Andrzej MIANOWSKI ? Department of Chemistry, Inorganic Technology and Fuels, Faculty of Chemistry, Silesian University of Technology, Gliwice, Poland

Please cite as: CHEMIK 2013, 67, 5, 423?434

Introduction

One can put forward a claim that the degree of civilization development depends on two factors: the way of obtaining energy and the way of energy consumption. Together with the sustained development strategy, which aims at slowing down the process of using up natural and energy resources and the irreversible changes in the natural environment of the Earth, two target models of human civilization development have appeared. Let us summarize ?Introduction? to monograph [1] by saying that the first model is a closed system of manufacturing and consumption of goods, which exchanges only energy with the surroundings. In the other model, the system is constructed from renewable sources of materials and energy carriers; consequently, the post-consumer waste is naturally degraded.

Thus, in the first model, civilization development and the level of technological progress depend not only on the way of manufacturing and consumption of goods, but also on the effective use of energy. The life cycle of materials defines the level of technological progress, but is linked with the necessity of preventing emissions, waste utilization and effective use of relevant sources of external energy, internal energy and recirculation. Links of this kind may be interpreted using the ?cross? principle. One only needs to turn Figure 1 by 90 degrees clockwise to see that manufacturing of goods, marked by the materials ? products axis, becomes a secondary issue in relation to using more or less advanced solutions in the scope of environmental protection.

The presented schema (Fig. 1) is the simplest illustration of Life Cycle Assessment from cradle to grave. Comparison of the systems shows us that nature deals very well with what it knows when natural proportions are preserved, whereas plastics manufactured by the man (anthropogenic plastics), nota bene mainly derived from crude oil, are foreign bodies which do not get naturally degraded in a reasonable period.

Recycling, or energy recovery of post-use (post-consumer) waste plastics (WP; Polish: OTS), is an important element of sustained development in Poland. Judging from illustrations and data included in monograph [1], the state in Poland is very distant from solutions used in Europe and remains highly unsatisfactory.

WP and alternative fuels

To put it simply, an alternative fuel is a fuel obtained in the recovery process of waste with a calorific value. Post-use waste plastics (WP), which constitute as much as 10% of the total waste mass, contain 65?75% of PE+PP (waste polyolefins ? WPO; Polish: OPO), 8?11% of polystyrene (PS), 7?10% of PET and 7?10% of PVC [3]; the shares of particular substances depend on the degree of recycling, which is linked with the level of civilization and ecology awareness.

In view of [3, 4] it is known that WP are valuable carriers of chemical enthalpy characterised by high calorific value ? see Table 1 [5]. WP contained in alternative fuels are predominantly a sum of PE + PP + PS and are characterised by a calorific value of over 40 MJ/kg. Plastics with lower calorific values are a minority. For instance, PVC is harmful as a fuel component due to chlorine content, while PETs form aggressive functional groups with oxygen during cracking and thus have an adverse effect both on the quality of motor fuel and on the possibility of terephthalic acid sublimation in its thermal processing. The presence of PVC and PET (summarized share) also results in the fact that, in thermal processing, the chlorine from PVC passes to the organic layer [6] and not to the aqueous layer in the form of HCl, which always exists in those processes.

Due to the abovementioned reasons, in the following part of the article, WPO are analyzed for the purposes of energy-related use. It is assumed that PS is an ?aromatic? polyolefin, but one should take into account the fact that lower aromatic hydrocarbons (benzene, toluene etc.) as well as PAH (polycyclic aromatic hydrocarbons) may form in the processes of its combustion or in the products of its processing.

WP are most valuable as solid fuels when they are a mixture of polyolefins (WPO), i.e. various kinds of PE with an addition of PP, possibly with a small amount of PS (up to 10%); unfortunately, they are often contaminated by PVC and PETs. Fulfilling expectations in the scope of high calorific value is not enough. A specific alternative fuel variety, increasingly better known in Poland as SRF (Solid Recovered Fuels), requires comparison with the classification presented in Table 2 at the beginning of the assessment.

One experiences a purely practical problem here: in view of the data in Table 1 for SRF acc. to CEN/TS 15359:2006, WPO fulfil the calorific value criterion, but it is extremely difficult to demonstrate lack of chlorine and fluorine, as well as mercury and other heavy elements (Sb, As, Pb etc.) on an established level. SRF cannot contain fossil fuels or dangerous waste. Currently in Poland the following standard is binding: ?Stałe paliwa wtórne ? wymagania techniczne i klasy? (Solid recovered fuels ? technical requirements and classes) PN-EN 15359:2012. In this case, excessive caution is exercised in industrial use because it is impossible to exclude the presence of the abovementioned harmful halogen elements, especially heavy elements, in municipal waste or in WPO incorrectly separated from the total WP mass.

Thus, using SRF in commercial and municipal energy management requires applying for appropriate certificates and permits. A basic difficulty is the fact that fuels containing waste with a particular code cannot be directly used in this sector. Table 3 shows the most valuable waste in terms of calorific value which could be used to manufacture formed fuels were it not for legal obstacles [7].

An example of a very interesting solution, though not yet applied in commercial and municipal energy management, is patent description no. PL 212399 [8]. PHU PETROMA S.J. company from Katowice owns a manufacturing installation in Siemianowice (see Figure 1). The following are used there to manufacture granulated fuel (data from 2010):
? coal slime from an own excavation line from the bottom of the Rzeczyce (Dzierżno Duże) water reservoir
? waste polyolefins (WPO) with a significant predominance of polyethylene
? plasticisers.

Coal slime as waste from the flotation enrichment of coal without dangerous substances has the 01 04 81 code, while coal slime excavated from water reservoirs is classified as combustible waste (alternative fuel) and has the 19 12 10 code.

As stems from Table 3, highly calorific WPO are classified as waste (they have an appropriate code) and an additional difficulty is the accidental share of waste with PVC (i.e. containing chlorine).

In rotary drying (temperature up to 150°C), in the coal-polyolefin mixture polyolefins begin to melt and granules are formed with the following (approximate) properties:
a. total humidity content ? 12%
b. ash content (working state) ? 14%
c. calorific value (working state) ? 20?28 MJ/kg ? depending on the share of WPO
d. the content of: chlorine ? 0.15%, sulphur ? 0.7% and mercury ? 0.6 ppm.

The fuel was tested and assessed by many competent institutions: Institute for Chemical Processing of Coal (IChPW), Central Mining Institute (GIG) and the Silesian University of Technology ? Department of Technologies and Installations for Waste Management. Multifaceted tests have shown that:
? acc. to the EU standard CEN/ST 15359:2006, it is a solid recovered fuel (GIG)
? it is given the following class of code: NCV 1, Cl 1 and Hg 2 (GIG), but also NCV 3, Cl 1, Hg 2 (GIG).

Additional analyses show a lower CO2 emission indicator in comparison to steam dusts/slimes with a similar calorific value.

There are many possibilities for unsorted WP, i.e. those which may contain chlorine (from PVC) and sulphur from fillers or from added and accidental substances. One technology was developed by IChPW (Zabrze) and Industrial Chemistry Research Institute (ICRI) (Warsaw) and is known as KARBOTERM? [9÷11].

According to the description in [9], the essence of this solution consists in homogenization of WP in the coal tar pitch or crude oil pitch in the recommended 4:1 ratio and the temperature of 350°C. The result is thermodestruction with depolymerisation and deep dechlorination (used to produce HCl). The hot, fluid thermolysate mixes with ground coal, whose quality depends on further use (mainly for the purposes of coking industry) because Karboterm may be considered as an orthocoking coal substitute. If steam coals are used in this technology, the resulting solid product with specified geometric forms can be used for heating purposes with the reservation that this is an expensive fuel. According to [9], the subsidies are estimated at the level of up to PLN 200/Mg of WP (2006).

Combustion of WP in industrial furnaces

The possibilities of energy recovery mainly from WPO are observed in industrial furnaces with full process hermetisation. One can distinguish the following:
? cement kilns
? forges, blast furnaces.

Cement kilns are leading installations for combusting (co-combustion) of a wide range of waste [12], including WP, but the possibility of combusting car tyres is a huge competition for that. It is understandable: handling cut tyres (with a lower calorific value than WPO) is easier than handling a WP mixture obtained in various ways, and the necessity to avoid chlorine content also matters here. Nonetheless, in many EU cement plants WP is used and relevant limits in the scope of the share of chlorinated organic compounds and heavy metals are regulated [13]. The share of sulphur compounds does not matter because the amount of sulphur in rubber waste from car tyres equals 1?2%, which is not disqualifying. In Poland, cement plants, which are virtually foreign entities, use rubber waste with success, often importing it (based on a relevant permit). The data from 2004 shows that in Poland, the share of energy obtained from waste generated in the process of baking clinker (cement plants) equalled 4%, while in the Netherlands this share equals 54% [13]. Still, we note significant progress in this matter; a dozen Polish cement plants act in the scope of energy recovery from packaging waste, processing those materials in cement kilns in the temperature of approx. 1400°C, where nearly all chemical compounds are decomposed. Grupa Ożarów SA owns a specialist line for combusting polymer materials which can process approx. 45,000 Mg of materials a year. This solution allows for decreasing coal use by 17,000 Mg, which is both economically and environmentally justified. Analogous examples of enterprises using that type of alternative fuels are: Dyckerhoff Polska Sp. z o.o. ? Nowiny Cement Plant in Sitkówka-Nowiny, Warta SA Cement Plant in Trębaczew, Chełm SA Cement Plant, Górażdże Cement Plant, Rejowiec SA Cement Plant and Małogoszcz Cement Plant. Already in 2006 it was estimated that heat recovery from alternative fuels constituted 18.3% of total energy required to manufacture cement clinker [14].

Figure 2 shows a typical rotary kiln for manufacturing cement (clinker) as outlined in item [15]. A much bigger potential exists in the blast furnace process owing to two possibilities of dosing WP, mainly as WPO:
1. acc. to the technology analogous to the one known as PCI (Pulverized Coal Injection), through the lances in the nozzle zone of the blast furnace: blow-in of ground plastics.
2. in the form of pellets, delivered alternately and in layers from the top together with the remaining compounds of the blast furnace charge (self-fluxing sinter, coke, admixtures, slags).

Figure 3 shows the possibility of preparing PCI-type WPO [16]. Theoretical considerations prove that this is a very reasonable technological solution [17] and industrial tests made by the Institute for Ferrous Metallurgy (IMŻ) showed that one can use 7 kg/Mg of pig iron [9]. Japanese analyses contain more beneficial indicators, i.e. 10 kg/Mg of pig iron [17]. The discussed concept of utilisation of ground (5?10 mm) WP was applied in the Stahlwerke Bremen steelworks (Germany), in NKK Keihin (Japan) and Pohang Works (South Korea) [9, 17]; in a different version, i.e. in the form of pelleted polymer plastics, it was implemented as a pilot installation in the Voestalpine Stahl Linz GmbH steelworks (Austria, 2003). This technology allows for saving 150,000 Mg of crude oil a year [18].

In these solutions, particular attention is paid to the presence of PVC; for instance, in Japan, chlorine volume was accepted at the level of max. 0.5% [9], or at least below 1% [19] due to the control of chlorine charge in the blast furnace charge, not higher than 0.05% [20]. Owing to these reasons, the blast furnace process should be supported by WPO without PVC, but the share of PS and PETs is not excluded. In Poland, raw steel steelworks are the property of a foreign company ? Arcelor Mittal Poland SA, so we do not known if the discussed solution is used there.

Waste polyolefins as liquid fuels

Direct pyrolysis of WPO, both in the thermal and thermalcatalytic process, enjoys huge interest. This time, WPO shall denote polyethylene (PE) (which dominates), polypropylene (PP) and small amounts (approx. 10%) of polystyrene (PS), as this one also appears in waste.

Thermal decomposition of polyethylene (PE) without the presence of a catalyst proceeds according to the radical mechanism [21, 22]. In the presence of acidic catalysts it may proceed according to the ionic mechanism. The following are formed in various process conditions:
? 80?85% of liquid or semi-liquid (solidifying) fraction
? 5?8% of gaseous fraction
? minimum 5% of post-reaction fine coke.

From the technological point of view, liquid fraction is the most valuable. It is usually a mixture of C5?C27 hydrocarbons with simple chains (n-alkanes) at first, but every break of an aliphatic bond results in formation of unsaturated hydrocarbons, alkenes and alkadienes, which is not beneficial as regards usefulness of motor fuels. The initiated pyrolysis process of the formed hydrocarbon from the polymer chain is clarified by the following notation; double bonds usually occur at the beginning of the chain [23]:

The amount of unsaturated hydrocarbons in a liquid mixture equals 45?55% w/w [24], but can be both much lower (20?24% w/w) [25] and much higher. In examinations of products from the industrial installation the amount of unsaturated hydrocarbons in the boiling fraction of up to 200°C (petrol) was determined to exceed 80%, while in the boiling fraction of 200?320°C (fuel oil ? FO) ? even 65%, which disqualifies that fraction as a ready component of FO. A certain amount of iso-hydrocarbons also forms, as well as ? if active acidic catalysts (such as zeolites) are used) ? aromatic hydrocarbons, i.a. benzene (unfavourable in this respect), which can also form from PS. Due to the economic usefulness in the scope of motor fuel blending, strict quality criteria are currently binding; these have changed significantly in the last 10 years (Table 4).

Remarks
1. CN = 58 is recommended.
2. Naphthalene is meant here by PAHs; the aim is the reduction of its share to 1% w/w.
3. Chlorine content: less than 100 ppm.
4. RON ? Research Octane Number.

Table 4 shows that both petrol and fuel oil (FO) must be sulphurless fuels (<10 ppm). The share of unsaturated hydrocarbons is restricted to 18% v/v in petrols (in FO they do not occur because the traded product has undergone hydrorefining/cracking); the share of aromatic hydrocarbons is also limited. Table 4 does not include other very important physical and chemical properties, i.e. the distillation curve, which defines the boiling range, and the rheological characteristics (viscosity, density). An important parameter for petrols is flash point (-51°C), while for FO ? flash point (+56oC) and the cold filter plugging point (cloud point is connected with it) ? even -32°C, but one more important aspect must be highlighted here. It is commonly assumed that the FO boiling range is determined by C12?C16 hydrocarbons. The boiling point at the atmospheric pressure for hydrocarbons with extreme parameters is 215?217°C for C12H26 dodecane and 283?286°C for C16H34 hexadecane (cetane). Still, the solidification point of dodecane (tt =17.5?18.5°C) is above 0°C, so the share of dodecane and its related homologues in FO should be limited. The abovementioned reasons point to the unavoidable necessity of hydrogen treatment for products coming from the thermal-catalytic decomposition of WPO.

In Poland, significant industrial technologies are based on three rather different technologies:
1. catalytic copyrolysis in process oil, where the share of WPO is 25% w/w in paraffin oil [28, 29]; in the version given in [30], it was possible to connect the main tank reactor (32 m3) with saturation reactors (4 m3), which increased the share of WPO to 40% w/w.
2. a thermal-catalytic process of a periodic nature, implemented in two-stage modules (melting and pyrolysis) acc. to first concepts by Speranda Sp. z o.o., as well as many other similar solutions.
3. a continuous catalytic process in a tubular reactor (scale: 200 Mg/ month) installed by TKF.

ARKA, Sp. z o.o., based on concepts by prof. J. Walendziewski and his associates. The technologies listed as item 1, 2 and 3 are discussed in [3, 4, 31], while references to technology 1 stem from the author?s participation in that undertaking. In Poland, liquid products have been given the KTS-F (?plastic component-fractions? ) symbol as a harmonised product ? PKWiU (Polish Classification of Goods and Services) no. 24.66.32?90.00,

CN:38?11 ? and were subject to material balancing by fiscal warehouses. In the case of solutions 1 and 2, KTS-F products were purchased by the former refinery in Jasło (currently Grupa LOTOS Jasło). The refinery also had its own Plastic Processing Plant (acc. to patent solutions [28, 29]). The purchased products and the products from the refinery?s own line were joined and then divided into two fractions:

as well as remains for composing heating oils.

Hydrogen treatment, acc. to the patent description in [32], was commissioned to the refinery in Jedlicze (currently Grupa ORLEN). Figure 4 is a simplified process schema of the whole solution. Technology 3 was implemented for own needs (a heating oil component). One should notice that in the final stage of operation, many units using technology 2 adjusted their installations to conduct copyrolysis with use of available (especially waste) oils or even crude oil, which led to discrepancies in excise rates.

Economic analyses performed by the refinery in Jasło have shown that the process is loss-making; the technical cost of manufacturing KTS-F with distillation is approx. PLN 2300/Mg [33]. However, the cost was lower for other units, which only manufactured the liquid product, and the process brought profit owing to the Regulation of the Minister of Finance [34], which exempted an entity from excise if the component was obtained as a result of catalytic processing of WP [35] according to established rates (Table 5).

In fact, in order to legally obtain the exemption from excise, it was sufficient if (§ 17, item 2 and 3 in [34]):
a. leaded and unleaded motor petrols contained at least 5% of the processed component
b. fuel oil contained at least 10% of it.

Owing to withdrawal of the exemption from excise, all installations related to manufacturing and refining of KTS-F for the variant of motor fuels were closed down on January 1st, 2007.

To sum up the period which ended on December 31st, 2006, one should state that:
1. as a result of a grass-roots economic initiative, a ?small? fuel sector appeared which manufactured motor fuels from hardto- decompose WPO; based on the agreement between Grupa LOTOS (Jasło) and Grupa ORLEN (Jedlicze) and domestic KTS-F manufacturers, valuable components of FO and petrols of the Pb 95 grade were produced.
2. in the scope of the KTS-F initiative, approx. 40% w/w of highboiling fractions could be used as heating oil components. The price of those oils on the market varies considerably ? the range is PLN 900?1900/Mg, so the connection within the fuel sector could have been complete due to competitiveness (Fig. 4).
3. a weak side of the undertaking was the sudden suspension of activity, which resulted in bankruptcy of companies manufacturing KTS-F (approx. 4,000 employees were made redundant [31]).
4. the remaining small share consisted of installations working to satisfy own needs (heating oil).

Assessment and summary

Prof. M. Górski [36] reckons that ?alternative fuel? does not have the nature of a legally defined term. The abovementioned waste with the 19 12 10 code are defined as combustible waste coming from the mechanical treatment of waste. These can be coal or rubber waste, WP recovered via mechanical processes or even alternative fuels (they were given that code, too). For the purposes of manufacturing liquid fuels via chemical recycling, waste with a defined purity degree are the most beneficial, preferably coming from a known source and not separated from municipal waste. According to [37], industrial tests were made in BASF (Ludwigshafen), Fuji Technology (Japan), Conrad (Canada), Hamburg Pyrolysis and BP Chemicals in various ways: in a reactor, in retorts or in a fluidized bed, but these methods are not attractive due to the loss-making nature of the process. The relatively advanced research conducted in Poland is only at the laboratory stage. Two interesting variants are: thermal-pressure processing of WPO in methanol (with use of catalysts) [38] and two-stage refining of KTS-F with syngas (2H2+CO from the decomposition of methanol) in a catalytic process at the atmospheric pressure [39].

It seems that the ?small? fuel sector with WPO, which existed in Poland in they years , had no counterpart in Europe as regards the organisational and technological aspect as well as the industrial scale: it is estimated that at least 50,000 t of KTS-F liquid fuels were manufactured in 2006 [3]. Looking back on the matter from 2007, the ?small? fuel sector will certainly not be restored. Such possibility was not even mentioned at the 2012 conference on fuels from waste held in Chorzów (listed in references of [36]). The issues of heating oil manufacturing are not discussed, either, which is surely related to a rather saturated market in this respect. Let us therefore pay attention to the problems and suggestions included in the introduction, together with the ?cross? principle and LCA, and think at what stage of development we are in this regard.

However, owing to the EU-imposed necessity to recover plastics from plastic (mainly polyethylene) packaging waste in the amount of 22.5% (deadline: 2014), one cannot exclude that greater attention will be paid to manufacturing WP (WPO) from alternative fuels, maybe under the acronym of SRF. Failure to comply with the obligation results in sanctions: EUR 200,000/day and 1% deficiency. Current estimations of the actual recycling level are too varied, but the widely available data of the PlasticsEurope Poland foundation are promising.

Literature
1. Kijeński J.: Wprowadzenie [w:] Odzysk i recykling materiałów polimerowych. Praca zbiorowa pod redakcją: J. Kijeński, A.K. Błędzki, R. Jeziórska. WN PWN, Warszawa, 2011.
2. Zieliński S.: informacja prywatna. Politechnika Wrocławska.
3. Mianowski A., Walendziewski J., Baraniec-Mazurek I., Siudyga T., Tokarska A.: Termiczny i termokatalityczny rozkład poliolefin (punkt 3.1 i 3.2) [w:] Odzysk i recykling materiałów polimerowych. Praca zbiorowa pod redakcją: Kijeński J., Błędzki A.K., Jeziórska R.. WN PWN, Warszawa, 2011.
4. Mianowski A.: Odpady z tworzyw sztucznych jako źródło paliw stałych i ciekłych. Instalacje przemysłowe w Polsce [w:] Odpady i opakowania ? nowe regulacje. Wyd. FORUM Sp. z o.o., Poznań, 2011, page 1?36 i 1?14.
5. Wandrasz J.W., Wandrasz A.J.: Paliwa formowane (biopaliwa i paliwa z odpadów w procesach termicznych). Wyd. ?Seidel-Przywecki? Sp. z o.o., Warszawa, 2006.
6. Mianowski A.: Wpływ podstawowych czynników technologicznych na jakość frakcji paliwowych powstałych z termodestrukcji wybranych tworzyw sztucznych. Z.N. Wydziału Budownictwa i Inżynierii Środowiska, Politechnika Koszalińska, 2005, 22, 533?544.
7. Wasielewski R., Sobolewski A.: Utylizacja odpadowych tworzyw sztucznych przez koksowanie ? przemysłowe próby koksowania mieszanki węglowej z dodatkiem przetworzonych OTS. Karbo 1998, 11, 347?350.
8. Domański M., Libiszewski Z., Rak S.: Sposób granulowania mułów węglowych. Patent polski nr 2121399 (zgłoszono 26.03.2009).
9. Sobolewski A., Wasielewski R.: Zagospodarowanie odpadowych tworzyw sztucznych w procesie wielkopiecowym. Chemik 2006, 59, 221?225.
10. Karboterm ? waste plastics conversion into coke. Prospekt IChPW i IChP.
11. Wasielewski R., Sobolewski A., Polaczek J.: Energetyczna waloryzacja odpadowych tworzyw sztucznych. INSTAL 1999, 10, 32?33.
12. Piecuch T.: Zarys metod termicznej utylizacji odpadów. Politechnika Koszalińska, Koszalin, 2006.
13. Pająk T.: Termiczne przekształcanie i współspalanie wysokokalorycznych frakcji odpadów komunalnych [w:] Postępy w technologii tworzyw sztucznych. PROCHEMIA 2005, Warszawa.
14. Żakowska H., Nowakowski K., Grochocka M.: Odpady opakowaniowe jako źródło energii. Opakowanie 2008, 11, 24.
15. Ann.: Odzysk energetyczny odpadów w piecach cementowni Górażdze. Wykład w ramach ?Dzień Górażdzy w AGH?, Kraków, 19.11.2007 r.
16. Asanuma M., Ariyama T., Sato M., Murai R., Nonaka T., Okochi I., Tsukiji H., Namoto K.: Development of waste plastics injection process in blast furnace. ISIJ International 2000, 40, 244?251.
17. Ziębik A., Stanek W.: Odpady plastikowe ? paliwo zastępcze w wielkim piecu [w:] praca zbiorowa pod redakcją Wandrasza J.W. i Nadziakiewicza J.: Paliwa z odpadów. Wyd. Helion, 2001, III, 65.
18. Stowarzyszenie Producentów Tworzyw Sztucznych Plastics Europe: Tworzywa sztuczne przekształcają rudy żelaza w stal. Recykling surowcowy w piecach hutniczych. 2009.
19. Okuwaki A.: Feedstock recykling of plastics in Japan. Polymer Degradation and Stability 2004, 85, 981?989.
20. Koszorek A., Mianowski A.: Możliwości i ograniczenia w wykorzystaniu klasycznego procesu koksowania jako metody utylizacji odpadów przemysłowych. Rocznik Ochrona Środowiska 1999, I, 27?56.
21. Lattimer R.P.: Pyrolysis field ionization mass spectrometry of polyolefins. J. Anal. Appl. Pyr. 1995, 31, 203.
22. Buekens A.G., Huang H.: Catalytic plastics cracking for recovery of gasolinerange hydrocarbons from municipal plastic wastes. Resources, Conservation and Recycling 1998, 23, 163.
23. Mianowski A., Tokarska A.: Wodór dla sektora małych i średnich przedsiębiorstw. Przemysł Chemiczny 2007, 84, 829?832.
24. Tokarska A.: Wodorowe uszlachetnianie ciekłych produktów pirolizy odpadowych poliolefin. Cz. I. Polimery 2011, 56, 484?488.
25. Tokarska A.: Wodorowe uszlachetnianie ciekłych produktów pirolizy odpadowych poliolefin. Cz. II. Polimery 2011, 56, 585?590.
26. Rozporządzenie Ministra Gospodarki z dnia 9 grudnia 2008 r. w sprawie wymagań jakościowych da paliw ciekłych (Dz. U. nr 221/2008, poz.1441).
27. Dyrektywa 98/70/EC z dnia 13 października 1998 r. odnosząca się do jakości benzyny oraz oleju napędowego, zmieniająca dyrektywę Rady 93/12/ EWG.
28. Kałyniak P., Mianowski A., Furtan J., Jelonek K., Kozaczko J., Kozłowski E.: Sposób wytwarzania paliw płynnych z odpadów z tworzyw sztucznych i urządzenie do realizacji tego sposobu. Patent polski nr 191341 (zgłoszony w 1999 r.).
29. Mianowski A., Tokarska A., Kałyniak P.: Zastosowanie addytywu mineralnego do termicznego rozkładu odpadowych poliolefin. Patent polski nr 195034 (zgłoszony w 2000 r.).
30. Mianowski A., Kałyniak P., Kiełtyka A., Bodora K., Siudyga T.: Sposób przygotowania i przechowywania odpadowych tworzyw sztucznych dla procesów termodestrukcyjnych. Patent polski nr 200499 (zgłoszony w 2003 r.).
31. Mianowski A.: Krajowe technologie wytwarzania paliw płynnych z odpadowych poliolefin. Recykling 2009, 9, 24.`
32. Tokarska A., Mianowski A., Kałyniak P., Kozłowski E.: Sposób wytwarzania paliw płynnych z odpadów z tworzyw sztucznych. Patent polski nr 192014 (zgłoszony w 2000 r.).
33. Franek J.: Przerób odpadowych tworzyw sztucznych w LOTOS Jasło SA. Prezentacja przedstawiona na seminarium w Jaśle, 27.09.2007 r.
34. Rozporządzenie Ministra Finansów z dn. 26.04.2004 r. w sprawie zwolnienia od podatku akcyzowego (Dz. U. nr 97, poz. 966, 2004).
35. Rozporządzenie Ministra Finansów z dn. 26.12.2004 r. w sprawie obniżenia stawek podatku akcyzowego (Dz. U. nr 279, poz.2763, załącznik nr 1, 2004).
36. Górski M.: Paliwa alternatywne w nowych przepisach o odpadach [w:] II Ogólnopolska Konferencja Szkoleniowa: Paliwa z odpadów ? rynek odpadów jako rynek energii. Chorzów, 30.05?1.06.2012 r.
37. Metecan I.H., Ozkan A.R., Isler R., Yanik J., Saglam M., Yuksel M.: Naphta derived from polyolefins. Fuel 2005, 84, 619?628.
38. Baraniec-Mazurek I., Mianowski A.: Liquid fuel from waste polyolefins. Część II. Chem. Eng. J. 2010, 163, 293?299.
39. Kijeński J., Śmigiera E., Osawaru O., Migdał A., Mianowski A., Korpoliński A., Nemtusiak M., Rogieński M.: Sposób uwodornienia frakcji węglowodorowej z przerobu odpadów polimerowych. patent polski nr 210518 (zgłoszony w 2009 r.).

Andrzej MIANOWSKI ? (SC.D., Eng.), Professor, is a graduate of the Faculty of Chemistry of the Silesian University of Technology (1970). Mr Mianowski obtained his doctoral degree in 1976 and the degree of habilitated doctor in 1988. He was awarded the title of Full Professor in the field of technical sciences in 2001. At the moment Mr Mianowski is employed as full professor in the Department of Chemistry, Inorganic Technology and Fuels of the Silesian University of Technology, and the Institute for Chemical Processing of Coal in Zabrze. Scientific interests: coal technology, solid waste disposal, technological and industrial aspects of thermal analysis. He is the author or co-author of over 150 publications, 30 patents granted and pending, including several implemented patents, the co-author of several books, course books and over 120 lectures. He promoted 11 doctors of technical sciences, including 3 with distinction, and is currently supervising another two doctoral candidates.
e-mail: ;
phone: