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IBP2127_12 HIDROTREATMENT OF WAXES PRODUCED BY LOW LINEAR DENSITY POLYETHYLENE PYROLYSIS USING INDUSTRIAL CATALYST 1 2 Anie D.M.

Lima , Daniele O. Rosas , Carmen L.T. da Silva2, Rafael L. Fonseca3, Elton M. Canto4, Maurcio B.S. Junior5, Maria L.M. Valle5
Copyright 2012, Brazilian Petroleum, Gas and Biofuels Institute - IBP
This Technical Paper was prepared for presentation at the Rio Oi & Gas Expo and Conference 2012, held between September, 1720, 2012, in Rio de Janeiro. This Technical Paper was selected for presentation by the Technical Committee of the event according to the information contained in the final paper submitted by the author(s). The organizers are not supposed to translate or correct the submitted papers. The material as it is presented, does not necessarily represent Brazilian Petroleum, Gas and Biofuels Institute opinion, or that of its Members or Representatives. Authors consent to the publication of this Technical Paper in the Rio Oil & Gas Expo and Conference 2012 Proceedings.

Abstract
Municipal plastic waste reprocessing is configured as an alternative to minimize environmental impacts. Therefore, it was performed a pyrolysis process, in laboratory, with package waste plastic as the feed, consisting mostly of linear low density polyethylene (LDPE), in order to obtain high quality waxes and lubricant base oils. It was found the presence of unstable compounds in the waxes obtained. In this work, it was studied the use of Hydrotreatment (HDT) technology to treat these compounds, especially olefins, in a batch reactor. Two industrial catalysts were compared; one based on a prereduced Ni, and a the other was a presulphided Ni-Mo. The operating conditions were: 300 C temperature, 50 bar pressure, 60 mL of feed, 1 g of catalyst and 6h reaction time. Temperature and pressure profiles of the hydrogenation reactions showed that the severity may be attenuated. The process allowed the reduction of olefin content from 54% to below 2% wt, according to chromatography, and a significant improvement in the characteristics of color and light stability. No differences were observed between the two catalysts in terms of process or quality product. The study showed that waxes made from LDPE pyrolysis could be treated in HDT reactors with common industrial catalysts and milder operating conditions than those used for petroleum products.

1. Introduction
In the modern society, the plastics discovery represented a phenomenon to the raw material industry due to its durability, cost and lightness characteristics. However, the large scale use of plastic resins also brings back to society the responsibility for giving a correct treatment after using. Brazil produces 230.000 t / day of urban solid waste according to IBGE (2000). The plastic resins are 15 % of the dry waste obtained from the selective collection (CEMPRE, 2010). But only 19 % of the plastic waste were recycled, which put Brazil in ninth place in the world in this regard. Most of this solid waste will be disposed in the environment and can take up to 500 years to be degraded (Grippi, 2003). The trend is that each year this amount will increase. In the segregation of plastic waste collected, polyethylene, that is most used in the packaging sector, is in larger quantity, followed by polyteraphthalate (PET), polypropylene (PP) and polyvinyl chloride (PVC) (CEMPRE, 2010). One of the alternatives for reusing plastic bags is the chemical recycling, which is still incipient in Brazil. The pyrolysis process of plastics promotes thermal breakage of the chains and can be optimized to maximize products in a distillation range above 300 C, similar to lubricants and waxes, which are obtained from petroleum refining. Those products are more valuable than fuel. However, thermal cracking processes can lead to formation of unstable compounds, such as olefins. Among the most important characteristics for the desired products, are light and

______________________________ 1 Master, Process Engineer Petrobras 2 Master, Petroleum Chemist Petrobras 3 Chemical Technician Gorceix 4 Chemical Technician Petrobras 5 P.h.D, Chemical Engineer - UFRJ

Rio Oil & Gas Expo and Conference 2012 oxidation stability, and for this reason, it is important to perform a treatment of the products obtained by pyrolysis. Hydrotreatment (HDT) is the most often treatment used in petroleum industry to reduce aromatic, sulfur, nitrogen, oxygen, metals and olefins content. Therefore, this technology was chosen to stabilize the products obtained by pyrolysis (Da Silva, 2007). This paper reports the hydrotreatment exploratory study phase of waxes obtained by pyrolysis of waste plastic, based on linear low density polyethylene, using known technologies from the oil industry. The process was carried out in a Parr reactor, in batch, under operating conditions that simulate an industrial reactor, with two commercial catalysts, a prereduced based on Ni, and the other based on a NiMo presulphided. At this stage of the work, the objectives were: to compare products obtained in processes using different catalysts, to evaluate the process and the possibility of treating a feed with high content of olefins, and to verify if the sulfiding of Ni-Mo catalyst could contaminate the final product increasing total sulfur content and reducing quality.

2. Fundamentals
The hydrotreatment technology intends to allow aromatics hydrogenation and heteroatom removal from the feed, through chemical reaction with hydrogen in the presence of a catalyst, under certain conditions of temperature and pressure (Da Silva, 2007). The severity of this process is related to the characteristics of temperature, hydrogen partial pressure and space velocity, and depends on the characteristics of the feed to be treated. According to Da Silva (2007), hydrotreating reactions are: hydrodesulfurization, hydrodenitration, hydrodeoxygenation and aromatics, olefins, and organometallic compounds hydrogenation. In general, it wouldnt be expected that the sample obtained from pyrolysis, used as the feed in this study, contained contaminants like compounds with sulfur, nitrogen, metals and aromatics. This is not common due to the absence in the polyethylenes composition. However, low content of these compounds may occur due to external environmental contamination. Aromatic compounds can be formed during pyrolysis, depending on the conditions employed. But it was chosen to optimize pyrolysis operating conditions in order to minimize such elements. The nitrogen may be detected due to the presence in the inert gas that was employed during thermal cracking. Olefins formation is reported by Miller et al. (2005). Olefins and diolefins hydrogenation are fast and highly exothermic, requiring significant control of reactor temperature (Da Silva, 2007). Moreover, as Grange et al. (1996), the olefins are easily hydrotreatable, not requiring a high severity when compared to the hydrogen consumption and temperature required for conversion of aromatic rings. The unsaturated hydrocarbons or poly-unsaturated compounds are converted to less reactive compounds at lower temperatures and moderate pressures (Braga, 2009). Mixed sulphides that comprise Mo or W (group VI B metal) and Co or Ni (group VIII metal) are the catalysts more frequently used in hydrotreatment processes. The most common combinations are Co-Mo, Ni-Mo and Ni-W supported on -alumina with addition of promoters (silica or phosphorus) in order to improve performance. The catalysts based on nickel molybdenum (NiMo) and cobalt molybdenum (CoMo) are the most used in industrial reactors for hydrotreating petroleum fractions (Da Silva, 2007). Badawi et al. (2008) & Braga (2009) observed that the effect of nickel in the catalyst composition is always larger than Cobalt, whatever the olefin, due to the selective characteristic of catalysts containing cobalt for hydrodesulfurization. It is also mentioned that the presence of cobalt favors the isomerization of olefins. For this reason, in these exploratory tests it was chosen to study a prereduced catalyst based on Ni and another one, based on NiMo that was presulphided.

3. Scientific Methodology
3.1. Feed Characterization A sample of wax obtained by pyrolysis of plastic material based on linear low density polyethylene was used as the feed for the hydrotreatment. This product was characterized and compared to a commercial grade of wax, produced by petroleum refining, which is 140/145, that represents the range of melting points in Fahrenheit degrees. The objective was to identify parameters associated with the composition, which could be influence in the determination of operating conditions and catalysts to be used in hydrotreating process. The characterization of waxes is based on that performed for products obtained from petroleum refining. Color and appearance of a melted sample, by ASTM D1500 / 156, may show the degree of refining or indicate the presence of contaminants (heavy residues and oxidation products), and are, therefore, related to product stability. The properties of density and refractive index are normalized according to the standards ASTM D1298 and D1218, and also indicate the degree of refining of the wax. 2

Rio Oil & Gas Expo and Conference 2012 For a set of waxes, the more refined is the wax, the more free of contaminants, which, in general, are associated with the remaining oil in the sample. Oils have higher content of contaminants than waxes. The method ASTM D445 is used to determine flow resistance through viscosity of the completely melted wax. The melting point of waxes determines the grade and it can be measured by ASTM D87. The depth in tenths of a millimeter to which a standard needle penetrates into the wax under defined conditions standardized by ASTM D1321 represents the penetration, which measures the hardness. According to the dominant type of crystallization, waxes can retain a larger or lesser quantity of oil during the process of deoiling, which influences in penetration measurement. Marbling is a generic term that expresses forms of imperfection in waxes appearance and is not a standard, but a visual assessment, usually performed on the commercial waxes, due to its primary application, the candles market. The oil content test is based on ASTM D721. Simulated distillation test is analyzed as in ASTM D2887 and reports the temperatures at which the mass percentage of the sample has been evaporated. It can be considered an indirect measurement of the yield of the fractions that were in the original sample. The distribution of carbon chain can be obtained from 13C nuclear magnetic resonance. To evaluate the efficiency of HDT, it was analyzed olefin content in the feed and products by supercritical fluid chromatography as in Albuquerque (1998). Iodine content was another important data, based on ASTM D1959 part 29, which indirectly measures the amount of unsaturation. The sulfur content was measured in the product in order to verify the influence of presulphided catalyst in the quality of HDTs products, according to ASTM D5453-09. 3.2. Experimental Procedure Parr 4842 reactor used in the hydrogenation experiment has 250mL of capacity and a controller coupled. Feed and catalyst were loaded into the reactor that was inserted into a furnace. The agitation and temperature parameters were set in the controller. The pressure parameter (psi) was adjusted in the inert gas (N2) valve. Each test was 6 hours longer and this was determined based on tests with waxes derived from petroleum, and was controlled by the test performer. Then, the reaction was started. After hydrotreating, it was necessary to perform a filtration procedure to recovery the catalyst. Products were analyzed by supercritical fluid chromatography to evaluate the efficiency of the process in terms of content of olefins. The operating conditions were set to simulate an industrial fixed bed HDT reactor with 1 h-1 space velocity (LHSV). Operating conditions used in the experiment can be viewed in Table 1. Table 1. Operating Conditions used in HDT reactor Parr Operating Conditions H2 Pressure (Bar) (at 20 C) Temperature (C) Agitation (RPM) Feed volume (ml) Catalyst mass (g) Commercial Catalyst Reaction Time (h) Teste 1 50 300 200 60 1 Ni Prereduced 6 Teste 2 50 300 200 60 1 Ni-Mo 6

4. Discussions and Results


4.1. Feed Characterization Table 2 shows a comparison between the results of HDT feed and a commercial wax characterization. It can be observed that the characteristics of density, refractive index and melting point of the pyrolysis product are close to the commercial wax. Regarding performance, the absence of marbling is a positive point; however, the penetration rate was very high. This is associated with the presence of shorter chains with lower boiling points, as demonstrated by distillation data, and high oil content. Also, the wax originated from pyrolysis has a wider distillation range than the commercial wax and it can be separated into fractions according to the final application. Although the initial appearance was white like a hydrotreated petroleum wax, the sample took only two days to get yellow, due to unstable compounds oxidation. If it is necessary for its final application, this wax can go through a deoiling process to reduce oil content. In Table 3, it is possible to see the determination of compounds by supercritical fluid chromatography, which reveals a high content of olefins present in the wax obtained from pyrolysis. The high iodine content also reveals the presence of unsaturation in the sample. 3

Rio Oil & Gas Expo and Conference 2012 Tabela 2. Comparison between feed and commercial petroleum wax characterization Analysis Appearance Density 70/4C Viscosity at 100C (cSt) Melting Point (C) Refractive Index 70C Marbling appearance Penetration (1/10 mm) Oil Content (%wt) Sulfur Content (%wt) The most abundant Carbonic Chain (RMN) Simulated Distillation (%wt) 5/10 40/50 95/FBP Pyrolysis wax Yellow in two days 0.7808 3.141 59.6 1.4363 No 222.9 32.31 <0.001 C24 (C) 214 / 252 381 / 413 571 / 648 412 / 424 464 / 472 524 / 582 Commercial Wax White 0.7811 4.646 62.4 1.4364 Sim 14.3 0.998 <0.001 C28

Tabela 3. Compounds distribution and iodine content of waxes obtained by pyrolysis (HDT Feed) Analysis Iodine Content Compounds Distribution Saturated Olefin Total aromatic Results (Iodine g /100g) 79 (% m) 39.0 54.6 6.4

4.2. HDT Tests Figures 1 and 2 show the profiles of pressure in the reactor during the tests 1 and 2. In the figures, the step of pressure drop in the reactor indirectly indicates hydrogen consumption and it is observed that the values are close for both tests. When pressure is stabilized, it means that the reaction is completed. Both reactions were completed in about 40 minutes and in the next step of this study, it can be employed smaller test times.
Pressure Profile - Reaction 1 893 Pressure (Psi) 850 48 845

750

0 :0 05

0 :0 06

0 :0 04

0 :0 02

0 :0 03

0 :0 01

Figure 1. Pressure profile of reaction in Parr reactor with prereduced Ni catalyst (Test 1).

0 :0 00

Time (H:Min)

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Pressure Profile- Reaction 2 1000 950 900 850 800 750 700
0 :0 00

992 54 938

Pressure (psi)

Figure 2. Pressure profile of reaction in Parr reactor with presulphided NiMo catalyst (Test 2). Temperature and pressure profiles for one reaction are shown in Figure 3. It can be emphasized that the pressure drop begins at the stage of reactor pre-heating, indicating that temperature may be reduced in subsequent studies. A similar result was found for reaction 2.
Temperature and Pressure Profiles
Temperature [C] and Pressure [Psi]

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Time (H:Min)

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1000 800 600 400 200 0


00 5: 00 3: 00 4: 00 2: 00 1: 00 0:

Time [H:min] Temperature Pressure

Figure 3. Pressure and temperature profiles of reaction in Parr reactor (Test 1). 4.3. Products Characterization Tests 1 and 2 products, after filtration to remove the catalysts, can be observed in the liquid state, in Figure 4. No differences were observed regarding visual appearance. In Figure 5, it is possible to compare visual aspects in the solid state between test 1 product and a hydrotreated commercial 140/145 wax, derived from petroleum refining.

Test 1

Test 2

Figure 4. Melted waxes obtained after hydrotreatment and filtration. 5

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140/145 Wax (a)

Test 1 Wax (b)

Figure 5. (a) Hydrotreated wax from petroleum refining (b) Hydrotreated wax from LDPE Pyrolysis. Table 4 shows the results for olefins, sulfur and iodine content. Tabela 4. Compounds distribution and iodine content of hydrotreated waxes (HDT products) Analysis Total sulfur content (% wt) Iodine content (iodine g /100g) Compounds distribution by SFC (% wt) Saturated Olefin Total aromatic Test 1 <0,001 <2,0 93,0 1,9 5,1 Test 2 <0,001 <2,0 94,8 1,0 4,2

Figures 3 and 4 show reactions 1 and 2 pressure drops. It is observed that in the second test, hydrogen consumption was slightly higher, which may explain the higher content of the saturated product.

5. Conclusions
This paper showed preliminary results for a study of hydrotreating waxes obtained by pyrolysis of plastics material, carried out with operating conditions and catalysts mostly used in petroleum industry. Tests were conducted under similar conditions, but with different catalysts, one prereduced (Ni) and another presulphided (Ni-Mo) and showed that both could be used for this purpose. The operating parameters of time and temperature can be optimized in subsequent steps of the research. Hydrotreatment process was able to reduce the content of unstable compounds (olefins) from 54% to less than 2% wt, fact verified by the reduction of iodine content as well. The tests products showed a visual appearance similar to waxes obtained by petroleum refining. In these exploratory tests, it is possible to conclude that according to process results and product quality evaluation, catalysts employed did not show differences. The study demonstrated that waxes produced by LDPE pyrolysis could be treated in HDT reactors with the same industrial catalysts, but milder operating conditions than those used in petroleum industry.

6. References
ALBUQUERQUE, F. C. Determinao de olefinas em destilados mdios por cromatografia em fluido supercrtico. Rio de Janeiro, Relatrio Interno PETROBRAS, CENPES, DIQUIM, p. 26, 1998. ANP. Agncia Nacional do Petrleo, Gs e Biocombustveis, REGULAMENTO TCNICO ANP N 004/99, Republicada no DOU de 30/09/99, 1999. ASTM DIGITAL LIBRARY (2007). Disponvel em: http://www.astm.org/cgi-bin/SoftCart.exe/DIGITAL_LIBRARY/ BADAWI, M., VIVIER, L., PROT, G., DUPREZ, D. Promoting effect of cobalt and nickel on the activity of hydrotreating catalysts in hydrogenation and isomerization of olefins. Journal of Molecular Catalysis A, Chemical, v. 293, p.5358, 2008. 6

Rio Oil & Gas Expo and Conference 2012 BRAGA, E.B. Modelagem de um Reator de Hidrogenao de Gasolina de Pirlise Industrial, Dissertao de Mestrado, Universidade Federal do Rio de Janeiro, Rio de Janeiro, maio de 2009. CEMPRE. Compromisso Empresarial para a Reciclagem. Pesquisa CicloSoft 2010- Coleta Seletiva. 2010. Disponvel em: http://www.cempre.org.br/ciclosoft_2010.php DA SILVA, R.M.F.C. Modelagem Composicional e Cintica de Hidrocraqueamento de Fraes de Petrleo. Tese (Doutorado) Universidade Federal do Rio de Janeiro, Programa de Ps-Graduao em Tecnologia de Processos Qumicos e Bioqumicos, 2007. GRANGE, P., LAURENT, E., MAGGI, R., CENTENO, A. & DELMON, B. Hydrotreatment of pyrolysis oils from biomass: reactivity of the various categories of oxygenated compounds and preliminary techno-economical study, Catalysis Today, v. 29, p.297-301, 1996. GRIPPI, S. Lixo-Reciclagem e sua historia, Guia para prefeituras Brasileiras, So Paulo, Interferncia, p. 132, 2003. MILLER, S., HUFFMAN, G. P. & SHAH, N. Conversion of Waste Plastic to Lubricant Base oil, Energy & Fuels, v.19, p. 1580-1586, 2005.