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Unconventional liquid fuel from municipality waste plastics mixture of polystyrene (PS) and low density polyethylene (LDPE).

Introduction

The use of plastic products low density polyethylene and polystyrene (LDPE & PS) has closely followed the growth of the welfare level in modern societies. Consequently, the amount of plastic waste has dramatically increased, causing a serious environmental problem. The currently prevailing practices in solid waste management are landfill disposal and too much lesser extent, incineration, with the latter practice enabling recovery of the energy content of the waste. Both practices lead, however, to serious environmental problems when applied also to plastic wastes, because plastic goods, by being more voluminous than organic wastes, quickly exhaust available landfill space, which is, in any case, becoming progressively more scarce and expensive; and [2] incineration of plastics produces toxic gaseous compounds and shifts the solid waste problem to one of air pollution, which is already prohibited and is becoming increasingly politically unacceptable in many countries? However, in times of accelerated depletion of natural resources, plastic waste presents a cheap source of raw materials, and hence, its recycling becomes a necessity. Among the various methods of polymer recycling, thermal and/or catalytic degradation of plastic waste to gas and liquid products is the most promising to be developed into a commercial polymer recycling process. The products of such a process could be utilized as fuels or chemicals. Because pure thermal degradation demands relatively high temperatures and its products require further processing to upgrading their quality, catalytic degradation of plastic waste offers considerable advantages [1].

It occurs at considerably lower temperatures and forms hydrocarbons in the gasoline range, eliminating the necessity of further processing. In such a recycling process, the most valuable product is obviously liquid fuel. Although gaseous products are useful too, as their burning can contribute to the energy demand of an endothermic polymer cracking process, excess gas production is not desirable. Gaseous products are considered low value because of their transportation costs. Consequently, the target of a commercially viable recycling process should be an increase of the liquid product yield. Despite these research efforts, product selectivity in the catalytic degradation of LDPE & PS is not high; various fuel fractions such as gas, gasoline, diesel, and heavy oil are concurrently formed. It is very important to study how the yield of particular fuel fractions can be maximized from the practical point of view. We believe it is reasonable to obtain the gasoline fraction from the degradation of LDPE & PS when solid acid catalysts are used because acidic catalysts are essentially suitable for producing branched and aromatic hydrocarbons with high octane numbers. However, the gasoline yields so far reported in the degradation of low density polyethylene and polystyrenes are sufficiently high, mostly higher than 80%.

The gasoline fraction containing high-boiling-point components such as a diesel fraction must be fractionated for its practical use, and the gasoline with low octane number must be upgraded by a subsequent reforming, which lead to complicated and costly operations. Therefore, it is of great importance to improve product selectivity in the degradation of LDPE & PS to obtain gasoline with high octane number in a good yield. In addition, reduction of the aromatic concentration in gasoline is also a recent requirement. Because the thermal degradation of low density polyethylene and polystyrenes, the main components of waste plastics, is usually a low selectivity reaction, successful application of catalysts to their conversion processes would be a key step toward the development of recycling technologies. There have been a number of investigations in the recent past concerning the use of solid acid catalysts for the degradation of LDPE & PS into fuel oils. The present authors have reported the activation behavior and detailed product distribution from degradation of polyethylene and other researchers have studied the effects of acid strengths and amounts on the product distribution [3] to [6].Some other researcher community also tried with waste plastic to fuel generation by using thermal degradation [7-10], pyrolysis [11, 12], catalytic cracking [13, 14, 15].

[FIGURE 1 OMITTED]

The raw materials were collection from local city restaurant and grocery stores. Collected waste plastic was mixed and comes with foreign materials such as food particles, paper, dust, sand and etc. Collected waste plastic separated out by manually and washes out by using soap. Collected waste plastics were mixture of LDPE, HDPE, PP, PS and PVC. From mixed waste plastic to separated only two types of waste plastic for this experiment. LDPE waste plastic and PS waste plastic mixture was used for this experiment and LDPE waste plastic was blue color garbage bin and PS waste plastic was red color drinking glass. These waste plastics were grinded and put into the reactor chamber for liquefaction process. Two types of waste plastic mixture to fuel production process was performed by using stainless steel reactor and temperature range was 50- 420 [degrees]C (see fig.1). Reactor was properly covered with screw and screws tighten to prevent any gas escape during conversion period. Reactor temperature was monitored by using watlow meter and reactor temperature capacity room temperature to 500 [degrees]C. LDPE and PS waste plastics mixture to liquid fuel production experiment was setup under laboratory fume hood without vacuum system. In this experiment did not apply any extra chemical or any kind of catalyst. In this experiment LDPE and PS waste plastics to liquid fuel production purposed only 750 gm initial feed was used in laboratory scale. In the fuel production diagram showed two type of mixture waste plastic putted into reactor chamber, reactor was heated up 50-420 [degrees]C and produced vapor passed through condenser unit, condensation to produced plastic fuel and fuel was liquid, during condensation period some light gas also generated that light gas (C1-C4) passed through alkali wash by using NaOH/ NaHCO3 solutions. After finished alkali wash then light gas pass through water wash system then light gas was stored in Teflon bag by using small pump. Produced fuel was purified by RCI technology provided RCI purification system and collected final plastic fuel. Residue was collected from reactor after finished whole process and residue was solid black color. In this experimental process electrical power supply was increased slowly from starting temperature to final temperature. When temperature was increased gradually from initial temperature to final temperature mixed plastics started to melt then turned into liquid slurry then liquid slurry to turned vapor when temperature cross more than 300 [degrees]C. In raw materials low density polyethylene melting point temperature is 120 [degrees]C and polystyrene plastic temperature melting point temperature is 240 [degrees]C for that reason in this experiment temperature profile was set up from 50-420 [degrees]C. Mixed waste plastics (LDPE and PS) compound bonds are not breaking in the low temperature range because waste plastics has short hydrocarbon chain to long hydrocarbon chain compounds for that long chain breaking down need higher range temperature like 420 [degrees]C. At 420 [degrees]C temperature mixed waste plastics was already converted into hydrocarbon liquid fuel and nothing is left over except solid residue. After the experimental process we separated all the liquid fuel and passed it through a RCI purification hydrocyclone system to remove all kind of contamination such as water portion and fuel sediments. Waste plastic color and paper level is not effecting the final produced fuel because they are left over as residue. Fuel color is bright yellow and transparent. This process conversion rate is 91% liquid fuel. During fuel production process some vapor are not turned into liquid form because of their boiling point negative. It's come out as light gas and named as natural gas. This gas percentage is 5%. This light gas we passed through liquid alkali solution to remove any harmful contamination then we passage the gas also water system at the end, collected into Teflon bag for future use or analysis purpose. From this experiment we got also some back coal/ residue. This residue percentage is 4%. This residue has higher Btu value. Light gas or natural gas we can use as waste plastic to fuel production period replace of heat source and reduce production cost. In this experiment mass balance calculation showed from 750 gm initial feed to liquid hydrocarbon fuel converted 628.5 gm, light gas converted 37.5 gm from 750 gm initial feed and leftover residue was reaming from 750 gm to 30 gm. Total experiment run time was 5-6 hours and input electricity was 7.25 kWh.

Results and Discussion

Analysis purposes Perkin Elmer Differential Scanning Calorimeter (DSC) was used of two types of mixed waste plastic to produced fuel and by using DSC measured fuel boiling point temperature and fuel enthalpy value are defined. DSC analysis purpose was used carrier gas nitrogen ([N.sub.2]) at rate 20 ml per minute. Temperature range was used for fuel analysis 5-400 [degrees]C and temperature increase rate was 10 [degrees]C/ minute up to 400 [degrees]C. Aluminum pan size was 50 uL and sample analysis purposed used only 50 [micro]L. DSC graph analysis result showed starting temperature 7.56 [degrees]C, finished temperature 169.87 [degrees]C and boiling point temperature is 158.19 [degrees]C (see fig.2). Highest peak level for concentration of fuel temperature is 162.98 [degrees]C, onset temperature is 158.19 and enthalpy delta H value is 34810.8130 J/g. DSC graph analysis result showed also 11.90% fuel was boiled at 50 [degrees]C, 60.49% was at 150 [degrees]C and 100% was 396 [degrees]C.

[FIGURE 2 OMITTED]

[FIGURE 3 OMITTED]

Gas chromatography and mass spectrometer (GC/MS) was used for fuel analysis purpose (see fig.3 and table 1). For GC/MS sample analysis purposed was used capillary column. Helium gas was used as a carrier gas. Elite -5MS capillary column used for gas chromatography and column length 30 meter, 0.25 mmID and 0.5 um df. Column temperature can go maximum 350 [degrees]C. Carrier gas was used for GC/MS as Helium gas. GC program setup initial temperature was 40 [degrees]C and final temperature was used 325 [degrees]C. Temperature ramping rate was 10 [degrees]C per minutes. Initial temperature hold for 1 minute and final temperature is hold for 15 minutes. Sample used for GC/MS 0.5 [micro]L and split flow rate is 101.0 mL/min. MS program setup for mass detection after GC run mass scan 35.00-528.00 EI+. Data format centroid, inter scan time 0.15/ sec and scan time 0.25 sec. According to Perkin Elmer GC/MS analysis chromatogram and compound table shown most of the hydrocarbon compounds are carbons--carbon single bond and hydrocarbon compounds carbon-carbon double bond but some compounds are benzene compounds present in the fuel. All benzene compounds are coming from polystyrene polymer when waste low density plastic and polystyrene heated up, is converted into mixing compounds. Such as at retention time 4.88 minute and trace mass 91, compound is Toluene ([C.sub.7][H.sub.8]), and the compound molecular weight is 92 as well as benzene compound found from this fuel such as retention time 6.48 and trace mass 91, compound is Ethyl benzene (C8H10), retention time 7.04 and trace mass 78, compound is Styrene ([C.sub.8][H.sub.8]), retention time 8.57 and trace mass 118, compound is a-Methylstyrene ([C.sub.9][H.sub.10]), retention time 16.14 and trace mass 168,compound is 1,1'-Biphenyl, 4-methyl([C.sub.13][H.sub.12]), and retention time 18.93 and trace mass 91,compound is Benzene, 1,1'-(2-butene-1,4-diyl) bis- ([C.sub.16][H.sub.16]) etc. In the fuel at retention time 1.63 and trace mass 41, 1st compound is 2-Butene, (E)- ([C.sub.4][H.sub.8]) and molecular weight is 56 and at retention time 26.07 and trace mass 57, long hydrocarbon compound chain is Octacosane ([C.sub.28][H.sub.58]). Aliphatic compounds like alkane and alkene compounds carbon chain start from small to long chain hydrocarbon showing in this fuel is [C.sub.4]-[C.sub.28]. Since benzene groups are present in this fuel with long chain hydrocarbon compounds for that fuel burning capacity is strong. Besides mentioned compounds also some compounds are described in the analysis which is available in the analysis index such as at retention time 1.65 and trace mass 43, compound is Butane ([C.sub.4][H.sub.10]), retention time 1.91 and trace mass 42, compound is Cyclopropane, ethyl-([C.sub.5][H.sub.10]), retention time 1.95 and trace mass 43, compound is Pentane ([C.sub.5][H.sub.12]), retention time 2.54 and trace mass 41, compound is 1-Hexene ([C.sub.6][H.sub.12]), retention time 2.61 and trace mass 41, compound is Hexane ([C.sub.6][H.sub.14]), retention time 3.66 and trace mass 41, compound is 1-Heptene ([C.sub.7][H.sub.14]), retention time 5.20 and trace mass 41,compound is 1-Octene ([C.sub.8][H.sub.16]), retention time 8.08 and trace mass 91, compound is Benzene, propyl-([C.sub.9][H.sub.12]), retention time 9.81 and trace mass 91, compound is Benzene, butyl-([C.sub.10][H.sub.14]), retention time 10.43 and trace mass 57, compounds is Undecane ([C.sub.11][H.sub.24]), retention time 11.42 and trace mass 91, compound is Benzene, pentyl-([C.sub.11][H.sub.16]), retention time 11.98 and trace mass 57, compound is Dodecane ([C.sub.12][H.sub.24]), retention time 13.43 and trace mass 57, compound is Tridecane ([C.sub.13][H.sub.28]) and ultimately retention time 14.70 and trace mass 41, compound is 1-Trideccene ([C.sub.14][H.sub.28]) etc.

[FIGURE 4 OMITTED]

FT-IR analysis of LDPE & PS mixture waste plastic to fuel (fig.4 and table 2) in according with wave number numerous compounds are found and their energy value are determined accordingly. Energy values are calculated, using formula is E=h[upsilon], Where h=Planks Constant, h =6.626x[10.sup.-34] J, u= Frequency in Hertz ([sec.sup.-1]), Where [upsilon]=c/[lambda], c=Speed of light, where, c=3x[10.sup.10] m/s, W=1/[lambda], where [lambda] is wave length and W is wave number in [cm.sup.-1]. Therefore the equation E=h[upsilon], can substitute by the following equation, E=hcW. According to their wave number 2880.33 [cm.sup.-1] functional group is [C-CH.sub.3] that's methyl group, energy value is 5.72x[10.sup.-20] J. Wave number 2731.73 [cm.sup.-1] functional group is C-CH3,calculated energy value is 5.42x[10.sup.-20] J, wave number 1871.59 cm-1,functional group is Non-Conjugated, calculated energy value is 3.71x[10.sup.-20] J, wave number 1603.29 [cm.sup.-1], functional group is Conjugated, calculated energy value is 3.18x[10.sup.-20] J, wave number 1467.96 [cm.sup.-1], functional group is [CH.sub.3], calculated energy value is 2.91x[10.sup.-20] J,wave number 1377.55 [cm.sup.-1] functional group is [CH.sub.3] and calculated energy value is 2.73x[10.sup.-20] J, wave number 1029.73 [cm.sup.-1], functional group is Acetates and calculated energy value is 2.04x[10.sup.-20] J, wave number 1020.53 [cm.sup.-1], functional group is Secondary Cyclic Alcohol and calculated energy value is 2.02x[10.sup.-20] J and wave number 990.91 [cm.sup.-1], functional group is -CH=[CH.sub.2], energy value is 1.96x[10.sup.-20] J and ultimately wave number 907.86 [cm.sup.-1] functional group is -CH=[CH.sub.2] and calculated energy value is 1.80x[10.sup.-20] J as well. Euclidean Search Hit List: 0.508 F91080 TRICHLOROACETONITRILE, 0.472 F37460 2,5-DIHYDROXYACETOPHENONE, 0.397 F65155 2-METHOXYPHENYLACETONITRILE, 0.384 F65470 3-METHYLACETOPHENONE, 0.284 F64700 2-METHOXYACETOPHENONE, 0.275 F54150 2-HYDROXYACETOPHENONE, 0.267 F22850 4-CHLOROACETOPHENONE, 0.248 F38558 3,4-DIMETHOXYACETOPHENONE, 0.242 F65156 3-METHOXYPHENYLACETONITRILE, 0.233 F00508 ETHYL ACETOHYDROXAMATE (Perkin Elmer FT-IR tutorial library).

Conclusion

The thermal degradation of mixed waste plastics (LDPE and PS) to liquid fuel production process was performed by using stainless steel reactor without adding any kind of catalyst. Produced fuel density is 0.79 g/ml and various techniques were used for fuel analysis purposed such as GC/MS, FT-IR and DSC. GC/MS analysis result showed produce fuel has aliphatic and aromatic group compounds. Aliphatic compounds are alkane, alkene group and aromatic compounds are benzene groups. Benzene group compounds were form in this fuel because initial material or initial feed was mixture of PS and LDPE waste plastics. GC/MS analysis result showed some benzene related compounds such as Toluene, Ethylbenzene, Styrene, Benzene, (1-methylethyl)-, [alpha]-Methylstyrene, Benzene, 2-propenyl-, Benzene, butyl-, Benzene, pentyl-, Benzene, 1,1'-(1,3-propanediyl)bis-, Benzene, 1,1'-(2-butene-1,4-diyl)bis-. Produced fuel short chain hydrocarbon to long chain hydrocarbon range is C4 to C28 determination by GC/MS analysis. FT-IR spectrum 100 analysis results determine fuel functional group band energy and band energy reflecting calorific value. By using this method could be solve LDPE and PS waste plastics problem and also landfill problem or boost up energy creation for next generation.

Acknowledgement

The author acknowledges the support of Dr. Karin Kaufman, the founder and sole owner of Natural State Research, Inc. The authors also acknowledge the valuable contributions of laboratory team members during the preparation of this manuscript.

References

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Moinuddin Sarker *, Mohammad Mamunor Rashid and Muhammad Sadikur Rahman

Natural State Research Inc, Department of Research and Development, 37 Brown House Road (2ndFloor), Stamford, CT-06902, USA * Corresponding Author E-mail: msarker@naturalstateresearch.com
Table 1: GC/MS chromatogram compound list of LDPE and PS mixture
plastics to fuel

Number Retention Trace Compound
of Time (M) Mass Name
Peak (m/z)

1 1.63 41 2-Butene, (E)-

2 1.65 43 Butane

3 1.91 42 Cyclopropane,
 ethyl-

4 1.95 43 Pentane

5 2.54 41 1-Hexene

6 2.61 41 Hexane

7 3.66 41 1-Heptene

8 3.78 43 Heptane

9 4.88 91 Toluene

10 5.20 41 1-Octene

11 5.35 43 Octane

12 6.48 91 Ethylbenzene

13 7.04 78 Styrene

14 7.08 104 1,3,5,7-
 Cyclooctatetraene

15 7.56 105 Benzene, (1-
 methylethyl)-

16 7.94 117 Benzene,
 cyclopropyl-

17 8.08 91 Benzene,
 propyl-

18 8.57 118 [alpha]-
 Methylstyrene

19 8.65 41 1-Decene

20 8.79 43 Decane

21 9.33 117 Benzene, 2-
 propenyl-

22 9.81 91 Benzene,
 butyl-

23 10.30 41 1-Undecene

24 10.43 57 Undecane

25 11.42 91 Benzene,
 pentyl-

26 11.85 41 1-Dodecene

27 11.98 57 Dodecane

28 13.31 41 1-Tridecene

29 13.43 57 Tridecane

30 14.70 41 1-Tetradecene

31 14.80 57 Tetradecane

32 16.00 41 1-Pentadecene

33 16.10 57 Pentadecane

34 16.14 168 1,1'-Biphenyl,
 4-methyl-

35 17.23 41 1-Hexadecene

36 17.31 57 Hexadecane

37 18.19 92 Benzene, 1,1'-
 (1,3-
 propanediyl)bis-

38 18.39 41 8-Heptadecene

39 18.48 57 Heptadecane

40 18.93 91 Benzene, 1,1'-
 (2-butene-1,4-
 diyl)bis-

41 19.50 55 3-Eicosene, (E)-

42 19.58 57 Octadecane

43 20.55 55 1-Nonadecene

44 20.62 57 Nonadecane

45 21.55 55 1-Docosene

46 21.62 57 Eicosane

47 22.58 57 Heneicosane

48 23.50 57 Heneicosane

49 25.23 57 Tetracosane

50 26.07 57 Octacosane

51 26.88 57 Octacosane

Number Compound Molecular Carbon- NIST
of Formula Weight Carbon Library
Peak Bonding Number

1 [C.sub.4] 56 Double 105
 [H.sub.8]

2 [C.sub.4] 58 Single 18940
 [H.sub.10]

3 [C.sub.5] 70 Single 114410
 [H.sub.10]

4 [C.sub.5] 72 Single 114462
 [H.sub.12]

5 [C.sub.6] 84 Double 500
 [H.sub.12]

6 [C.sub.6] 86 Single 61280
 [H.sub.14]

7 [C.sub.7] 98 Double 107734
 [H.sub.14]

8 [C.sub.7] 100 Single 61276
 [H.sub.16]

9 [C.sub.7] 92 Double/ 291301
 [H.sub.8] Benzene

10 [C.sub.8] 112 Double 1604
 [H.sub.16]

11 [C.sub.8] 114 Single 229407
 [H.sub.18]

12 [C.sub.8] 106 Double/ 158804
 [H.sub.10] Benzene

13 [C.sub.8] 104 Double/ 291542
 [H.sub.8] Benzene

14 [C.sub.8] 104 Double 113230
 [H.sub.8]

15 [C.sub.9] 120 Double/ 228742
 [H.sub.12] Benzene

16 [C.sub.9] 118 Double/ 113961
 [H.sub.10] Benzene

17 [C.sub.9] 120 Double/ 113930
 [H.sub.12] Benzene

18 [C.sub.9] 118 Double/ 2021
 [H.sub.10] Benzene

19 [C.sub.10] 140 Double 118883
 [H.sub.20]

20 [C.sub.10] 142 Single 291484
 [H.sub.22]

21 [C.sub.9] 118 Double/ 114744
 [H.sub.10] Benzene

22 [C.sub.10] 134 Double/ 47535
 [H.sub.14] Benzene

23 [C.sub.11] 154 Double 5022
 [H.sub.22]

24 [C.sub.11] 156 Single 114185
 [H.sub.24]

25 [C.sub.11] 148 Double/ 113915
 [H.sub.16] Benzene

26 [C.sub.12] 168 Double 107688
 [H.sub.24]

27 [C.sub.12] 170 Single 291499
 [H.sub.26]

28 [C.sub.13] 182 Double 107768
 [H.sub.26]

29 [C.sub.13] 184 Single 114282
 [H.sub.28]

30 [C.sub.14] 196 Double 69725
 [H.sub.28]

31 [C.sub.14] 198 Single 113925
 [H.sub.30]

32 [C.sub.15] 210 Double 69726
 [H.sub.30]

33 [C.sub.15] 212 Single 107761
 [H.sub.32]

34 [C.sub.13] 168 Double/ 113287
 [H.sub.12] Benzene

35 [C.sub.16] 224 Double 69727
 [H.sub.32]

36 [C.sub.16] 226 Single 114191
 [H.sub.34]

37 [C.sub.15] 196 Double/ 229725
 [H.sub.16] Benzene

38 [C.sub.17] 238 Double 113620
 [H.sub.34]

39 [C.sub.17] 240 Single 107308
 [H.sub.36]

40 [C.sub.16] 208 Double/ 152950
 [H.sub.16] Benzene

41 [C.sub.20] 280 Double 62838
 [H.sub.40]

42 [C.sub.18] 254 Single 57273
 [H.sub.38]

43 [C.sub.19] 266 Double 113626
 [H.sub.38]

44 [C.sub.19] 268 Single 114098
 [H.sub.40]

45 [C.sub.22] 308 Double 113878
 [H.sub.44]

46 [C.sub.20] 282 Single 290513
 [H.sub.42]

47 [C.sub.21] 296 Single 107569
 [H.sub.44]

48 [C.sub.21] 296 Single 107569
 [H.sub.44]

49 [C.sub.24] 338 Single 34731
 [H.sub.50]

50 [C.sub.28] 394 Single 134306
 [H.sub.58]

51 [C.sub.28] 394 Single 134306
 [H.sub.58]

Table 2: FT-IR Spectrum compound functional group list of LDPE and
PS to fuel

Number Band Functional
of Number Group Name
Peak ([cm.sup.-1])

1 2880.33 C-C[H.sub.3]

2 2731.73 C-C[H.sub.3]

3 2671.52 C-C[H.sub.3]

4 1871.59 Non-Conjugated

5 1816.78 Non-Conjugated

6 1799.72 Non-Conjugated

7 1743.84 Non-Conjugated

8 1719.06 Non-Conjugated

9 1685.69 Non-Conjugated

10 1630.29 Non-Conjugated

11 1603.29 Conjugated

12 1467.96 C[H.sub.3]

13 1377.55 C[H.sub.3]

14 1029.73 Acetates

15 1020.53 Secondary
 Cyclic Alcohol

16 990.91 -CH=C[H.sub.2]

17 907.86 -CH=C[H.sub.2]
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Author:Sarker, Moinuddin; Rashid, Mohammad Mamunor; Rahman, Muhammad Sadikur
Publication:International Journal of Applied Environmental Sciences
Date:Sep 1, 2012
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