its cold flow properties.