PRODUCTION OF DIESEL GAS OIL COMPONENT FROM WASTE ANIMAL FATS

THESES OF PhD DISSERTATION PRODUCTION OF DIESEL GAS OIL COMPONENT FROM WASTE ANIMAL FATS Made by: PÉTER BALADINCZ Chemical Engineer, M.Sc. Doctoral School of Chemical Engineering and Material Science, University of Pannonia Supervisor: Dr. Jenő Hancsók Chemical Engineer, Eur. Ing., DSc., Professor University of Pannonia Faculty of Engineering Institute of Chemical and Process Engineering MOL Department of Hydrocarbon and Coal Processing Veszprém, Hungary 2016-1-

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INTRODUCTION AND OBJECTIVES The need of decreasing the dependence on imported energy carriers and the more rigorous environmental regulations forced the research and development of alternative fuels and amongst them the bio derived engine fuels. Inside the European Union base on the tendencies of the last 10 years the research, development and application of bio derived diesel fuels is of great significance because of energetic and environmental point of view. The rise of the biofuel markets also caused increase in the price of the crops which can serve as a feedstock base for them. Therefore to make the production of bio engine fuels more economic is becoming an important factor. A good solution for this problem is the utilization of cheaper, waste feeds e.g. like waste animal fats. These materials cannot simply be used for the production of biodiesels, but their hydrogenation and conversion to biofuel can be an adequate alternative to produce bio derived diesel fuel. According to the above and because of the incomplete and uncertain results of the few articles on this topic, the main objective of my PhD activity was the investigation of the heterogeneous catalytic hydrogenation of waste animal fats for the production of bio derived diesel fuel. On the course of this, the hydrogenation and conversion to biofuel of contaminated waste animal fat in itself and with gas oil fractions were investigated with the utilization of bimetallic supported catalysts commonly used in refining technologies. The ways to pre-treat and clean was also investigated. -3-

EXPERIMENTAL In accordance with the previously presented, the objective of the research work was the investigation of the hydrogenation and conversion of waste animal fats to bio derived diesel fuel. The feedstocks of the heterogeneous catalytic experiments were different waste animal fats with different contamination levels. During the catalytic experiments the hydrogenation of waste fats themselves and together with gas oil fractions were investigated (applying different process parameter combinations). Long term experiments were also carried out and were compared to the promising results of the previous experiments. During these, the effects of the different contaminants on the catalytic system were investigated. Different feedstock pre-treatment and cleaning experiments were also carried out to remove the contaminants which can affect the catalytic system. During the catalytic experiments bimetallic supported catalysts (NiMo/Al 2 O 3, CoMo/Al 2 O 3 ) commonly used in refining technologies were utilized. The effect of different activation methods (sulphide state or non sulphide state) were also investigated during the experiments. The catalytic experiments were carried out in a laboratory scale reactor system of the MOL Department of Hydrocarbon and Coal Processing of University of Pannonia. The experiments were carried out in continuous state (with 0-24 hour monitoring). The composition of the feedstocks and the products obtained during the heterogeneous catalytic experiments were determined by different gas chromatography methods, while their properties were determined with standardised methods and calculations. -4-

NEW SCIENTEIFIC RESULTS 1. It was concluded that with choosing suitable auxiliary materials e.g. maleic acid anhydride high cleaning efficiency (> 80-95 %) can be achieved during pre-treatment, even in one process step. 2. It was pointed out that the yield of the gas oil product is lower in case of the hydrogenation of animal fats (93 % of theoretical value) than in case of vegetable oils (practically total conversion). The cause of this is the higher content of contaminants (basic nitrogen compounds and phospholipids next to oxygen heteroatom) in the animal fats. 3. It was proved that from supported bimetallic hydrogenation and desulphurization catalysts, NiMo/Al 2 O 3 gives better results than CoMo/Al 2 O 3 in the course of hydrogenation of animal fats to engine fuel. 4. It was stated that on the course of animal fat hydrogenation and under the same conditions, the product yields are higher with sulphided catalysts than with catalyst activated in hydrogen. Also, in case of sulphided catalysts, the decarbonylation/decarboxylation reactions are dominant, in which shorter carbon chained paraffins are forming. 5. It was pointed out that for fuel purpose hydrogenation of animal fats their co-processing with gas oil streams is the most appropriate method. 5.1. It is stated that during co-processing the impurities in the fat have smaller effect on the performance and stability of the catalytic system. Mainly because of the cleaning effect of the gas oil part. -5-

6. It was proved that during co-process of animal fats and gas oil streams, the high contaminant and heteroatom content of the fat (oxygen, sulphur, basic nitrogen, phosphorus, metals) adversely affect the desulphurisation and slightly the dearomatisation of the gas oil part. Therefore to ensure the appropriate quality of the product made in one step it is necessary to adjust the ratio of the feedstocks to maximum 5-10 % fat content. 6.1. Appropriately selected fat to gas oil feedstock ratio (5-10 % waste fat content) was determined which can be applied for the production of biofuel containing diesel fuel with the utilization of process parameter range (360-380 C, 60-80 bar, 0,5-1,0 h -1, 600 Nm 3 /m 3 ) commonly used in hydrodesulphurization processes. The obtained products are of high quality and energy content and can be utilized in Diesel engines as fuels even in themselves. 7. It was confirmed by results obtained during long term experiments that the low contaminant content (metal and phosphorus content < 10 mg/kg) of the fat is criteria for the long service life of the catalyst. -6-

INDUSTRIAL APPLICABILITY OF THE RESULTS To encourage the research and utilization in increasing quantities of biofuels the European Union continuously defines new directives and regulations. Until now it seemed that the objectives set by these regulations can be achieved with the utilization of biodiesel made by transesterification of different vegetable oils. However the biodiesel - and its manufacturing process also - is sensible for the quality of its feedstock. Moreover the increasing demand for biodiesel caused increase in the price of crops which are normally used as food and feed. The result of the research aimed to replace biodiesel is the bio gas oil, which is made by fuel purpose hydrogenation of triglycerides containing materials. The bio gas oil product is a mixture of paraffin compounds which are ideal fuels because of their high energy content. Another advantage that the hydrogenation process is not sensible on the quality of the feedstock, thus good quality product can be made from waste material, too. Very big advantage of the fuel purpose conversion of waste materials that the products made from these kinds of feeds are count as double when calculating the share of biofuels (10 e% till 2020). According to the results of the experiments on the hydrogenation of animal fats on NiMo/Al 2 O 3 and CoMo/Al 2 O 3 supported bimetallic catalysts widely used in refineries it was stated that the hydrogenation-desulphurisation technologies - which are available in any refinery - are suitable for fuel purpose hydrogenation of animal fats (after pre-treatment, highly contaminated waste fats also) and for coprocessing them with gas oil streams. Based on the results the proper hydrotreater units maybe with slight modification - of a refinery are applicable and capable for the production of bio gas oil and/or bio gas oil containing gas oil. These products can be valuable components of diesel fuels because of their high energy content. With the utilization of waste animal fats as co-feedstocks of hydrotreating technologies, the refineries can be able to meet the objectives made by the Union with minimal investment cost. Because of the most promising prospects, industrial scale experiments started (also in Hungary) and data collection is already under way for the possible implementation of the process and the waste feedstock. -7-

LIST OF PUBLICATIONS AND PRESENTATIONS 1. PUBLICATIONS CONCERNING THE TOPIC OF THE DISSERTATION 1.1. Publications in foreign languages published in foreign journals: 1.1.1. Hancsók, J., Baladincz, P., Kasza, T., Kovács, S., Tóth, Cs., Varga, Z., Bio gas oil production from waste lard, Journal of Biomedicine and Biotechnology, 2011, Article ID 384184, 9 pages ((IF: 2.436 (2011)). 1.1.2. Baladincz, P., Hancsók, J.: "Fuel from waste animal fats, Chemical Engineering Journal, 282., 2015, 152-160. ((IF: 4.321, (2014)). 1.2. Publications in foreign languages published in Hungarian journals: 1.2.1. Baladincz, P., Tóth, Cs., Hancsók, J.: Expanding feedstock supplies of the second generation bio-fuels of diesel-engines, Hungarian Journal of Industrial Chemistry, 2010, 38(1) 1-7. 1.2.2. Baladincz, P., Tóth, Cs., Kovács, S., Hancsók, J.: Investigation of the hydroconversion of lard and lard-gas oil mixture on Pt,Pd/USY catalyst, Hungarian Journal of Industrial Chemistry, 2011, 39(1), pp. 7-13. 1.2.3. Baladincz, P.; Ludányi, A.; Leveles, L.; Hancsók, J.: Production of gas oil components from waste fats, Hungarian Journal of Industrial Chemistry, 2012, 40(1), pp. 45-52. 1.3. Presentations in foreign languages at international conferences with full-text publications: 1.3.1. Baladincz, P., Tóth, Cs., Hancsók, J.: Production of second generation renewable diesel fuel via coprocessing of lard and straight run gas oil mixtures, 8 th International Colloquium Fuels 2011, Germany, Stuttgart/Ostfildern, 19-20. January 2011., In Proceedings (ISBN 3-924813-75-2), 383-389. 1.3.2. Baladincz, P., Tóth, Cs., Kovács, S., Hancsók, J.: Investigation of the hydroconversion of lard and lard - gas oil mixture on Pt,Pd/USY catalyst, 45 th International Petroleum Conference, Slovakia, Bratislava, 13-14. June 2011., In Conference CD, ISBN 978-80-969792-2-6. 1.3.3. Baladincz, P., Tóth, Cs., Kovács, S., Hancsók, J.: Investigation of the conversion of lard on hydrotreating catalysts, Interfaces 11, (MKE) Sopron, Hungary, 28-30. September 2011., pp. 11. 1.3.4. Baladincz, P., Hancsók, J.: Investigation of the hydroconversion of rancid lard and lard-gas oil mixture in NiMo/Al 2 O 3 catalyst in oxide and in sulfide state, 2 nd European Conference of Chemical Engineering (ECCE 11), 10-12. December 2011., Puerto de La Cruz, Tenerife, Spain, Proceedings (ISBN 978-1-61804-057-2), 64-70. 1.3.5. Baladincz, P., Tóth, Cs., Hancsók, J.: Production of diesel fuel via hydrogenation of rancid lard and gas oil mixtures, PRES2012, Czech Republic, Prague, 25-29 August 2012., Conference CD, ISBN 978-80-905035-1-9, No.: 1297, I5.10. 1.3.6. Baladincz, P., Tóth, Cs., Hancsók, J.: Production of diesel fuel via hydrogenation of rancid lard and gas oil mixtures, Chemical Engineering Transaction, 2012, 29(Part 2), 1237-1242. 1.3.7. Baladincz P., Leveles L., Hancsók J.: "Production of Diesel fuel via co-processing of waste fat and gas oil mixtures on commercial hydrogenation catalyst", 46 th International Conference on Petroleum Processing, Slovakia, Bratislava, 7. June 2013., CD Proceedings (ISBN: 978-80-969792-4-0) 12 pp. -8-

1.4. Presentations at Hungarian conferences with full-text publications: 1.4.1. Baladincz, P., Tóth, Cs., Hancsók, J.: Diesel-motorokhajtására alkalmas második generációs biomotorhajtóanyagok nyersanyagbázisának szélesítése, MOBILITÁS és KÖRNYEZET: a járműipar kihívásai az energetika, a szerkezeti anyagok és környezeti kutatások területén conference, University of Pannonia, Veszprém, Hungary, 23-25. August 2010. 1.4.2. Baladincz, P., Tóth, Cs., Hancsók, J.: Megújítható Diesel-motorhajtóanyag előállítása sertészsír és gázolajpárlat elegyeinek együttes feldolgozásával, Műszaki Kémiai Napok 2011, Veszprém, Hungary, 27-29. April 2011., Proceedings (ISBN 978-615-5044-07-6), 14-20. 1.4.3. Baladincz, P., Tóth, Cs., Hancsók, J.: Avas sertészsír és gázolajjal képzett elegyeinek hidrogénező átalakíthatóságának vizsgálata szulfidált és nem szulfidált állapotú NiMo/Al 2 O 3 katalizátoron, Műszaki Kémiai Napok, Veszprém, Hungary, 24-26. April 2012., (ISBN 978-615-5044-54-0), 282-293. 1.4.4. Baladincz, P., Hancsók, J.: Diesel-motorhajtóanyag előállítása állati zsiradék és gázolaj elegyek hidrogénezésével, Műszaki Kémiai Napok, Veszprém, Hungary, 23-25 April 2013., (ISBN 978-615- 5044-79-3), 177-184. 1.5. Presentations in foreign languages at international conferences with summary publications: 1.5.1. Baladincz, P., Tóth, C., Hancsók, J.: Production of bio gas oil from rancid lard via catalytic hydrogenation on different state CoMo/Al 2 O 3 catalysts, International Symposium on "Catalysis for Clean Energy and Sustainable Chemistry", CCESC2012, Alcobendas, Madrid (Spain), 27-29 June 2012., In proceedings P-50. 1.6. Presentations at Hungarian conferences with summary publications: 1.6.1. Baladincz, P., Tóth, Cs., Kovács., S., Hancsók, J.: Sertészsír és sertészsír-gázolaj elegy hidrogénező átalakításának vizsgálata Pt,Pd/USY katalizátoron, Mobilitás és Környezet 2011 - A járműipar kihívásai az energetika, a szerkezeti anyagok és környezeti kutatások területén, Veszprém, Hungary, 29 August 1 September, 2011., Conference CD. 1.6.2. Baladincz, P., Hancsók, J.: Diesel motorhajtóanyag előállítása hulladék állati zsiradék és gázolaj elegyek együttes feldolgozásával, Környezetbarát anyagok és technológiák konferencia és 56. Magyar Spektrokémiai Vándorgyúlés konferencia, Veszprém, Hungary, 1-3. July 2013., In CD Proceedings. 1.7. Other presentations: 1.7.1. Baladincz, P., Hancsók, J.: Motorhajtóanyagok hulladék zsiradékokból, Bioenergetikai Kerekasztal, TÁMOP-4.2.3-08/1-2009-0018 Tudományos eredmények disszertációja és tehetséggondozás a minőségi képzésért a Pannon Egyetemen, Veszprém, Hungary, 16. September 2011. 1.7.2. Baladincz, P.: Vágóhídi zsiradékok motorhajtóanyag célú hidrogénezése, MKE Symposium, Veszprém, Hungary, 7. December 2011. -9-

2. PUBLICATIONS NOT DIRECTLY REALTED TO THE TOPIC OF THE DISSERTATION 2.1. Publications in foreign languages published in foreign journals: 2.1.1. Tóth, Cs.,Baladincz, P., Kovács, S., Hancsók, J.: Producing Diesel Fuel by Co-Hydrogenation of Vegetable Oil with Gas Oil, Chemical Engineering Transactions, 2010, 21, 1219-1224. 2.1.2. Tóth, Cs.,Baladincz, P., Kovács, S., Hancsók, J.: Producing clean diesel fuel by co-hydrogenation of vegetable oil with gas oil, Clean Technologies and Environmental Policy, 2011, 13(4) 581-585. ((IF: 1.753 (2011)). 2.1.3. Tóth, Cs., Baladincz, P., Hancsók, J.: Production of biocomponent containing gas oil with the coprocessing of vegetable oil gas oil mixture, Topics in Catalysis, 2011, 54, 1084 1093. ((IF: 2.624 (2011)). 2.1.4. Tóth, Cs., Baladincz, P., Hancsók, J.: Production of bio gas oil containing diesel fuel with upgraded cold flow properties by co-processing, Chemical Engineering Transaction, 2012, 29(Part 2), 613-618. 2.1.5. Baladincz, P., Sági, D., Szepesi, M., Hancsók, J.: Co-processing of FCC Light Cycle Oil and Waste Animal Fats with Straight Run Gas Oil Fraction, Chemical Engineering Transactions, 2014, 39(Part 2), 1159-1164. 2.1.6. Sági, D., Baladincz, P., Varga, Z., Hancsók, J.: Co-processing of FCC light cycle oil and waste animal fats with straight run gas oil fraction, Journal of Cleaner Production, 111. A, 2016, 34 41. ((IF: 3.844, (2014)). 2.2. Publications in foreign languages published in Hungarian journals: 2.2.1. Kasza, T.,Baladincz, P., Hancsók, J.: Production of bio-isoparaffins by hydroisomerisation of bioparaffins, Hungarian Journal of Industrial Chemistry, 2009, 37(2), 95-99. 2.2.2. Tóth, Cs.,Baladincz, P., Hancsók, J.: "Fuel production from triglycerides containing gas oils", Hungarian Journal of Industrial Chemistry, 2009, 37(2), 101-106. 2.3. Presentations in foreign languages at international conferences with full-text publications: 2.3.1. Krár, M., Kasza, T., Tóth, Cs., Baladincz, P., Hancsók, J.: Hydrotreating of triglyceride containing gas oils, 4th International Bioenergy Conference, Finland, Jyväskylä, 31. August 4 September, 2009., In Proceedings, Part II. (ISBN 978-952-5135-44-2), 629-638. 2.3.2. Tóth, Cs., Kasza, T., Kovács, S., Baladincz, P., Hancsók, J.: Investigation of catalytic conversion of vegetable oil/gas oil mixtures, 44 th International Petroleum Conference, Slovakia, Bratislava, 21-22 September 2009., In CD Proceedings (ISBN 978-80-969792-1-9). 2.3.3. Kasza, T., Tóth, Cs., Baladincz, P., Kovács, S., Hancsók, J.: Investigation of upgrading of natural triglyceride containing gas oil, 44 th International Petroleum Conference, Slovakia, Bratislava, 21-22 September 2009., In CD Proceedings (ISBN 978-80-969792-1-9). 2.3.4. Tóth, Cs., Baladincz, P., Kovács, S., Hancsók, J.: The effect of different sulphur content of the feedstocks on the catalytic conversion of the vegetable oil gas oil mixtures, International Symposium on Motor Fuel 2010, Slovakia, Tatranské Matliare, 14-17 June 2010., In CD Proceedings (ISBN 978-80-969710-5-3), MF-2537. 2.3.5. Tóth, Cs., Baladincz, P., Kovács, S., Hancsók, J.: Producing Diesel Fuel by Co-Hydrogenation of Vegetable Oil with Gas Oil, 13 th Conference on Process Integration, Modelling and Optimisation for -10-

Energy Saving and Pollution Reduction, Prague, Czech Republic, 28 August 1 September, 2010., In CD Proceedings (ISBN 978-80-02-02210-7). 2.3.6. Tóth, Cs., Baladincz, P., Wáhlné Horváth, I., Hancsók, J.: Co-processing of rapeseed oil and gas oil mixture to produce diesel fuel, 19 th EU Biomass Conference & Exhibition, Germany, Berlin, 6-9 June 2011., CD Proceedings, ISBN 978-88-89407-55-7, 2070-2076. 2.3.7. Solymosi, P., Baladincz, P., Hancsók, J.: Production of motor fuels by hydrogenation of rapeseed oil with high euric acid content, 19 th EU Biomass Conference & Exhibition, Germany, Berlin, 6-9 June 2011., CD Proceedings, ISBN 978-88-89407-55-7, 2077-2081. 2.3.8. Tóth, Cs., Baladincz, P., Hancsók, J.: Production of biocomponent containing diesel fuel in one step, 45 th International Petroleum Conference, Slovakia, Bratislava, 13-14 June 2011., In Conference CD, ISBN 978-80-969792-2-6. 2.3.9. Tóth Cs., Baladincz, P., Hancsók, J.: The effect of the sulphur content of the feedstock on the coprocessing of gas oil vegetable oil mixture, Interfaces 11, (MKE) Sopron, Hungary, 28-30 September, 2011. 2.3.10. Tóth, Cs., Baladincz, P., Hancsók, J.: Production of bio gas oil containing diesel fuel with upgraded cold flow properties by co-processing, PRES2012, Czech Republic, Prague, 25-29 August, 2012., Conference CD, ISBN 978-80-905035-1-9, No.: 1318, P7.188. 2.3.11. Baladincz, P., Sági, D., Szepesi, M., Hancsók, J.: Co-processing of FCC Light Cycle Oil and Waste Animal Fats with Straight Run Gas Oil Fraction, 17th Conference on Process Integration, Modelling and Optimisation for Energy Saving and Pollution Reduction PRES 2014, Prague, Czech Republic, 23-27 August 2014., Conference CD, ISBN: 978-80-02-02555-9, Serial Number: 0586. 2.4. Presentations at Hungarian conferences with full-text publications: 2.4.1. Tóth, Cs., Kasza, T., Kovács, S., Baladincz, P., Hancsók, J.: Motorhajtóanyagok előállítása trigliceridtartalmú gázolajokból, Műszaki Kémiai Napok 09, Veszprém, Hungary, 21-23 April 2009., Proceedings, (ISBN 978-963-9696-68-6), 208-214. 2.4.2. Baladincz, P., Tóth, Cs., Hancsók, J.: "Dízel-motorhajtóanyag előállítása növényolaj és gázolaj együttes feldolgozásával", Műszaki Kémiai Napok 2010, Veszprém, Hungary, 27-29 April 2010., Proceedings (ISBN 978-963-9696-93-8), 18-24. 2.4.3. Kovács, S., Baladincz, P., Hancsók, J.: "Trigliceridek katalítikus átalakíthatóságának vizsgálata NiMo/Al 2 O 3 katalizátoron", Műszaki Kémiai Napok 2010, Veszprém, Hungary, 27-29 April 2010., Proceedings (ISBN 978-963-9696-93-8), 28-34. 2.4.4. Tóth, Cs., Baladincz, P., Hancsók, J.: Az alapanyag aromástartalmának hatása növényolajgázolaj elegyek együttes feldolgozására, Műszaki Kémiai Napok 2011, Veszprém, Hungary, 27-29. April 2011., Proceedings (ISBN 978-615-5044-07-6), 46-51. 2.5. Presentations in foreign languages at international conferences with summary publications: 2.5.1. Tóth, Cs., Baladincz, P., Hancsók, J.: Production of biocomponent containing gas oil with the coprocessing of vegetable oil - gas oil mixture, 14 th Nordic Symposium on Catalysis, Denmark, Helsingør, 29-31 August 2010., Book of Abstracts P32. 2.5.2. Tóth, Cs., Baladincz, P., Kovács, S., Hancsók, J.: Effect of aromatic content of the feedstock to the co-processing of vegetable oil gas oil mixture, 2nd International Symposiumon Air Pollution Abatement Catalysis, Poland, Krakow, 8-11 September 2010., Book of Extended Abstracts, 533-535. -11-

SUMMARY OF PUBLICATIONS SCIENTOMETRIC DATA Publications In total Publications concerning the topic of the dissertation Articles in journals Publications in foreign languages published in foreign journals 2 Publications in foreign languages published in Hungarian journals 2 Publications in conference proceedings Full-text publications in proceedings of International conferences 7 Full-text publications in proceedings of Hungarian conferences 4 Impact factor of publications concerning the dissertation 6.757 Publications in total 46 Total impact factor of publications 14.978 Number of independent references/citations 27 Veszprém, Hungary, 2016. -12-