J Mater Cycles Waste Manag DOI 10.1007/s10163-013-0204-z
ORIGINAL ARTICLE
Bio-oil production by fast pyrolysis of cellulose/polyethylene mixtures in the presence of metal chloride A. Solak • P. Rutkowski
Received: 1 November 2011 / Accepted: 13 September 2013 Ó Springer Japan 2013
Abstract Cellulose/polyethylene mixture (3:1 w/w) and Tetra Pak wastes with and without metal chloride (ZnCl2, AlCl3, CuCl2, FeCl3) addition were subjected to a fast pyrolysis process at 350–500 °C and heating rate 100 °C/s to evaluate the possibility of liquid product formation with a high yield. The addition of zinc, aluminum, iron and copper chlorides has influenced the range of samples decomposition as well as the chemical composition of resulting pyrolytic oils. It was found that formation of levoglucosan, the main product of cellulose thermal decomposition, and phenol and its derivatives decreased in a presence of metal chlorides. Non-catalytic fast pyrolysis of polyethylene leads to the formation of solid long chain hydrocarbons, whereas the addition of metal chlorides promotes the formation of more liquid hydrocarbons. Keywords Pyrolytic oil Cellulose Polyethylene Tetra Pak Metal chloride
Introduction The production of global polymers (265 million tonnes in 2010) and their consumption has increased steadily over the past decades, leading to increased waste generation. Proper handling of post-consumer polymers waste is still a serious problem. Worldwide waste polymers recycling and recovery rates rise and landfill decreases. In Poland, the
A. Solak P. Rutkowski (&) Departament of Polymer and Carbonaceous Materials, Faculty of Chemistry, Wrocław University of Technology, Gdan´ska 7/9, 50-344 Wrocław, Poland e-mail:
[email protected]
main part of plastic waste (over 70 %) was dumped at landfills, this being the cheapest method [1]. Carton packages (including Tetra Pak, SIG and other) became one of the most popular beverage storage systems. Aseptic carton packages are formed from multilayer packaging material, including paper, polyethylene and aluminum foil. Non-aseptic packages do not have a layer of aluminum foil. According to Tetra Pak Company, in Europe in 2007, 33 % of all drink cartons were used to generate energy. Therefore, there is a potential to use such materials for chemical or energy recovery. In view of the coexistence of cellulose and polyolefins in carton packages and municipal solid wastes, their thermochemical co-conversion seems to be an attractive aspect of use and recycling [2]. Pyrolysis as one of the thermochemical conversion processes could be an alternative and attractive way of recycling packaging wastes, particularly in comparison to landfill or incineration. Pyrolysis leads to the formation of char, tar/oil and gas as main products, but their relative proportions strongly depend on the pyrolysis method and process conditions. While solid product of pyrolysis may be used as fuel or active carbon precursor, gas product can be utilized in a combustion process for energy production (reactor heating). The liquid product of pyrolysis process may be applied in the production of liquid fuels, chemicals and solvents. Therefore, pyrolysis has the potential to be an attractive and important method for biomass and/or organic wastes utilization [3]. As it has been described in some papers, the co-pyrolysis process could have potential for environmentally friendly transformation of lignocellulosic materials and plastic waste to valuable products [4–11]. Waste plastics can be converted toe fuel oil by noncatalytic or catalytic thermal processes. There were many reports on the hydrocarbon polymers degradation processes
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that led to the formation of liquid fraction [12–16]. As authors know, there is little information on the catalytic pyrolysis of cellulose/polyethylene blends, including beverage carton packages. Iron and copper are present in many kinds of plastics or plastic-contained wastes. The chlorides of these metals are frequently suspected of the catalytic formation of harmful unwanted compounds [17]. There have also been many studies on the effect of transition metal chlorides on the pyrolysis of various polymers [17–20]. In their works, Blazso´ et al. [18, 19] have demonstrated the significant influence of iron and copper chlorides in the modification of the thermal decomposition reactions taking place in polyethylene pyrolysis. The aim of this preliminary study was to evaluate the possibility of catalytic fast pyrolysis application as a method of thermochemical recycling of organic solid wastes. Fast pyrolysis of cellulose/polyethylene mixture and Tetra Pak with and without catalyst was performed to determine the influence of metal chloride on the yield and the chemical composition of liquid products.
Materials and methods Starting materials Waste beverage carton package (Tetra Brik Aseptic—TA), commercial cellulose (C) and powdered low-density polyethylene (PE) were selected for this study. Cellulose/ polyethylene (CPE) mixture in a 75:25 (w/w) ratio was prepared in a blender from powdered samples. Such a ratio of cellulose and polyethylene corresponds to their ratio in Tetra Pak samples. Starting materials were used as a model system for co-pyrolysis of cellulose and polyethylene. All samples (TA and CPE) were also mixed with 10 wt% metal chloride (ZnCl2, AlCl3, CuCl2, FeCl3) before pyrolysis. The main characteristics of the initial samples are given in Table 1. Elemental composition was determined by a CHNS Vario El analyzer (Elemental Analysensysteme GmbH). Oxygen content was calculated by difference. Proximate analysis and high heating value of cellulose, polyethylene and Tetra Pak samples were determined according to Polish Standards (corresponding to ISO standards). Pyrolysis The pyrolysis processes of Tetra Pak sample (TA) or CPE mixture with and without metal chloride addition were carried out in a horizontal oven with an infrared heating system and dynamic cooling system, as given in Fig. 1.
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Table 1 Ultimate and proximate analyses of starting materials C
PE
TA
Cdaf (wt%)
42.5
85.5
65.4
Hdaf (wt%)
6.5
14.2
9.7
Ndaf (wt%)
–
–
0.2
O(diff) (wt%)
51.0
0.3
24.7
Ma (wt%)
6.9
0.1
5.54
Ad (wt%)
0.3
0
6.5
Vdaf (wt%)
92.9
100
90.2
Qai (MJ/kg)
15.2
43.2
20.3
C cellulose, PE polyethylene, TA TetraBrik Aseptic, daf dry, ash free
0.2 g of sample was placed in quartz reactor and heated up to 350–500 °C with a heating rate of 100 °C/s. Decomposition products were evacuated in nitrogen flow of 10 dm3 h-1 to a liquid reservoir placed in a liquid nitrogen bath. The pyrolysis process was repeated at least twice to check reproducibility and to calculate an average yield of products. Liquid products collected in the liquids receiver were transferred with benzene-methanol (60:40, vol./vol.) mixture into the measuring flask. Next, bio-oil was analyzed by means of gas chromatography–mass spectrometry (GC– MS). Afterwards, methanol and some of the benzene were removed by rotary evaporator (volume reduced to c. 5 ml). The anhydrous sodium sulfate was added to the bio-oil solution and stirred for several minutes. Finally, after physical separation of sodium sulfate, bio-oil was dried in a rotary evaporator. Infrared spectroscopy The Fourier transform–infrared spectroscopy (FT-IR) spectra of dried bio-oils were recorded on Vector 22 (Bruker GmbH) spectrophotometer. All samples were analyzed in the wave number range of 600–3600 cm-1. GC–MS analysis The bio-oils dissolved in benzene-methanol mixture were analyzed by an HP6890 gas chromatograph equipped with an HP5973 mass selective detector and a HP-1701 capillary column (30 m 9 0.25 mm i.d., 0.25 lm film thickness, 14 %-cyanopropylphenyl-86 %-dimethylsiloxane polymer). As a carrier, gas helium (purity 99.999 %) was used. The column temperature was programmed from 40 to 260 °C at 10 °C/min after an initial 4 min isothermal period, and kept at the final temperature for 10 min. The inlet was set at 250 °C. Sample injection was made in the split mode (1:10). Mass spectrometer was set at an ionizing voltage of 70 eV with mass range m/z 15–400. The identification of
J Mater Cycles Waste Manag Fig. 1 Scheme of reactor system. 1 gas inlet, 2 temperature controller, 3 sample boat; 4 oven, 5 quartz reactor, 6 condenser, 7 liquid nitrogen reservoir, 8 gas outlet
8 3
1 4
5 6
2
7
organic compounds was accomplished by comparing mass spectra of the resolved components using electronic library search routines.
Results and discussion Characteristics of initial samples The ultimate composition and basic properties of all investigated samples are characteristic and typical for these types of materials (Table 1). Cellulose is characterized by high oxygen content, whereas polyethylene is composed of carbon and hydrogen. Tetra Pak sample is composed of cardboard (68 %), low-density polyethylene (26 %) and aluminum (*6 %). Its elemental composition nearly follows the additivity rule. As expected, cellulose and Tetra Pak sample contain significant amounts of moisture. Both samples are characterized by high volatile matter content. Moreover, Tetra Brik Aseptic is rich in ash content related to the presence of aluminium foil. Polyethylene is almost free of moisture and ash. The high heating value of the two materials is clearly different, i.e. as low as 15.2 MJ kg-1 for cellulose and as high as 43.2 MJ kg-1 for polyethylene, which is a result of their elemental composition. Tetra Pak is characterized by a heating value as high as 20.3 MJ kg-1, which is related to the cellulose/polyethylene ratio. The effect of pyrolysis conditions on the yield of products Bio-oils obtained during pyrolysis of the cellulose/polyethylene 3:1 (w/w) mixture and Tetra Brik Aseptic differ from each other by color, state and odor, depending on the presence of metal chloride. Pyrolytic oils obtained from the
CPE mixture and Tetra Pak are composed of three well separated phases, i.e. water, brown organic liquid and yellow wax. The metal chlorides used in this study, i.e. ZnCl2, CuCl2, AlCl3 and FeCl3 are well-known Lewis acids acting as acidic catalysts. Pyrolysis of CPE and TA in the presence of metal chlorides lead to the increased formation of organic liquids instead of wax accompanied by the increased formation of water. The addition of metal chlorides to cellulose/polyethylene mixture and Tetra Pak resulted in the formation of bio-oils composed of two phases, i.e. water and organic liquid phase. The pyrolytic bio-oils produced from CPE and TA with the zinc chloride and copper(II) chloride addition are yellow-orange liquids with well-separated water and oil phases. This fact suggests the deeper degradation of polyethylene and decreased formation of waxes. The pyrolytic liquids produced from CPE and TA with the addition of aluminum chloride and iron(III) chloride are brown liquids with well-separated water and oil phases. Dark color of bio-oil is probably due to the fact of partial aluminum and iron(III) chlorides evaporation during pyrolysis process. Cellulose/polyethylene 3:1(w/w) mixture and Tetra Brik Aseptic samples investigated in this study were pyrolyzed non-catalytically for use in comparison to the pyrolysis experiments in the metal chloride presence at 500 °C and a heating rate of 100 °C/s. The degree of sample decomposition is given in Fig. 2 as a product distribution. Fast pyrolysis process performed at 500 °C leads to the deep degradation of the cellulose/polyethylene mixture and the formation of liquid product, with yield as high as 80 %. A char and gaseous products are formed with minor contribution. The thermal degradation of Tetra Pak is also intense, but the yield of liquid product does not exceed 70 %. It is probably related to the nature of cellulose types present in CPE mixture (powdered cellulose) and Tetra Pak
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81
90 char
liquid
gas
58.4
60.9
51.2
52.1
60
51.7
53.2
60.4
70
65
80 66.9
Fig. 2 Products yield of fast pyrolysis at 500 °C of cellulose/ polyethylene mixture (CPE) and Tetra Brik Aseptic (TA) with and without 10 wt% of metal chloride
50
25.2 16.4
20
28.8
29.1 18.8
22.5 12.5
10.5
20.7
27.0
21.3
23.1
18.4
8.5
10
23.7
19.6
17.0
20
13.5
30
22.6
40
0
(fibrous cellulose). As previously reported, paperboard (long cellulose fibers) separated from Tetra Aseptic gives c. 74 wt% of liquid product [21], whereas pure microcrystalline cellulose give 79 wt% of liquid product at the same pyrolysis conditions [22]. It confirms the influence of cellulose structure or its origin in the pyrolysis products distribution. It should be noted that high contribution of wax is observed for bio-oils obtained in non-catalytic pyrolysis process. The wax is included as part of the bio-oil, but formally, it is a solid product that condenses in the receiver of the liquids. In both cases, i.e., pyrolysis of cellulose/polyethylene mixture and pyrolysis of Tetra Pak, the addition of metal chloride, particularly CuCl2 and FeCl3, leads to the significant decrease of the pyrolytic oil yield accompanied by an increase of char and gas yields, Fig. 2. On the one hand, it is a result of dehydration and condensation of the cellulose matrix, resulting in higher char formation. On the other hand, deeper degradation of polyethylene in the presence of metal chloride and the formation of short-chain hydrocarbons lead toa greater evolution of gaseous products. The influence of pyrolysis process temperature on the products distribution of selected samples is given in Fig. 3. As can been seen, the non-catalytic process (CPE) is much more effective in liquid product formation at higher temperatures, at least 450 °C. It is mainly related to the deeper decomposition of polyethylene. On the other hand, the effect of temperature on the formation of liquid products is less important when the pyrolysis of CPE and TA is carried out in the presence of metal chlorides. Taking into account other products of cellulose/polyethylene mixture thermal decomposition, it can be noted that metal chlorides
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promote more intense evolution of gaseous products and much lower formation of char with increasing temperature. The increased gas formation during catalytic pyrolysis of CPE blend may be attributed to the enhanced gasification reactions taking place in the presence of metal chloride. During the pyrolysis process of CPE blend with the addition of AlCl3, the initial increase in temperature leads to an increased formation of liquid product, but a further increase in temperature leads to an intensive evolution of gas at the expense of the liquid and the solid product. It shows the enhanced the activity of AlCl3 in gasification reactions at higher temperatures. The activity of copper(II) chloride during pyrolysis of CPE blend leads to enhanced evolution of gas accompanied by decreasing formation of char. The formation of liquid products gradually decreases from 59.5 wt% at 350 °C to 52.1 wt% at 500 °C. Such a results confirm the influence of acidity strength of metal chlorides on the behavior of CPE blend at various temperatures. Aluminum and iron(III) chlorides are recognized as strong Lewis acids, whereas copper(II) and zinc chlorides act as moderate-strength Lewis acids. The influence of metal chloride addition to cellulose/polyethylene mixture on chemical composition of bio-oil The chemical composition of resultant pyrolytic oils clearly depends on the starting material and on the presence of metal chloride during the fast pyrolysis process, as can be seen in Figs. 4 and 5 and in Table 2. All results presented in the following parts of the study describe bio-oils obtained at 500 °C.
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80
CPE 79.5 73.5
60
54.0
20
the range 1760–1665 cm-1 are of medium intensity. Both bio-oils signals in the range of wave number 3500–3200 cm-1 are broad and overlapping C–H stretching vibrations near 3000 cm-1. That suggests the presence of high amounts of organic compounds rich in hydroxyl groups, i.e. levoglucosan, other sugars and water. Adsorptions associated with the O–H stretching vibrations existing in the regions 3500–3200 cm-1 remain intensive, indicating the presence of high amounts of compounds rich in hydroxyl groups. Instead of the addition of metal chlorides to cellulose/ polyethylene mixture, the changes of infrared spectra of the resultant bio-oils are minor. Contrarily, the addition of metal chlorides to Tetra Pak promotes the decrease of signals corresponding to the oxygen-containing groups, in particular, O–H vibrations. The most effective are zinc chloride and iron(III) chloride well known as good dehydrating agents. The significant removal of the carbonyl group what is demonstrated with the lack of signals with a maximum between 1718 and 1680 cm-1 for bio-oil obtained from TA_ZnCl2, TA_AlCl3 and TA_FeCl3.
0
GC–MS of bio-oils
80
81.0 char gas
60
oil 45.5 40
40 19.0
20
12.5
0.5 0 350
20
10.5
7.5 8.0 400
8.5
0 500
450
Temperature [°C] 80
80
char
CPE+10%CuCl2
gas 60
40
60
oil 59.5
58.0
53.4
52.1
25.9
29.1
20.7
18.8
40
37.0 24.2
20 3.5 0 350
17.9 400
450
500
Temperature [°C] 80
CPE+10%AlCl3
80
71.8 60
69.1
57.7
58.4
60
char
Oxygen containing organic compounds
gas 40
39.4
2.9 0 350
40
oil 19.6
20
The GC–MS analyses of bio-oils show that the metal chloride addition to cellulose/polyethylene mixture or Tetra Pak affects the composition of pyrolytic liquids to a large extent. To conserve space, only selected GC–MS results are presented in Table 2 and Fig. 5 as examples.
8.5 400
18.6 12.3 450
25.2 20 16.4 0 500
Temperature [°C] Fig. 3 Influence of temperature on the yield of fast pyrolysis of cellulose/polyethylene mixture (CPE) with and without copper(II) chloride and aluminum chloride
Fourier transform-infrared spectroscopy The FT-IR spectra of investigated bio-oils are presented in Fig. 4. The bio-oils obtained from cellulose/polyethylene mixture (CPE) and Tetra Brik Aseptic (TA) are characterized by a high proportion of oxygen groups, represented on the FT-IR spectra as intensive adsorptions associated with the O–H stretching vibrations existing in the regions 3500–3200 cm-1. The C=O stretching vibrations present in
Non-catalytic pyrolysis of raw material containing 30–40 % oxygen leads to the formation of large quantities of oxygen-containing organic compounds. Cellulose is the main component of initial samples. The effect of their pyrolysis is a high proportion of compounds typical for the decomposition of cellulose in bio-oil. The oxygen-containing compound that is formed during the pyrolysis of cellulose/polyethylene or Tetra Pak in the largest quantities is levoglucosan (LG), containing three hydroxyl groups (see Fig. 5). Other organic compounds of different classes, i.e. furfural (FF), furan derivatives, levoglucosenone (LGO)—a highly dehydrated sugar, dianhydro-a-glucopyranose (DAGP), phenol, and phenol derivatives, have been also identified in analyzed oils. There is a clear difference in the pyrolytic degradation of both materials, i.e. CPE mixture and Tetra Pak, which must be related to the differences in their composition (see Fig. 5 and Table 2). A main reason for such difference in levoglucosan formation during non-catalytic pyrolysis is likely the cellulose type. Powdered cellulose used for CPE mixture preparation decomposes with a LG formation,
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J Mater Cycles Waste Manag Fig. 4 FT-IR of bio-oils obtained during fast pyrolysis at 500 °C of cellulose/ polyethylene mixture (CPE) and Tetra Brik Aseptic (TA) with and without metal chloride addition (ZnCl2, zinc chloride; FeCl3, iron(III) chloride; AlCl3, aluminum chloride)
(a)
(b) CPE
TA
TA_CuCl 2
CPE_CuCl 2
TA_FeCl 3
CPE_FeCl 3 TA_AlCl 3
CPE_AlCl 3
TA_ZnCl 2
CPE_ZnCl 2
4000
3500
3000
2500
2000
wave number, cm
whereas fibrous cellulose of Tetra Pak is more thermally stable. It was found that the addition of metal chlorides significantly decreases the formation of levoglucosan during pyrolysis of cellulose/polyethylene mixture. When Tetra Pak sample was pyrolyzed in the presence of metal chlorides, the formation of levoglucosan was severely limited. The formation of 1,6-anhydro-b-D-glucofuranose (AGF) is also limited during catalytic pyrolysis of CPE and TA. A slightly increased formation of furfural (FF), levoglucosenone (LGO) and dianhydro-a-gluco-pyranose (DAGP) was observed when catalytic pyrolysis was conducted; see Fig. 5. Hydrocarbons The second component of initial samples is low-density polyethylene in the amount of circa 25 wt%. Therefore, chain saturated and unsaturated hydrocarbons, i.e. alkanes, alkenes and dienes, were identified in large quantities in pyrolytic oils. All three groups of hydrocarbons were identified in a wide range of the carbon skeleton length (C8–C34). To describe the degradation of polyethylene during pyrolysis, hydrocarbons were divided into two groups, i.e. liquid (HCliq) and solid (HCsolid). It was found that both the initial sample and the presence of metal chloride influences the composition of hydrocarbon part and its proportion in bio-oil. It was observed that during pyrolysis of both cellulose/ polyethylene mixture and Tetra Pak, high amounts of solid hydrocarbons ([C20) were formed (see Table 2). However, non-catalytic pyrolysis of Tetra Pak compared to CPE results in increased formation of liquid hydrocarbons.
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1500
1000
-1
4000
3500
3000
2500
2000
wave number, cm
1500
1000
-1
As can be seen in Fig. 5, the addition metal chlorides to CPE and TA enhances depolymerization of polyethylene with the formation of higher quantities of liquid hydrocarbons. Among the metal chlorides studied in this work, the presence of iron(III) chloride shows the greatest influence on the thermal degradation of polyethylene. Conclusions It should be noted that the lab scale reactor used in this study may have limitations in comparison to the large reactor. Both the yield and characteristics of bio-oil may be much different. Nevertheless, it gives important information on the chemistry of Tetra Pak pyrolysis in the presence of metal chlorides. The thermal decomposition of cellulose/polyethylene and Tetra Pak samples through rapid pyrolysis leads to the production of bio-oil with yields as high as 67–80 %. The products of non-catalytic degradation of CPE and TA contain, in addition to chain hydrocarbons, high amounts of levoglucosan and smaller quantities of 1,6-anhydro-b-Dglucofuranose, furfural, phenol and derivatives. The results clearly show that the addition of ZnCl2, CuCl2, AlCl3 or FeCl3 significantly changes the degree of cellulose/polyethylene blend and Tetra Pak decomposition during rapid pyrolysis at 500 °C. Metal chlorides act as a Lewis acid, resulting in dehydration and cross-linking reactions leading to the increased char formation. The production of bio-oil is decreased in the presence of metal chloride, but the decomposition of polyethylene is enhanced and more liquid hydrocarbons are produced instead of wax.
J Mater Cycles Waste Manag
TA
LG
C20 C20
DGF
C22 C24
FF FF
DGF
FF
DAGP
LGO
DAGP
LG
FF
DGF
DAGP FF
25.00
30.00
35.00
LGO
LGO
LG
TA AlCl 3
TA FeCl 3
CPE_FeCl 3
20.00
C22
C18 C18
LGO
C14
TA_ZnCl 2
DGF
DAGP
LGO
FF
CPE_AlCl 3
15.00
C24
C16
FF LG
CPE_ZnCl2
10.00
C16
C14
C22
C24
C20
C18
DGF
FF
LGO
DAGP
C14
C16
LG
CPE
40.00
45.00
50.00
55.00
60.00
Fig. 5 GC–MS for oils from pyrolysis of cellulose/polyethylene mixture (CPE), Tetra Brik Aseptic (TA) and their compositions with 10 wt% of metal chloride (ZnCl2, zinc chloride; FeCl3, iron(III) chloride; AlCl3, aluminum chloride). LG, levoglucosan; LGO,
10.00
15.00
20.00
25.00 30.00 35.00 40.00 45.00 50.00 55.00 60.00
levoglucosenone; FF, furfural, DAGP, 1,4:3,6-Dianhydro-a-D-glucopyranose; AGF, 1,6-anhydro-b-D-glucofuranose; C14–C20, n-chain hydrocarbons with a specified number of carbon atoms
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J Mater Cycles Waste Manag Table 2 Peak area % of selected compounds identified in bio-oils obtained by fast pyrolysis at 500 °C from cellulose/polyethylene blend (CPE) or Tetra Brik Aseptic mixed with various metal chlorides (10 wt%) Compound
Symbol
CPE CPE_ZnCl2
CPE_AlCl3
CPE_FeCl3
TA
TA _ZnCl2
TA_AlCl3
TA _FeCl3
2-Furancarboxaldehyde
FF
0.0
1.2
0.9
1.1
0.2
0.4
0.3
0.4
2-Furanethanol-b-methoxy-(S)-
MFE
0.5
1.9
0.6
1.1
0.3
7.71
2.1
3.1
Levoglucosenone 1.4:3.6-Dianhydro-a-D-glucopyranose
LGO DAGP
0.9 2.5
0.6 1.2
3.1 2.4
0.7 1.2
0.1 0.4
0.6 –
1.0 –
0.4 –
2-Furancarboxaldehyde-5-hydroxymethyl
HMF
0.2
–
0.2
0.2
–
–
–
–
1.5-Anhydro-4-deoxy-D-glycero-hex-1-en3-ulose
APP
0.3
1.6
–
3.2
0.4
0.2
1.9
–
Levoglucosan
LG
20.5
16.2
10.2
5.5
13.7
2.6
1.5
1.0
1.6-Anhydro-b-D-glucofuranose
AGF
1.6
1.4
0.8
0.7
0.6
–
–
–
Hydrocarbons containing a specified number of carbon atoms
C B 19
27.0
29.2
31.6
28.9
21.6
40.4
37.3
49.5
C C 20 Hliq/Hsolid
37.0 0.73
36.6 0.80
35.7 0.88
38.0 0.76
45.6 0.47
47.5 0.85
49.5 0.75
46.1 1.07
The effect of metal chlorides on pyrolysis of the cellulose part of initial samples (cellulose/polyethylene, Tetra Brik Aseptic) is significant. In metal chloride catalyzed pyrolysis, levoglucosan formation is lowered (cellulose/ polyethylene blend) or strongly limited (Tetra Pak), accompanied by an increased formation of furfural, levoglucosenone and 1,4:3,6-Dianhydro-a-D-glucopyranose. These preliminary results show that Tetra Pak or organic wastes containing cellulose and polyolefin can be useful recycling resources. With such an improved liquid hydrocarbon-rich oil production from Tetra Pak, fast pyrolysis of beverage package waste seems to be an alternative route for recycling such material.
7.
8.
9.
10.
11. Acknowledgments The State Committee for Scientific Research in Poland supported this work. Project No. N209146036.
12. 13.
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22. Rutkowski P (2013) Characteristics of bio-oil obtained by catalytic pyrolysis of beverage carton packaging waste. J Anal Appl Pyrol http://dx.doi.org/10.1016/j.jaap.2013.05.006 (in press)
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