Clean Techn Environ Policy (2008) 10:121130 DOI 10.

1007/s10098-007-0132-5

ORIGINAL PAPER

Catalytic and thermal cracking of selected polyolens

Jozef Mikulec Miriam Vrbova

Received: 9 February 2007 / Accepted: 28 May 2007 / Published online: 11 January 2008 Springer-Verlag 2007

Abstract Feedstock recycling is a promising alternative for the management of plastic wastes, as it may allow these residues to be transformed into valuable products for renery and/or petrochemical industry. Catalytic degradation of polyolen was carried out in a pilot scale reactor Blowdec operating in the temperature range of 340 470C. The catalysts used in this study were natural zeolite Clinoptilolite, ZSM-5, HZSM-5 and their mixture in various volume ratios. Both thermal and catalytic cracking of low-density polyethylene (LDPE), high-density polyethylene (HDPE), polypropylene (PP) and their mixture have been investigated. Liquid products were checked in selected renery and petrochemical processes as feedstocks on the model pyrolysis equipment and with the help of MAT test (microactivity test). Keywords Catalytic degradation Plastics Zeolites

Introduction Various kinds of waste became an inherent part of our lives. Waste may split out of our control, but even so may not... it depends how we shall be able to manage it. Mass-produced plastics (PE, polyethylene; PP, polypropylene; PS, polystyrene; PVC, polyvinylchloride) and technical oils represent the major source of waste from crude oil products (Vesely 1967). Plastics belong to the materials, which are hard to recycle and are most harmful for the environment, because they can be found in various
J. Mikulec (&) M. Vrbova Slovnaft VURUP, a.s., Vlcie Hrdlo, P.O. Box 50, 820 03 Bratislava, Slovak Republic e-mail: jozef.mikulec@vurup.sk

forms in the market. Current forms of managing this type of waste are not satisfactory even in the advanced countries. The key factor of the present situation is represented mostly by the economic aspects. Economically and logistically demanding collection of waste (primarily of plastics), its subsequent treatment (sorting, cleaning) prior to recycling increases the overall costs, and the nal recycling products are more expensive than equivalent products made from crude oil directly. Thermal or catalytic cracking of waste plastics is one of the possible methods of their utilization. The main part of waste plastic materials for which raw material (chemical) recycling is applicable includes PET, PP, LDPE, HDPE, PVC and polystyrene (Vesely and Mostecky 1989). Chemical recycling represents a feedstock saving, and thus is very interesting for renery and petrochemistry (Garforth et al. 1997). Using processes such as pyrolysis, gasication, coking, hydrogenation and depolymerization, the fractions rich in gasoline, kerosene, gas oil, heating oil are formed with the quality that is fully comparable to those of the primary products (Hronec et al. 1995).

Experimental section Materials and analytical procedures As the processed feedstocks, polypropylene TATREN MI 927, polyethylene BRALEN LDPE RF 01, a mixture of polyethylene HDPE TIPELIN BA 550-13 with polyethylene HDPE FS 471-02 manufactured by Slovnaft a.s. in a mass ratio of 1:1 and a mixture of LDPE/PP/PS in a volume ratio of 6:4:1 (LDPE and PP were produced by Slovnaft a.s. PS from an out-of-function refrigerator was used) were investigated.

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To analyze the products of PP, LDPE, HDPE and their mixture, the following standard analytical techniques currently used for the characterization of crude oil fractions were applied: density at 40C according to STN EN ISO 12 185 or STN EN ISO 3838 kinematic viskosity at 40, 70 and 100C according to STN EN ISO 3140AC off-gas GC analysis according to UOP 53987 GC analysis of depolymerization products according to ASTM D 5134 distribution by boiling temperature (simulated distillation) of depolymerization products according to ASTM D 2887 bromine number according to STN 656185 FIA according to ASTM D 1319 and STN 65 6152 aromatics distribution according to STN EN 12 916.

Due to the fact that catalysts based on Na-forms of zeolites (ZSM-5) do not cause additional catalysis of reactions taking place by the carben ions mechanism, ion exchange and subsequent testing of catalytic properties of HZSM-5 were applied. Ion exchange was made under laboratory conditions, with 2 M solution of NH4NO3 at 60C, in triple stechiometric ratio of NH4 and Na. Table 1

Used experimental equipment and procedures To process plastic waste, a BLOWDEC (BLOWing DEComposition) equipment was used (Madar I: Slovak patent No 27 9397). Into the equipment, sand or a catalyst (25%) related to feedstock was added. Trial runs were performed by depolymerization of individual types of plastic materials at various reaction temperatures in Blowdec reactor with simultaneous withdrawal of three kinds of samples: two of liquid and one gaseous product,

recording at the same time the mass and volume of the samples owing through the sampling device. The sampling apparatus served the precise sampling of the gaseous products from a pipeline, the transfer of the process gas from the reactor to a quench column and the gas condensation. At the same time, amount of noncondensable gas samples was determined. The apparatus was designed as to resist high input temperatures of the process gas (up to 480C) and be also suitable for the use in eld conditions of pilot operation. To meet the above requirements, the apparatus was made of stainless steel. Within depolymerization of plastics, also a considerable amount of linear-chain hydrocarbons with a higher pour point is formed. In one-stage condenser, parafns (lower n-alkanes and n-alkenes) present in samples would solidify at temperatures of cooling liquid (40C), clog the equipment and put it (it relates particularly to the condenser) out of order. The rst step is therefore cooling by 65C water, i.e. above the temperature of parafns crystallization, the constant temperature being kept by a thermostat. The second step is cooling by well water. The test was carried out in ve kinds of reaction environments, with a turbulent bed containing inert particules of quartz sand, turbulent bed bearing the catalytically active natural zeolite Clinoptilolite (fy Zeocem), and a turbulent bed bearing the mixture of the catalytically active natural zeolite Clinoptilolite and ZSM-5 (HZSM-5) in a volume ratio of 1:1, 1:3 (1:3). Natural zeolite Clinoptilolite was used as delivered, without additional treatment.

Results and discussion At decomposition of selected polyolens using a pilot equipment, Blowdec, one gaseous and two liquid fractions were obtained. Gaseous samples were subjected to a complete chromatographic analysis; liquid products of depolymerization were free of water and subsequently ltered at 60C. Liquid depolymerisates were distilled to three fractions: below 180C, 180330C, and the rest above 330C, for better identication of hydrocarbons distribution. Thermal cracking was performed at the temperature range 435470C, catalytic cracking between 340 and 450C. Polyolens cracking is signicantly sensitive to the temperature and catalyst used. The presence of a catalyst enables the process to run at relatively lower temperatures. The results of mass balances of thermal and catalytic cracking processes of the selected polyolens are listed in Table 2. As you can see, an increase in the cracking temperature leads to a reduction of the formed liquid depolymerization products.

Table 1 Summary of ZSM-5 details Chemical composition of dry ZSM-5 (%wt.) Na2O CaO Al2O3 SiO2 SiO2/Al2O3 Thermal stability of ZSM-5 RAKH2 O at 3% RV RAKH2 O at 43% RV RAKC6 H6 at 3.5 kPa 2.683 0.528 3.717 93.072 42.94 Up to 9501,000C 3.56.5% hm 6.510.5% hm 1012% hm

RAK equilibrium adsortion capacity, RV relative humidity

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Catalytic and thermal cracking of selected polyolens Table 2 Product distribution to gaseous products from cracking of polyolenes (% wt.) T (C) PP 350 360 370 380 390 400 410 420 430 440 450 470 24 33.5 35 49

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PP cat 1 PP cat 3 PP cat 4 LDPE cat 1 LDPE cat 2 LDPE cat 3 LDPE cat 4 HDPE cat 1 HDPE cat 3 Mix cat 3 8 8 10 14 21 26 27.5 34 46 50 36 38 42 42 11 12 17 17 25 51 53 57 46 61 67 50 59 63 66 14 16 22 24 35 46 65 66 70 17 24

Catalyst No. 1: natural zeoliteClinoptilolite Catalyst No. 2: mixture of ZSM-5 and Clinoptilolite, 1:1 volume ratio Catalyst No. 3: mixture of ZSM-5 and Clinoptilolite, 1:3 volume ratios Catalyst No. 4: mixture of HZSM-5 and Clinoptilolite, 1:3 volume ratios Mix: mixture of LDPE/PP/PS in volume ratio 6:4:1

Evaluation of gaseous products from depolymerization of polyolens Comparison of catalytic cracking using various catalysts revealed that cat. No. 1 (pure Clinoptilolite) is not active and selective enough with respect to formation of gaseous fractions and yields of polypropylene; this is relative to by acid ZSM-5 centers of zeolite as well. The highest yield of gaseous fraction was achieved at 400C with catalyst No. 3 (as much as 50 wt.%). On the whole, catalyst No. 3 appeared to be the most selective with respect to propylene formation (17. 5 wt.%.). Conversely, it was rather surprising that with catalyst No. 4 the yield of isobutene was almost twice as high (6.3 wt.%) at 410C (Tables 3, 4). From all the cracking catalysts used, catalyst No. 4 leads to the highest selectivity of gaseous products at 400C (as much as 63 wt.%). The production and distribution of gaseous products are the result of two factors: high acidity of ZSM-5, HZSM-5 and considerable number of accessible acid centers on the surface of the catalysts. Unlike LDPE, HDPE has branched structure. The presence of tertiary carbon provides very favorable positions for chain initiation, and more moderate conditions are needed for its activation than for that of secondary carbon. During cracking with catalyst No. 1, primarily C2 and C3 fractions are produced. Catalyst No. 1 is not active enough, and this fact resulted in low yields of individual constituents in gaseous fractions; however, this is sufcient with respect to signicant production of liquid product. Having compared catalytic cracking with catalysts No. 2, 3 and 4 at 400C, it

Table 3 Yield comparison of composition of hydrocarbons in gas products from catalytic cracking of PP with different catalysts Yield (%wt.) PP, cat 1 T (C) Methane Ethylene Propylene Isobutene Gas yield
a

PP, cat 3

PP, cat 4

380 400 410 380 400 410 380 400 410 0.19 0.15 2.28 1.9a 8 0.43 0.62 0.05 0.13 0.23 0.07 0.17 0.2 0.36 0.52 0.7 1.63 0.27 1.34 2.05 2.14 2.61 3.17 11.8 16.8 17.5 11.3 14.3 14.7 2.1a 2.7a 3.2 3.8 3.7 6.0 6.5 6.3 10 13.5 34 45.5 50 36 42 42

In mixture trans-2-butene + i-butene

Table 4 Yield comparison of composition of hydrocarbons in gas products from catalytic cracking of LDPE with different catalysts Yield (%wt.) T (C) Methane Ethylene Propylene Isobutene
a

LDPE, cat 1 400 0.29 0.51 2.02 1.8a 420 0.89 1.15 3.0a 17

LDPE, cat 2 400 0.12 3.1 5.2 57

LDPE, cat 3 380 0.06 1.02 15.8 7.3 46 400 0.11 2.85 20.1 8.7 61 420 0.23 4.76 21.4 7.4 67

LDPE, cat 4 380 0.14 2.83 18.3 8.3 58 400 0.16 3.13 20.3 9.1 63

3.56 13.8

Gas yield 10.5

In mixture trans-2-butene + i-butene

can be said that the yields of the main fractions C3 and C4 are generated at 1:1 ratio and their volume is almost identical (approximately 25%). The lowest yields of

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propylene were achieved with catalyst No. 2, while the volume of generated propane is double with respect to other catalysts. The highest isobutene yields were achieved during cracking with catalyst No. 4 (at 400C, as much as 9.1 wt.%); within the thermal gradient of cracking, the inuence of temperature on the volume of generated isobutene is not strong (Table 5). The main products of catalytic cracking of HDPE with catalyst No. 3 are light hydrocarbons C3C5 with considerable volume of olens, primarily of polypropylene (23.3 wt.%). Compared to parafns (i-C4/C4 and i-C5/C5), the volume of isoparafns is twice as high at 400C. Increased volume of i-C4 is generated by cracking of oligomers and higher possibility of carben ions isomerization prior to cracking (Table 6). According to the literature, polystyrene decreases the yield of gaseous fractions, where primarily methane (up to 40%) and ethane are produced (de la Puente and Sedran 1998). Our observations gave the same result. Compared to the yield of gaseous fractions during cracking of LDPE (the most numerous constituent) at 400C, that of gaseous fractions under the same conditions is lower by more than three times. Similarly, propylene and i-butene yields are 3.5- and 4.6-times lower, respectively. The main products of catalytic cracking of polyolenic mixture are represented by C3 and C4 fractions, which represent 76%.

Evaluation of liquid products from depolymerization of polyolens Liquid depolymerisates were distilled to three fractions: below 180C, 180330C, and the rest above 330C [14]. In the fraction below 180C, mostly C5 + C7 olens were produced, the maximum of approx. 20 wt.% from HDPE. In general, approximately 4769 wt.% of olens, 1736% of aromatics, and 1417% of saturated hydrocarbons were produced Gasoline fraction up to 180C is highly unsaturated and further hydrogenation step is necessary (Walendziewski and Steiniger 2001). It could be useful to realize olens hydrogenation on typical hydrogenation catalyst Pt/Al2O3. After hydrogenation, gasoline with the quality fully comparable to that of motor gasoline could be obtained. In the 180330C fraction, C10C15 hydrocarbons represented the main constituent; in all samples, approx. 11 12 wt.% of C12C13 hydrocarbons were produced. According to FIA analysis (Tables 8, 9, 10), the highest volume of olens (above 90 wt.%) were produced by catalytic cracking of PP (catalyst No. 3), while the least volume was produced by catalytic cracking of LDPE (catalyst No. 2), only 49 wt.%. With the remaining samples, the production of olens prevailed over that of aromatics, similarly to PP. In fact, saturated hydrocarbons were not produced. Tables 7, 8, 9, 10, 11, 12, 13. In the fraction above 330C (Tables 11, 12, 13), only group composition was specied; primarily non-aromatics were produced, in numerous HDPE depolymerisates (catalyst No. 3) higher volume of polar substances are produced (up to 14 weight %); however, aromatics are produced as well (Figs. 1, 2, 3, 4, 5, 6, 7). Distribution of liquid depolymerisates is signicantly affected by temperature, the catalyst used, and by the mixture used as raw material. By catalytic cracking of PP (catalyst No. 4), mainly C6C9 carbohydrates were produced in the temperature section. The highest yield of C5C6 fraction was produced at 390C. With all samples, the volume of hydrocarbons in the fraction above 330C was afliated to C22+ hydrocarbons. During catalytic cracking of LDPE (catalyst No. 2), the highest yield of C7C8 fraction was produced at 400C, while the lowest yield was produced with catalyst No. 4; however, this catalyst showed the highest selectivity as to the production of C5C6 fractions. In polyolenic mixture in narrow temperature section, approximately the same yields of individual hydrocarbon fractions were observed; with respect to the presence of PS in the raw material, mostly C8C9 fractions were produced. Catalytic cracking at 400C with catalyst No. 3 produced clearly the highest volume of C5C8 fraction from HDPE, while C6 fraction was produced in twice as high ratio to LDFE, and seven times as high ratio to the mixture.

Table 5 Yield comparison of composition of hydrocarbons in gas products from catalytic cracking of HDPE with different catalysts Yield (%wt.) T (C) Methane Ethylene Propylene Isobutene Gas yield
a

HDPE, cat 1 400 0.43 0.55 3.4 3.1a 14 410 0.61 0.79 3.91 3.5a 16 420 0.94 1.16 4.89 4.1a 22

HDPE, cat 3 380 0.07 2.83 19.86 9.8 65.5 390 0.07 2.08 22.8 10.9 66 400 0.1 2.73 23.3 10.7 70

In mixture trans-2-butene + i-butene

Table 6 Hydrocarbons distribution in gas products from catalytic cracking of mixture of polyolens, cat 3 Yield (%wt.) Methane Ethylene Propylene Isobutene Gas yield 400C 0.3 0.67 5.06 1.88 17 405C 0.35 0.45 4.91 1.94 15 410C 0.37 1.15 8.12 3.25 24

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Catalytic and thermal cracking of selected polyolens Table 7 The selected properties of gasoline fraction from catalytic cracking of HDPE and a mixture of polyolens Sample Reaction temperature ( C) Catalyst Density at 15C, kg/m3 Be (%vol.) To (%vol.) Aromatics (%vol.) Olenes (%vol.) MON RON T 50 (C) T 90 (C) FBP (C) HDPE 365 Cat 3 745.2 \0.1 1.5 8.4 68.3 72 86.4 106.1 167.4 203.5 HDPE 380 Cat 3 759.9 0.35 3.8 13.6 44.6 70.7 85.8 100.6 150.5 183.4 HDPE 390 Cat 3 743.3 \0.1 2 9.5 58 72.8 87.6 92.2 156.2 190.3 HDPE 400 Cat 3 750.7 0.39 3.1 12.5 54.2 73.3 88.8 97.3 157.4 194.5 Mix 400 Cat 3 775.3 0.74 5.2 3.9 49.5 66.1 75.5 104.5 121.2 162.4 Mix 405 Cat 3 759.1 \0.1 1.8 \0.1 69 65.8 72.3 98.8 109.2 148.2

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Mix 410 Cat 3 765 0.45 2.8 \0.1 60.5 68.1 77.5 100.7 121.3 160.1

Table 8 Composition of liguid fraction from 180 to 330C from cracking of PP T (C) Catalyst 410 cat 3 400 cat 3 410 cat 4 400 cat 4

Table 10 Composition of liguid fraction from 180 to 330C from cracking of HDPE and mixture of polyolens Sample T (C) Catalyst HDPE 400 cat 3 Mix 410 cat 3 Mix 400 cat 3

Aromatics distribution (%wt.) MonoDiPolyFIA (%vol.) Saturated Olens Aromatics 0 89.4 10.6 0 94.7 5.3 0 93.6 6.4 0 91.6 8.4 6.7 1.6 0.1 4.8 1.2 0.1 5.4 1.2 0.1 5.6 1.2 0.1 Aromatics distribution (%wt.) MonoDiPolyFIA (%vol.) Saturated Olens Aromatics 3.4 62.6 34 1.8 79.1 19.1 4.3 76.3 19.4 24.5 6.6 0.7 5.9 5.4 0.5 11.4 3.9 0.5

Table 9 Composition of liguid fraction from 180 to 330C from cracking of LDPE T (C) Catalyst 400 cat 2 400 cat 3 420 cat 3 410 cat 4 400 cat 4 Table 11 Composition of liguid fraction above 330C from cracking of PP T (C) Catalyst 22.4 5.9 0.3 0 67.5 32.5 22.3 5.1 0.4 0 62.7 37.3 17.7 4.1 0.3 1.7 69.8 28.6 3.1 0.1 1.91 78.4 19.7 410 cat 3 400 cat 3 410 cat 4 400 cat 4

Aromatics distribution (%wt.) MonoDiPolyFIA (%vol. B) Saturated Olens Aromatics 0 49.4 50.6 23.7 7.5 0.2 16.7

Aromatics distribution (%wt.) MonoDiPolySaturated Aromatics Polar 2.1 1.1 0.6 94.7 3.4 1.9 1.5 0.1 0.3 92.6 4.7 2.7 2.7 1.2 0.5 94.6 3.6 1.8 2.3 0.8 0.4 94.7 3.0 2.2

Group composition (%wt.)

With all depolymerisates from pure polyolens, the same trend of the effect of the catalyst on the distillation curve can be seen. When more acid catalyst is used, hydrocarbons with lower boiling point are produced, and distillation range becomes reduced. The most pronounced

difference can be seen with HDPE; here the temperature required for distillation of 50 vol. % was 249C with catalyst No. 1 and only 98C with catalyst No. 3. Similarly effect could be seen on products from cracking of PP (10%

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126 Table 12 Composition of liguid fraction above 330C from cracking of LDPE T (C) Catalyst 400 cat 2 400 cat 3 420 cat 3 410 cat 4 400 cat 4

J. Mikulec, M. Vrbova

Aromatics distribution (%wt.) MonoDiPolySaturated Aromatics Polar 5.5 1.6 1.1 90.0 6.9 3.1 6.4 2.4 1.0 90.2 6.6 3.1 7.4 2.2 2.0 87.4 9.6 3.0 6.9 2.5 1.8 88.2 10.3 1.5 6.5 1.9 1.1 75.0 22.6 2.4 Fig. 2 Carbon number distribution of liquid products from catalytic cracking of LDPE (reaction temperature 400C) Table 13 Composition of liguid fraction above 330C from cracking of HDPE and mixture of polyolens Sample T (C) Catalyst HDPE 400 cat 3 Mix 410 cat 3 Mix 400 cat 3

Group composition (%wt.)

Aromatics distribution (%wt.) MonoDiPolySaturated Aromatics Polar 11.5 4.3 4.1 68.1 18.2 13.7 5.9 2.0 2.3 64.4 29.1 6.4 8.5 3.2 2.4 74.4 18.1 7.5

Group composition (%wt.)

Fig. 3 Carbon number distribution of liquid products from catalytic cracking of LDPE (catalyst no. 4)

Fig. 1 Carbon number distribution of liquid products from catalytic cracking of PP (catalyst no. 4)

vol. were distilled at half temperature using of catalyst No. 3 and 4). PS increases the temperature required for distillation of 5 weight % polyolenic mixture. Enormous difference between the main constituent of the mixture (LDPE) and polyolenic mixture was observed at the temperature required for distillation of 50 weight %, 152C

Fig. 4 Carbon number distribution of liquid products from catalytic cracking of HDPE (catalyst no. 3)

for LDPE and the temperature of the mixture increased to 282C, and this was reected in considerably thicker consistence of depolymerisates from the mixture. At distillation end there is no pronounced difference.

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Catalytic and thermal cracking of selected polyolens

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Fig. 5 Carbon number distribution of liquid products from catalytic cracking of mixture of polyeolns (catalyst no.3)

the raw material and pyrolysis on the model equipment with 2 kg/h capacity. Using the model pyrolysis equipment, pyrolysis of heavy gasoline was made with 2.57 kg/h raw material feedstock dosage; the steam/feedstock material ratio was 0.6, temperatures were 665705C. Using correlation coefcients, possible yields which can be assumed at 22 t/h feedstock dosage and steam/feedstock ratio = 0.6 were calculated. To heavy gasoline raw material, 5 weight % of depolymerisates from PP, LDPE, and HDPE were added (Tables 14, 15). The research of possible pyrolysis of PP, LDPE, and HDPE depolymerisates after distillation up to 300C as 5 weight % addition to heavy gasoline was continued. Tests of unmodied and modied heavy gasoline were made at 800, 820 and 840C, with 0.6 gas/raw material ratio. The results of individual products were compared (Tables 16, 17).

Evaluation of the possibilities to use liquid products by microactivity test (MAT) Liquid products were tested as potential addition to the raw material for uid catalytic cracking by help of MAT (microactivity test) ASTM D 390792. Microactivity test performed according to ASTM D 390792 provides data for evaluation of a relative production using a FCC catalyst. Since the results are inuenced by the feedstock quality, testing apparatus, build-up time of catalyst, operational parameters, observation of this method is a premise for correct interpretation of the results. Maximum cracking activity was reached at about 80% conversion (Kucera 2001, 2002). The catalyst Briliant 225 XB was deactivated by water steam at 800C during 5 h prior to use. Reaction parameters at MAT test: Reaction temperature: Mass of catalyst: Catal./feedstock ratio: 520C 4g 4

Fig. 6 Simulated distillation curves from cracking of PP (reaction temperature 400C)

Fig. 7 Simulated distillation curves from cracking of HDPE (reaction temperature 400C)

Evaluation of the possibility to use liquid fractions for pyrolysis Suitability of depolymerisates as the raw material for feedstock dosage of pyrolysis was checked by addition to

Suitability of using depolymerisates as a raw material for feedstock dosage for pyrolysis and FCC (uid catalytic cracking) was checked on the model equipment and with the help of MAT test (microactivity test). The most suitable application in the FCC process seems to be reserved for LDPE and HDPE products of depolymerization. Polyolens involved in depolymerization products increase the yield of petrol fraction and this yield increases with growing temperature. The addition to feedstock exhibits a positive effect for C5C12 petrol fraction, reduces the formation of LCO, MCB and coke, which is very desirable at petrol production (Table 18).

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128 Table 14 Comparison pyrolysis of heavy gasoline with and without addition of liquid products from HDPE, LDPE, PP crackingethylene yield

J. Mikulec, M. Vrbova

Yield (wt.% basis feed)

Pyrolysis temperature (C) 800 810 820 830 840

Pyrolysis of heavy gasoline Ethylene Ethylene Ethylene Ethylene 25.22 15.28 24.00 23.87 25.89 16.75 24.36 24.5 26.22 17.69 24.72 25.16 27.02 18.05 25.06 25.49 27.44 19.5 26.71 26.69 Pyrolysis of heavy gasoline with addition of liquid products from HDPE cracking Pyrolysis of heavy gasoline with addition of liquid products from LDPE cracking Pyrolysis of heavy gasoline with addition of liquid products from PP cracking

Table 15 Comparison pyrolysis of heavy gasoline with and without addition of liquid products from HDPE, LDPE, PP cracking pyrolysis gasoline yield

Yield (wt.% basis feed)

Pyrolysis temperature (C) 800 810 820 830 840

Pyrolysis of heavy gasoline Pyrolysis gasoline Pyrolysis gasoline Pyrolysis gasoline Pyrolysis gasoline 23.06 45.72 24.15 23.25 22.09 42.21 23.89 22.1 21.18 38.31 23.14 21.02 20.22 37.66 20.96 20.77 19.32 36.02 16.92 20.15 Pyrolysis of heavy gasoline with addition of liquid products from HDPE cracking Pyrolysis of heavy gasoline with addition of liquid products from LDPE cracking Pyrolysis of heavy gasoline with addition of liquid products from PP cracking

Table 16 Comparison pyrolysis of heavy gasoline with and without addition of liquid products (fraction up to 300C) from HDPE, LDPE, PP crackingethylene yield

Yield (wt.% basis feed)

Pyrolysis temperature (C) 800 820 840

Heavy gasoline Ethylene Ehtylene Ethylene Ethylene 25.62 19.43 27.74 24.91 26.86 20.93 28.66 25.7 28.23 21.22 28.77 27.01 Heavy gasoline with addition of liquid products from HDPE cracking Heavy gasoline with addition of liquid products from LDPE cracking Heavy gasoline with addition of liquid products from PP cracking

Table 17 Comparison pyrolysis of heavy gasoline with and without addition of liquid products (fraction up to 300C) from HDPE, LDPE, PP crackingpyrolysis gasoline yield

Yield (wt.% basis feed)

Pyrolysis temperature (C) 800 820 840

Heavy gasoline Pyrolysis gasoline Pyrolysis gasoline Pyrolysis gasoline Pyrolysis gasoline 22.81 36.41 20.1 22.11 21.05 33.64 19.97 20.74 19.2 32.82 16.53 19.89 Heavy gasoline s addition of liquid products from HDPE cracking Heavy gasoline with addition of liquid products from LDPE cracking Heavy gasoline s with addition of liquid products from PP

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Catalytic and thermal cracking of selected polyolens Table 18 Product composition of MAT test by addition of 5 or 10%wt. of depolymerisates of waste plastics Yield (%wt.) MAT C1, C2 C3, C4, Gasoline LCO MCB Coke Standard FCC feed 75.5 5.2 14.0 56.3 13.0 6.0 5.5 +5 %wt. depol. LDPE 80.2 6.3 14.8 59.1 8.8 6.0 5.0 +10 %wt. depol. LDPE 85.8 7.3 15.2 63.3 3.9 5.2 5.1 +5 %wt. depol. HDPE 81.3 6.5 15.0 59.2 8.3 5.8 5.2 +10 %wt. depol. HDPE 86.0 7.4 15.5 63.1 3.7 5.0 5.3 +5 %wt. depol. PP 81.9 10.8 17.6 53.5 7.9 5.4 4.8

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+10 %wt. depol. PP 87.2 14.6 23.8 48.8 3.1 4.6 5.1

MAT (%)conversion expressed by yield below 225C Gasoline (weight %)fraction in 39225C temperature range LCO (weight %)light cycle oil in 225355C temperature range MCB (weight %)fraction above 355C Coke was specied according to mass loss of the catalyst heated at 650C

Conclusions Catalytic cracking was made using four catalyst types (Clinoptilolite, NaZSM-5Clinoptilolite mixture in 1:1 and 1:3 ratios, HZSM-5Clinoptilolite mixture in 1:3 volume ratio). Activity and selectivity of catalysts to production of gaseous fractions and yields of propylene, etylene and of individual hydrocarbon fractions is related to, among other things, the number of acid ZSM-5 centers. During catalytic cracking of PP, catalyst No. 3 appeared to be the most selective to the production of gaseous fractions (50 weight %) and of propylene (17.5 weight %). The use of catalyst No. 4 resulted in the highest volume of isobutene (6.3 weight %). During catalytic cracking of LDPE at 400C, catalyst No. 4 leads to the highest selectivity to gaseous products (as much as 63 weight %.). Unlike HDPE, LDPE has branched structure. The presence of tertiary carbon provides very good positions for chain initiation; for its activation more moderate conditions are required than for that of secondary carbon. The PS constituent in polyolen mixture decreases the yield of gaseous fractions three times at 400C (18 weight %) compared to the yield of gaseous fractions of LDPE as the most numerous constituent. Similarly, propylene and i-butene yields are 3.5- and 4.6times lower, respectively. The main products of catalytic cracking of polyolenic mixture are represented by C3 and C4 fractions, which represent 76 %. In the liquid fraction below 180C mostly C5+C7 olens were produced. In general, approximately 4769 %wt. of olens, 1736 %wt. of aromatics, and 1417 %wt. of saturated hydrocarbons were produced. In the 180330C fraction, the main constituent were C10C15 hydrocarbons. In all samples approx. 1112 weight % of C12C13 hydrocarbons were produced.

According to FIA analysis, the highest volume of olens (above 90 weight %) were produced by catalytic cracking of PP (catalyst No. 3), while the least volume was produced by catalytic cracking of LDPE (catalyst No. 2), only 49 weight %. With the remaining samples, the production of olens prevailed over that of aromatics, similar to PP. In fact, saturated hydrocarbons were not produced. In the fraction above 330C, primarily non-aromatics were produced. Combining the Blowdec process with renery technologies such as FCC is a feasible solution for the processing of waste plastic materials with economic goal. Compared to combustion in power stations, the use of waste plastics in renery will result in a visible economical effect. Liquid products of LDPE and HDPE depolymerization are a suitable feedstock for pyrolysis and FCC as well.
Acknowledgments The authors are grateful to the Slovak Agency for Research and Development and to the Slovak Ministry of Economy for nancial support received for this work.

References
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