Prednáška otvorí problematiku seminára a súhrnne sa dotkne súčasného a budúceho stavu vo výskume a vývoji biosložiek pre dopravu

Diskusia o možnosti výroby biopalív druhej generácie v podmienkach ČR: kritický pohľad.

Predstavenie novej európskej smernice o podpore využívania energie z obnoviteľných zdrojov energie 2009/28/EC

Kritické hodnotenie situácie v oblasti spotrebných daní a štátnej pomoci pri výrobe a distribúcii biozložiek a motorových palív s ich obsahom

Bioetanol je objemovo najviac vyrábanou biozložkou pridávanou do palív. budú prezentované nové poznatky v oblasti výroby bioetanolu z rôznych surovín a možnosti výroby iných bioalkoholov.

jedna z technológií premeny biomasy sú termické a termo-katalytické procesy. v prednáške budú prezentované najnovšie technologické pokroky v tejto oblasti

Abstrakt: Letecký petrolej JET A-1 je takmer vždy výrobok s vyššou pridanou hodnotou a i s vyšším dosahovaným „crack-spreadom“, ako má motorová nafta. Preto aj samotná výroba leteckých palív  je pomerne atraktívnou podnikateľskou činnosťou rafinérií, hlavne v blízkosti významnejších letísk. Príspevok popri analýze súčasnej situácie na trhu poukazuje aj na práve prebiehajúci vývoj leteckých alternatívnych biopalív. Upozorňuje, že vysoký nárast cien ropy v roku 2008 inicioval nárast úspešných testovacích letov na rôzne druhy alternatívnych leteckých palivá, vyprodukovaných nielen z biomasy, ale aj zo zemného plynu a uhlia. Treba brať aj do úvahy, že letecká doprava po roku 2012 vstúpi do systému obchodovania so skleníkovými plynmi (ETS), čo mierne zvýši i už dnes pomerne vysoké prevádzkové náklady aerolínií (o cca 5%). Nové technológie druhej generácie bio-palív pravdepodobne poskytnú vysokokvalitné uhľovodíkové frakcie, použiteľné aj pri výrobe leteckého petroleja v kvalite JET A-1. Je to ďalšia výzva pre rafinérie adekvátne zareagovať na novú situáciu na pomerne náročnom trhu s leteckými palivami.

Kľúčové slová: letecké biopalivá, JET-A1, crack-spready leteckého petroleja,  alternatívne letecké palivá, oxid uhličitý, emisie, ETS

Vodík je veľmi žiadaný produkt, naopak časť biomasy má veľmi nízky stupeň využitia. Možnosť výroby vodíka parciálnou oxidáciou je atraktívnou možnosťou výroby biovodíka.

 Abstrakt: Koncepce použití biomasy, nebo biologického materiálu ke snížení závislosti globální ekonomiky na přírodních zdrojích a k potlačení škodlivých emisí je často některými autory oslavována jakožto řešení problému globálního oteplování. Jiní odborníci ji odmítají s poukazem na omezování rozlohy orné půdy pro produkci potravin kvůli produkci biosložek paliv. Tato protichůdná stanoviska jsou dramaticky vyhrocována záměry EU zvýšením obsahu biosložek v motorových palivech do roku 2020 na 20 procent za současného snížení emisí oxidu uhličitého o stejné procento. V tomto ohledu je jistě užitečné hledat pro odpady biologické povahy vhodné racionální využití. Jinou alternativu pro úsporu fosilních surovin pro výrobu motorových paliv při současném snížení emisí oxidu uhličitého představuje striktní omezování rychlosti vozidel a modernizace vozového parku.

       Při produkci rostlinných olejů lisováním olejnatých semen (jsou surovinou pro biodiesel) odpadá šrot, který z důvodů ochrany spodních vod nelze skládkovat či kompostovat a kromě toho jeho zemědělské využití závisí na poptávce po přísadách do krmných směsí. Problém v tomto směru představuje logistika, transportní náklady a omezené stavy hospodářských zvířat, regulované legislativou EU.

            Odpadní šrot má ovšem také svoji energetickou hodnotu, nicméně jeho spalování představuje pouze triviální řešení problému jeho likvidace. Hlubší energetické zpracování odpadního šrotu parciální oxidací v přítomnosti vodní páry na syntézní plyn s významným obsahem vodíku představuje velkou výzvu pro výzkum a vývoj [1,2]. Technologie parciální oxidace odpadního šrotu může být řešena v návaznosti na parciální oxidaci ropných zbytků, která se desítky let využívá v ropných rafineriích pro petrochemickou produkci vodíku. Hlavní rozdíl mezi zpracováváním ropných zbytků a odpadní biomasy spočívá v tom, že struktura biomasy obsahuje kromě uhlíku a vodíku další biogenní prvky (kyslík, síra, dusík, fosfor) a také popeloviny. Nicméně lze předpokládat, že spolu-zplyňováním ropných zbytků a řepkového šrotu bude možné tuto biomasu racionálně využít.

            V práci jsou prezentovány výsledky projektu „BIOVODÍK“, který od roku 2007 finančně podporuje Ministerstvo průmyslu a obchodu ČR (grant MPO programu Trvalá prosperita ev.č. 2A-2TP1/024).   

Literatura:

[1] T.A. Mihne, C.C. Elam and R.J. Evans, „Hydrogen from Biomass  - State of the Art and Research Challenges“, A Report for the International Energy Agency Agreement on the Production and Utilization of Hydrogen Task 16, Hydrogen from Carbon-Containing Materials, 2002.

[2] H. Haykiri-Acma, S. Yaman, „Interpretation of biomass gasification yields regarding temperature intervals under nitrogen-steam atmosphere“, Fuel Processing Technology 88 (2007) 417 – 425.

Klíčová slova: vodík, biomasa, parciální oxidace, řepkový šrot

T. Brányik¹, P. Novák², I. Brányiková^1,3, B. Maršálková¹, K. Melzoch¹, J. Doucha³, V. Zachleder³

 1 Vysoká škola chemicko-technologická v Praze, ² TERMIZO a.s., ³ Mikrobiologický ústav AVČR, v.v.i.

Transformácia CO2 je aktuálny problém, v spojení s pestovaním rias na využitie do palív má perspektívne veľký význam.

Přednáška bude informovat o projektu, jenž si klade za cíl navrhnout a dlouhodobě ověřit technologii využívání odpadního oxidu uhličitého ze spalin optimálně provozované spalovny komunálních odpadů TERMIZO a.s. Liberec a to v řasových kulturách schopných rychlé tvorby biomasy s vysokým obsahem škrobů a lipidů. Budou prezentovány výsledky úpravy kultivačních podmínek řas k dosažení maximálních výtěžků. Následná konverze biomasy řas na bioetanol fermentací představuje alternativu fosilních paliv a výroby etanolu klasickým zemědělským způsobem.

V prednáške bude v krátkosti uvedený legislatívny rámec a bariéry produkcie bioplynu v SR. Budú predstavené typy bioplynových staníc a používané substráty. V závere prednášky bude diskutovaná prevádzka prvej bioplynovej stanice na Slovensku na spracovane cielene pestovaných energetických plodín

Zkušenosti s mísením, přepravou a skladováním směsí biopaliv z pohledu distributora

Účelem prezentace je seznámit odbornou veřejnost s řešením problematiky aplikace biopaliv v ČR v rámci distribuční společnosti zabývající se nejen skladováním, přepravou prodejem a výdejem zboží pro velkoobchodní účely, ale i skladováním a ochrannou strategických zásob pro potřeby Správy státních hmotných rezerv a armády ČR a NATO.

Právě skladování pro strategické účely znamená určitá omezení, která je nutno respektovat.

Vzhledem ke skutečnosti, že legislativa ČR předepisuje povinnou aplikaci biosložek a oproti tomu strategické zásoby a pohonné hmoty určené pro armádu tyto komponenty obsahovat nesmí, zvolilo ČEPRO, a.s. řešení přímého on-line dávkování v okamžiku expedice pohonné hmoty.

Součástí prezentace je postup zavádění aplikace biopaliv, popis stávajícího stavu včetně seznámení s realizací podpůrných projektů sloužících k objasnění „bílých míst“ problematiky biopaliv jako jsou otázky:

-         vlivu dlouhodobého skladování na změny kvalitativních parametrů a fyzikálně chemických vlastností pohonných hmot s obsahem biokomponent

-         vlivu společné přepravy čistých ropných produktů a produktů s obsahem biopomponent produktovodním systémem na jakost

Zkušenosti s užitím nízkokoncentrovaných směsí v dopravě. Sortiment a kvalita. Vývoj legislativy užití čistých biopaliv, rostlinných oleju a vysokokoncentrovaných směsí

Zkušenosti s uplatněním biopaliv a další vývoj jejich užití v ČR

Autoři: Ing. Václav LOULA, BENZINA s.r.o. Praha, Miloš PODRAZIL, Česká asociace petrolejářského průmyslu a obchodu, Praha.

     V ČR bylo používání biopaliv zahájeno v září 2007mísením methylesterů řepkových olejů do motorové nafty. V lednu 2008 bylo zahájeno mísení bioethanolu do automobilových benzinů.

V přednášce je popsán dosavadní vývoj v ČR se zaměřením na praktické zkušenosti s mísením biopaliv do fosilních motorových paliv  a kvalitu. Jsou uvedeny praktické zkušenosti s užitím v automobilech, přepravě a skladování. Dále je popsán vývoj legislativy k užití biopaliv  v ČR  a rozebrány aktuální problémy. Součástí přednášky je i predikce vývoje užití biopaliv první generace v ČR v návaznosti na směrnici 2009/30/ES a její rozpracování v tuzemských podmínkách.

Aktuálny stav zavádzania motorových palív

s prídavkom biozložiek v Slovnafte Bratislava

Michal Šingliar SLOVNAFT, a.s., Bratislava – člen skupiny MOL

Abstrakt

V príspevku je uvedená postupnosť krokov ako aj súčasný stav vo využívaní biopalív pri výrobe motorových palív v rafinérii Slovnaft Bratislava.  Za hybnú silu sa považuje podpora Európskej únie ako aj legislatíva všetkých jej členských štátov. Pri výrobe palív s prídavkom biopalív sa dáva dôraz na súčasné ako aj očakávané európske kvalitatívne normy (EN 228, EN 590, EN 14 214 a EN 15 376). Proces využitia biopalív pri výrobe motorových palív v Slovnafte začal laboratórnymi testami v roku 2004 – miešaním motorovej nafty s metylesterom rastlinného oleja (MERO). Prevádzka na výrobu Metyl-terc-butyl-éteru (MTBE) bola konvertovaná na výrobu Bio-etyl-terc-butyl-éteru (bio-ETBE), čo umožnilo vykonať podobné testy s miešaním benzínu s ETBE, neskôr aj s prídavkom bioetanolu.  Po počiatočných testoch začala rutinná výroba výrobkov B5 (nafta s prídavkom 5% MERO) a E5 (benzín s prídavkom 5% ETBE a etanolu). V súčasnosti sa vyrába nafta typu B5 a B7, benzín typu E5 a perspektívne sa uvažuje s výrobou motorových palív B10 a E10.

Tel.: +36 23 553 230

Fax: +36 23 551 109

E-mail: athernesz@mol.hu

Market perspective implies substantial challenges to all players of the mobility business, including customers, car makers and refiners. Next to the evident consequences of the economical situation, pressure rapidly emerging on the automotive industry to minimize GHG emission makes new engine technologies, whereas tightening fuel quality requirements in the Fuel Quality and Renewable Directives keep pushing refiners to produce cleaner and greener motor fuels.

Management with outstanding track record of operational efficiency and integration, experienced and efficient onshore upstream operation have made MOL Group a pace-setter among the regional players. Downstream focus areas for MOL Group include meeting the growing demand for lighter product slates, especially diesel. Timely investments in premium refinery assets have enabled the company to be in the forefront with fuel quality supplied. Another priority has been the successful integration of the currently available biofuel components including bio-ethanol and bio-diesel.

When developing roadmaps for investments into future refinery technologies, decarbonization concepts of transportation fuels, quality requirements of evolving engine technologies and sustainability prerequisites of alternative fuels must be thoroughly investigated.

PYROLYSIS TECHNOLOGIES FOR BIOMASS AND WASTE TREATMENT TO FUELS AND CHEMICAL PRODUCTION

Martin BAJUS

Slovak University of Technology, Faculty of Chemical and Food Technology, Institute of Organic Chemistry, Catalysis and Petrochemistry, Department of Petroleum Technology and Petrochemistry, Radlinského 9, SK-812 37 Bratislava, Slovak Republic

e-mail: martin.bajus@stuba.sk

            The second generation of biofuels processes should differ from the first in a) utilizing the whole plant as a feedstock and b) use of “non-food” perennial crops (woody biomass and tall grasses) and lignocellulosic residues and wastes. Possible options for the conversion of these liqnocellulosic plant materials include: thermal cracking, catalytic cracking, pyrolysis, carbonisation, catalytic reforming, steam reforming, gasification, Fischer-Tropsch sythesis, hydro-dehydrogenisation, hydrocracking, hydrorefining and decarboxylation. The main goal of biorafinery is to produce high-value low-volume chemicals (levoglucosan) and low-value high-volume fuels with a series of unit operations.

            Thermal processes must be included among the attractive basic recycling technology for polymers for which thermal cracking and pyrolysis enable the conversion of polymer materials into fuels, monomers and other valuable products.  The subject of the research were the thermal and catalytic processes for the production of motor fuels from polymer material from industrial material or municipal trash sources turning it into sulfur free, nonaromatic and ecological fuel via chemical recycling to replace fossil fuels mainly from oil sources. The key is the liquefaction of polymer materials to oil/waxes that can be distilled to provide gasoline, diesel fuels and heating oils that can be used directly or after hydrorefining.

            We found a way, how incorporate polymer waste into conventional liquid steam cracking feedstocks. Polyalkene oils and waxes decompose during copyrolysis. Amount of desired alkenes (ethylene, propene) increases or is slightly less in dependence on polymer type. Mixture of waxes in heavy naphtha (10-20% mass) exhibits short tendency to coking. Feedstock and chemical recycling of polyalkenes oils and waxes via copyrolysis is a very promising method treatment of polymer waste.

            We have developed Deep Scavanger Steam Cracking process or Steam Cracking Activation process (DSSC/SCA) for thermal cracking of used tyres and rubber waste, that works in a flow reactor. Basically, we received three fractions from the thermal cracking of used tyres-gases, liquid oils (d, l- limonene) and solid residues (coke, carbon, steel).

Acknowledgment

We would like to thank the VEGA Scientific Grant Agency of the Slovak Republic, for financial support of this research through the Research Project No. 1/0012/09.

Nowadays, the growth of the mobility seems to be instoppable, and by the increasing number of the vehicles even in the underdeveloped regions, the demand for various automotive fuels is increasing. In the developed regions such as European Union, the contribution of transportation to environmental pollutions has been recognized, thus the regulations for the automotive fuels has become stricter and stricter. As a potential method for the satisfaction of the quality and quantity demands, the opportunity of the use of automotive fuels derived from biomass has been intensively investigated.

For the partial replacement of gas oil produced from fossil sources, the biodiesel is used in these days, however, several disadvantages have been recognized up to now through its manufacturing and use. To avoid these disadvantages, the investigation, the producing in pilot plants and using of the second-generation biofuels as blending component has been started. Bio gas oil having the same boiling point range as the gas oils, excels from the second-generation biofuels. The bio gas oil is a mixture of iso- and normal-paraffins derived from the heterogeneous catalytic hydrogenation of vegetable oils (triglycerides). It can be applied in pure form or as blending component as well. In the last case, the separated conversion of the vegetable oil into bio gas oil is not definitely necessary. By the conversion of a mixture of vegetable oil and gas oil, the production of the bio gas oil could be achieved in just one catalytic step.

Key words: bio gas oil, hydroisomerisation

The developing of fuel processing from biomass is not only explained by environmental considerations but the energy dependence of Europe. According to the directive supporting the utilisation of bio fuel and to the new energy policy the recommended bio fuel consumption is 5,75% (based on energy content) by 2010, furthermore 10 % by 2020.

These bio fuels are easily biodegradable fuels and they have lower CO₂ emission in the course of their production, storage, transportation and utilisation regarded to the whole life cycles.

A promising solution of the production of gas oil boiling range products could be the hydrogenation of gas oil and vegetable oil mixtures. It is well-known, that in the petrol chemistry catalyst layers with different composition are used in a reactor to ensure the favourable direction of catalytic conversions, for example in case of deep hydrodesulphurisation of gas oils.

During our research we investigated the catalytic conversionability of gas oil and vegetable oil mixtures to diesel fuel on catalyst bed framed up from different catalyst layers containing different metals and support.

The paper brings information concerning to impact of bioethanol and/or biobutanol content in blends with fossil petrol on the final motor fuel properties measured by commonly used laboratory test methods according to EN 228.

For tests were used four groups of model samples as follows:

• Blends of bioethanol and/or biobutanol with fossil petrol containing from 0 to 25 % V/V of alcohols,
• E85 and Bu85 fuels (70 – 85 % V/V alcohols in blends with petrol),
• Products from AB fermentation (acetone + butanol-1)
• Products from ABE fermentation (acetone + butanol-1 + ethanol).

The measured results show that besides using of both bioethanol and biobutanol for the “low blending” according to valid EN 228 standard the blends with their higher content (20-25 % V/V) also can be used. On the other hand, as very interesting and perspective can be considered also fuels for spark ignition engines, which are (will be) produced from renewable sources only by AB fermentation or by ABE fermentation. The production of these fuels is absolutely independent on the crude oil supplying.

DIESEL FUELS FROM RENEWABLE SOURCES

Martina Slezáčková, Daniel Bratský

martina.slezackova@vurup.sk, daniel.bratsky@vurup.sk

Key words: Pure plant oils, Bio-ethanol, Bio-butanol, Diesel engines, Laboratory and   

 engine tests

Abstract

The idea to use pure plant oils as fuels for diesel engines is more than one hundred years old. It was published that one prototype of a new small diesel engine designed in accordance with the patent by Rudolf Diesel and built by French Otto Company presented at the World Exhibition in Paris in 1900 was operated on peanut oil. The engine was built for mineral oil and was used for the plant oil without any alterations being made. To be more precise five diesel engines were shown at the Paris Exposition and one of them was apparently operating on peanut oil. Due to the fact that petroleum based fuels were available at comparatively low prices for relatively long time period, except for some attempts at utilising renewable sources of energy during World War II, it was only in 1970s and early 1980s that the world-wide oil crises and a growing ecological awareness led to the rediscovery of vegetable as possible alternatives to hydrocarbon-based fuels.

There are several problems at the application of plant oils as diesel fuel which had to be overcome (high viscosity, poor low temperature properties, fuel atomisation, tendency for thermal and/or oxidative polymerisation, dilution and degradation of lubricating oil, sticking of piston rings, etc.). The mentioned problems can be solved either by adapting the engine to the fuel (this way seems to be more convenient for automotive industry) or by adapting the fuel to the engine.

The paper will review published information and mainly findings from own research concerning to the application of straight vegetable oils and their blends with bio-ethanol and/or with bio-butanol as fuels for diesel engines.  On the other hand, using of fossil diesel fuel containing bio-ethanol or bio-butanol will be also presented for comparison. For tests were used three groups of model samples as follows:

• Blends of bio-ethanol or bio-butanol with vegetable oil containing from 0 to 15 % V/V of alcohols,

• Ternary blends of vegetable oil, bio-ethanol and bio-butanol (5 to 15 % V/V of alcohols),

• Blends of bio-ethanol or bio-butanol with fossil diesel fuel containing from 0 to 15 % V/V of alcohols.

The positive and also the negative aspects of above mentioned renewable fuels for diesel engines will be documented by the results of specific (in-house) and commonly used laboratory testing methods and also by engine tests realised using diesel engine powered car on chassis dynamometer - power output, torque, fuel consumption characteristics and exhaust emission composition.

PRODUCTION OF NAPHTA FROM WASTE TRIACYLGLYCEROLS BY HYDRODEOXYGENATION
MIKULEC, J.*; CVENGROŠ, J.; JORÍKOVÁ, Ľ.; BANIČ, M.; SLEZÁČKOVÁ, M.* SLOVNAFT VURUP, a.s.

Abstract

The study is devoted to the issue of direct transformation of triacylglycerols (TAG) to diesel fuels applying a commercially available NiMo and NiW hydrorefining catalysts. It was proved that TAG can be converted to the fuel biocomponent by adding 6.5 % (vol.) of TAG to atmospheric gas oil.  In this way, after hydroprocessing at mild conditions (temperature 320-360 ^oC, pressure 3.5-5.5 MPa, LHSV = 1 h^-1 and ratio H₂:HC = 500-1000 Nm³/m³, catalyst presence), gas oil containing 5-5.5 % of biocomponent was prepared, characterized with standard performance and emission parameters. Long-term stability test of the catalyst was carried out and sufficient catalyst life was confirmed. Performance and emission tests documented that even 5% (vol.) portion of bio-components reduces the controlled and uncontrolled emissions.

The theme of this presentation is the characteristics of lubricating greases produced with calcium-sulphonate compared to traditional greases and the benefits experienced by the customers.

Balint Szilagyi bszilagyi@mol.hu Key words: antifreeze, coolant, corrosion, inhibitor By the continuous technology development new trends are appearing in engine and cooling system design. The direction of engine and heat exchanger system developments move toward the lower weight, higher power output and even more sophisticated and compact designed systems. In practice the newest engines and heat exchanger systems contain high amount light metals (Al alloys), narrower coolant passages and operates on higher temperature. Due to ensure adequate heat transfer and corrosion protections for the newly designed systems basically new coolant formulations are needed. In the early years of 20th century the base fluid was methanol and water mixture. The first ethylene-glycol based coolants become available in 1927. The only drawback of ethylene-glycol and water mixture is their aggressive corrosive characteristic. This phenomenon initiated the long way of the development of corrosion inhibitors. Corrosion is the destructive attack to metal by a chemical or electrochemical reaction with its environment. A corrosion inhibitor is a material that forms a protective layer on metal surface, providing a protective barrier film, which stops the corrosive reaction from developing. The first generation of ethylene-glycol based antifreeze coolants contained mainly inorganic compounds for example molybdates (MoO42-), chromates (CrO42-), phosphates (PO43-), nitrates (NO3-) and nitrites (NO2-). The biggest disadvantage of these inorganic inhibitors is their short depletion time and for this reason the relatively short drain interval of coolant fluids with inorganic additive system. In the beginning of 90’s new organic compound based additive technology have developed and introduced to market. The nowadays broadly used new generation antifreeze coolants contains organic corrosion inhibitors like alkylbenzoic acid (wherein alkyl group is C1-C5), aliphatic (C8-C12) mono- or dicarboxyl acids salts or hydrocarbon triazole compounds behalf of inorganic salts. These inhibitors ensure much better corrosion protection, they have significantly longer depletion time and the environmental properties of them are much better than the inorganic ones. In the future, the spread of glycerol as base fluid is expected. Since the glycerol modulates the chemical and physical properties of the antifreeze coolants it will have an effect on the antifreeze additive formulations.

The paper is aimed at using of waste polymers, waste rubber as modificators in asfalt compositions. The qualitative characteristics of these mixtures are compared with the proprerties SBS and EVA modified asphalts. Standard tests, viscosity properties, storage stability of polymers in asphalt and affinity between aggregates and asphalt mixtures with polymers were compaunded.

In 2006 started a project, focusing on the application of IEC 61508 and IEC 61511 Process Safety Standards in the Slovnaft Refinary. The project was performed SIL4S Ltd and YOKOGAWA in co-operation. SIL4S was responsible for preparing HAZOP study and SIL calculation, even pre validation of the existing Shut Dowmn Systems of all Plant of Slovnaft Refinary. In the first phase of the project we were dealing with the firing furnace. The big challange was how and why to apply the Process safety Standards in co-operation with existing Burner Management Standards. In our presentation we would like to demonstrate our result of this harmonasiation of interdiscipline standards resulting Furnace HAZOP templates. We also would like to present the methodoly using in this project and the results of the HAZOP study and SIL calculation. We will show the revealed problems and the solution suggested. In conclusion we will show the advantage of this project and important result in the safety culture of the Refinary. György Baradits

Alkylation of benzene with linear 1-alkenes belongs to typical Friedel-Crafts reactions. It is a complex process, which consists of main reaction, alkylation and several side reactions. At the alkylation of benzene with long chain 1-alkenes are created also beside products as isomers from monoalkylated benzene, smaller amount of dimmers and dialkylbenzenes. The total conversion on monoalkylbenzenes and the selectivity to 2-phenyl isomer, amounts and type of beside products is dependent on type of used catalysts and reaction conditions. It is a great effort to solve environmental problems with FC-catalysts by their replacing with acid heterogeneous catalysts mainly on the base of zeolites.

CATALYTIC OXIDATION OF BIOGLYCEROL TO MONO- AND DICARBOXYLIC ACIDS

Magdaléna Štolcová, Andrej Ševčík and Alexander Kaszonyi

Department of Organic Technology, Slovak University of Technology, Radlinského 9, 81237 Bratislava, Slovakia

Key words: glycerol oxidation, carboxylic acids, Pd-Bi catalysts, microgel resin support

Abstract:

Catalysts containing Pd and Pd-Bi species supported on cationic resin (Dowex 1x4, gel type poly(styrene-co-divinylbenzene) with –N(CH₃)₃⁺Cl^- groups, particle size 100-200 mesh) were prepared and studied in the liquid phase oxidation of glycerol. The catalysts were prepared by reduction of anionic chloro complexes of palladium(II) and palladium(II)-bismuth(III) immobilized in the resin. Different reduction methods for sodium borohydrate and gaseous hydrogen were employed. The catalytic activity is shown to be dependent not only on the metal species but also on the concentration of the metals loaded. The choice of the metal particles reduction methods slightly influenced the rate of the reaction and the selectivity to mono- and dicarboxylic acids formation. High selectivity to tartronic and glyceric acids was produced at almost 90 % conversion of glycerol over the palladium-bismuth catalyst at pH 12. The deactivation of the catalysts studied during 6-8 cycles was less than 6%.

The basical aim of the research was to use the nanostructured iron oxide material as a mild oxidative catalyst, able to selectively epoxidize olefins (in contrast with bulk metal oxides which lead to radical reaction mechanism and combustion). We have studied the gas-phase epoxidation of propylene to propylene oxide exploiting nitrous oxide as an oxidant. The purpose of the present work was to understand the formation of iron oxide nanoparticles on mesoporous silica matrix, as well as on halide-based supports to set the parameters of the preparation which influence their diameter and distribution and understand the mechanism of their stabilization on the surface. These materials exhibit improved catalytic activity in the epoxidation of propylene using nitrous oxide as an oxidant, exhibiting progressive increase in PO yield upon reactivation.

STRUCTURE-ACTIVITY COMPARISON OF BULK AND SILICA SUPPORTED CU-FE-P-O CATALYSTS FOR METHANE DIRECT OXIDATION TO FORMALDEHYDE Magdaléna Štolcová, Róbert Polnišer and Milan Hronec Department of Organic Technology, Slovak University of Technology, Radlinského 9, 81237 Bratislava, Slovakia Key words: methane partial oxidation, formaldehyde, Cu-Fe-pyrophosphate catalysts Abstract: Crystalline and silica supported bimetallic pyrophosphate catalysts of CuIIFeIII2(P2O7)2 were synthesized by incipient wetness method. The crystalline phase formation of both supported and unsupported catalysts is influenced by calcination temperatures and loading on the support. The XRD analysis confirmed the single phase of CuIIFeIII2(P2O7)2 formation of the bulk catalyst calcined at 800C for 72h. Crystalline phase of supported catalysts appeared when the loading was higher than 28 wt.%. On the surface of unsupported and silica supported catalysts the presence of very strong acid sites are determined. Activity and selectivity of the catalysts significantly influence the loading of pyrophosphate. Increase of CuIIFeIII2(P2O7)2 loading from 5 wt.% to 42 wt.% suppresses the conversion of methane from 14 % to 9 %, however, increases the selectivity to formaldehyde up to 11%.

Catalytic system for selective aerobic oxidation of amines to imines or nitriles involves commercially available copper(I) or (II) chloride as catalyst, toluene as solvent, and MS3A as dehydrating agent under an atmospheric pressure of oxygen. A variety of amines can be used as substrates for this oxidation system to get corresponding nitriles from primary amines (up to 97% yield; TON, up to 60) and the imines from secondary amines (up to 90% yield; TON, up to 45)[1]. High catalytic activity of Ru/Al2O3 catalyst was also observed at similar conditions[2]. It is possible to oxidize amines in the gas phase at higher temperatures and at atmospheric pressure molecular oxygen as an oxidizing agent [3]. The aim of the gas phase oxidation of amines was to discover potentially important reaction products. For the selective oxidation of amines different catalysts, based on alumina were used. All catalysts were made from γ-Al2O3. Alumina was impregnated with polyoxomatelates (NanH4-n[Si(W3O10)4].xH2O (n=0-4)) and zinc in deionized water. The oxidation of amine was performed in a fixed bed reactor with molecular oxygen (30-35 vol. % in the mixture with nitrogen) at atmospheric pressure and at temperatures of 180 - 185 °C. The reaction products were analyzed by GC (Chrompack GC9000) and identified by GCMS (Shimadzu QP 5000). Results and discussions: During the oxidation of linear aliphatic amines (N-hexyl, N-hepyl , and N–octylamine) in the gas phase the main oxidation products were nitriles. By the time on stream the amount of dimers were increased. Also oximes and nitrous compounds were observed in the reaction products in low concentrations. The conversion of amines approached 40-50%. The main products of the oxidation of cycloalkylamines were oximes and the condensation products of cyclohexanone and cyclohexylamine. The overall selectivity of oxime formation reached 40%, in the case of cyclohexanone oxime over 70 %. The dimeric by-products of amine condensation were also detected. The maximum of amine conversion approached 50-60% after 3 hour of time on stream and then it began to decrease. According to the obtained data of isobutyl- and isopentylamine oxidation, the products contained high amount of dimers. The isobutylamine was more resistant to the selective oxidation than isopentylamine. In the reaction products of these amines only traces of nitriles and imines were observed. Financial support from the Slovak Grant Agency VEGA 1/0768/08 is gratefully acknowledged.

The sedimentation of heavy glycerol phase is used as the first purification step
in biodiesel production.
In this paper, several models are presented, which satisfactory describe the sedimentation
of emulsion of the glycerol phase from the ester phase. The emulsion
for sedimentation measurements was gained after transesterification, demethanolisation
of the whole heterogeneous reaction mixture and adding of water.
Measurements are based on changes of the light absorption during the sedimentation
and monitoring of sediment amount (glycerol phase) by photographic
records. One model is derived from formal kinetics conception; the distribution
functions of particles of glycerol phase and simple sedimentation concept are
the basis of other models. The aim of creating models is to get reliable parameters,
which can be used for detecting of effects of raw material quality and
technological procedures. The knowledge of these parameters allows determining
the sedimentation stage in certain time as well as the time necessary to
reach request separation quality.

The distribution of ethyl esters, triglycerides, diglycerides and monoglycerides between the ester and glycerol phase were investigated after the ethanolysis of rapeseed oil at various reaction conditions. The determination of these substances in the ester and glycerol phase was based on the GC chromatography method. The amount of ethyl esters in the glycerol phase was unexpectedly high and therefore the effect of a heterogeneous reaction mixture composition on this amount was investigated. The distribution coefficients and weight distributions of each investigated substance were calculated and compared with each other. The distribution coefficients increase in this sequence: monoglycerides, diglycerides, ethyl esters and triglycerides. Soaps and monoglycerides in the reaction mixture cause worse separation of ethyl esters from the reaction mixture.

Catalytic cracking is a thermal decomposition of TAG in the presence of a catalyst (zeolites). The benefit of catalytic cracking before the pyrolysis is then in lower working temperature, lowered up to 100 °C in comparison to pyrolysis. Zeolite catalysts are crystalline alumino-silicate materials based on a three dimensional network of AlO₄ and SiO₄ tetrahedrally linked through oxygen atoms. Zeolites are porous and contain dimensionally defined pores with regions of high electrostatic field associated with the presence of cations. Pore size can be altered according the requirements on the product. The cracking occurs at the acidic centres in the inner part of the channels. The yield of process (catalytic cracking) is high; the share of liquid condensate represents 80 to 90 % wt. besides about 5 % wt. of gaseous products and about 5 % wt. of bituminous residue. There are no problematic wastes; the cracking residue can be used for energetic purposes. The liquid condensate has similar properties to fossil fuels –gasoline and diesel fuel. The type of input oil/fat affects the composition of liquid cracking condensate only in low measure.

By catalytic cracking of vegetable oils and animal fats at the presence of zeolite catalyst in batch operation at temperatures of 350 – 440 °C the liquid condensate is obtained with the yield of 80 – 90 %. After the light fraction removal by evaporation up to 150 – 180 °C in amount of 5 – 10 %, the treated condensate has similar GLC as that of fossil diesel fuel. In the article are results obtained with the synthetic catalyst NaY and with natural catalyst clinoptilolite are presented. The activities of both studied catalysts are practically the same. Liquid condensate after hydrotreating shows similar properties to fossil diesel fuel except the worsen CFPP parameter. A special two catalyst system allows significant lowering the acid value of the liquid condensate. The parameters of the blends of fossil naphtha and cracking products in amount of 7 % meet the standard EN 590. The cracking technology is simpler in comparison with transesterification of TAG to FAME with lower energy demand and does not need high quality oil/fat input.   

UTILIZATION OF BIOCOMPONENTS IN MOTOR FUELS PRODUCTION AT SLOVNAFT BRATISLAVA

Michal Šingliar SLOVNAFT, a.s., Bratislava, Member of MOL Group

Series of steps as well as a recent stage of the biofuels utilization process in motor fuels production at Slovnaft refinery is presented. Directives and support from the European Union and appropriate legislation of all member states are regarded as driving forces in this process. At motor fuels production with biofuels additivation a main emphasis is given on the European quality norms (EN 228, EN 590, EN 14 214 and EN 15 376). The process of biocomponents utilization in motor fuels production at Slovnaft started in 2004 by laboratory tests – mixing of fossil diesel with FAME. The plant for MTBE production was converted to bio-ETBE production plant in 2006 and consequently similar mixing tests of gasoline with ETBE and later on with bio-ethanol were performed. After successful tests, routine production of B5 (diesel with 5% FAME) and E5 (gasoline with 5% ETBE and ethanol) started. At the present time, diesel type B5 and B7 are produced and gasoline E5 as well. In perspective, B10 as well as E10 are under consideration.  

Glycerol phase is a sideproduct of biodiesel production, which contains also many another materials (soaps,rests of catalyst, water, esters …) formed by process of biodiesel production.The content of glycerol in this side product (glycerol phase) is 30-60 %.The target is to gain single components in more usable form by easy purificationand treatment of the glycerol phase. In this paper, it is presented haw to gainglycerol (purity 90 %) and mixture higher fatty acids with esters (1:1) oronly mixture of fatty acids (purity 99 %). The side product of thistreatment is potash-phosphate fertilizer. The optimal conditions of preparationof fatty acids mixture and glycerol were investigated.

Fatty acid methyl esters (FAME) were proven as alternative diesel fuels from renewable sources. Their drawback is limited availability, high price and the competition with food production. The attention is then oriented on non-edible oils/fats (jatropha oil, castor oil, tall oil), waste oils/fats and also on used frying oils (UFO) produced in high-capacity frying units. The procedure of FAME preparation from pretreated UFO is principally the same as that from virgin oils/fats. But the chemical changes in oils/fats during the trying are so extensive that they limited the utilization of such FAME for use as diesel fuel. In some cases the products of oxidation, hydration, decomposition and polymerization are present at higher level and FAME do not meet the standard EN 14 214. Lower ester content, higher viscosity, lower oxidation stability and higher CCT are observed despite the high conversion of acylglycerols to methyl esters. In the article, we discuss the possibilities of diagnostics of problematic components present in UFO as well as the treatment of UFO or final FAME to meet the standard quality

Vegetable oils and animal fats can be used directly without chemical conversion as a fuel in standard diesel engines provided that their viscosity is lowered. The high viscosity hinders the effective fuel atomization in the cylinder. Besides blending, micro-emulsions, cracking and transesterification, the fuel viscosity can be reduced also by fuel heating. Dual fuel operation of engine represents a new approach to solve the viscosity problem. Two fuel tanks are here, one for fossil diesel and second heated for oil/fat. The optimum operation is controlled by microcomputer between these two fuels. In the article are presented the power and emission characteristics of this way modified vehicle fueled by rapeseed oil, lard and chicken fat. Slightly lowered engine power output is caused by lowered energy content of used biocomponent. Emission characteristics and opacity are better or comparable with these of fossil naphtha.

Glycerol carbonate is a multifunctional compound usable as a solvent, chemical intermediate, additive etc. Synthesis of glycerol carbonate from bioglycerol and urea in the presence of suitable catalyst is an attractive method of production. Catalysts with Lewis acidic sites as compounds of zinc and zeolites produce satisfying results with significant yields. For the decomposition of intermediate product proper combination of temperature (110-150 °C ) a nd pressure (below 10 kPa) is very important.