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Article
The Use of Supercritical Water for the Liquefaction of Polypropylene into Oil
Wan-Ting (Grace) Chen, KAI JIN, and Nien-Hwa Linda Wang
ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/
acssuschemeng.8b03841 • Publication Date (Web): 10 Jan 2019
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Page 1 of 37 ACS Sustainable Chemistry & Engineering
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4 1 The Use of Supercritical Water for the Liquefaction of
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7 2 Polypropylene into Oil
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10 3 Wan-Ting Chen, Kai Jin, and Nien-Hwa Linda Wang*
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4 School of Chemical Engineering, Purdue University, West Lafayette, IN 47907, USA
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5 * Corresponding author. 480 W Stadium Avenue, West Lafayette, Indiana, 47907; phone: +1-765-494-
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18 6 4081; fax: +1-765-494-0805; email: wangn@ecn.purdue.edu
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21 7 Abstract
22 8 About five billion tons of plastic waste have accumulated in landfills and the natural
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9 environment over the past 50 years. Polypropylene (PP) waste accounts for about 23% of the total
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27 10 plastic waste. Converting PP waste into useful products can reduce the accumulated waste and
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29 11 associated risks to the environment and human health. In this study, model PP was converted into
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12 oil using supercritical water at 380-500°C and 23 MPa over a reaction time of 0.5-6 hr. Up to 91
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34 13 wt.% of model PP was converted into oil at 425°C with a 2-4 hr reaction time or at 450°C with a
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36 14 0.5-1 hr reaction time. Higher reaction temperatures (>450°C) or longer reaction times (>4 hr) led
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38 15 to more gas products. The oil products consisted of olefins, paraffins, cyclics, and aromatics. About
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41 16 80-90 wt.% of the oil components had the same boiling point range as naphtha (25-200°C) and
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43 17 heating values of 48-49 MJ/kg. Reaction pathways for converting model PP into oil under the
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45 18 tested conditions were proposed. Preliminary analyses indicate that this conversion process is net-
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19 energy positive and potentially has a higher energy efficiency and lower greenhouse gas emissions
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50 20 than incineration and mechanical recycling. The oil derived from PP has potential to be used as
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52 21 gasoline blendstocks or feedstocks for other chemicals.
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ACS Sustainable Chemistry & Engineering Page 2 of 37
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3 23 Suggested Keywords: Plastic recycling, polypropylene, supercritical water, hydrothermal
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5 24 processing, naphtha
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9 26 INTRODUCTION
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11 27 The plastic produced and the plastic waste in the landfills and oceans have continued to
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28 rise exponentially over the past 50 years.1 About six billion tons of plastic waste had been
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16 29 generated globally as of 2015.2 The majority (76%) of the waste was landfilled, 12% was
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18 30 incinerated, and 3% ended up in the oceans.2, 3 Current global recycle rates indicate that only 9%
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31 of the total plastic waste is being recycled. If the current trend continues, the planet will have 12
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23 32 billion tons of plastic waste in landfills or the natural environment, leading to more plastics than
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25 33 fish in the oceans by 2050.1, 4 Huge gyres of floating plastics trash (twice the size of Texas) are
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27 34 already circulating in the world’s oceans.5 Annually mismanaged plastic waste released to land is
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30 35 23 times that released to oceans.6 Most plastics take hundreds of years to degrade in the
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32 36 environment. As they degrade slowly, they release toxic particles and chemicals into the
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34 37 environment, causing contamination of surface water, ground water, and the oceans.7 This
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38 pollution poses serious threats to our ecosystems, drinking water, food supply, and human health.3,6
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39 39 The fast accumulation is mainly due to the rapid rise in the production of virgin plastics,
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41 40 slow degradation of the waste plastics, and the low incineration rate (12%) and recycling rate (9%).
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41 Consignment to landfills has been the least costly and financially preferred method for waste
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46 42 plastic disposal. The low recycling rate is mainly due to two reasons. First, only 14% of the plastic
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48 43 waste was collected.4 Second, a significant fraction of the collected mixtures is too complex to be
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50 44 economically recycled as most of the current collection systems result in mixtures of various types
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53 45 of plastic waste.2, 3 The options for making high-value products using the complex mixtures are
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55 46 limited.
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58 2
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3 47 Incineration is the most mature method of reducing the amount of plastic waste but less
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6 48 preferred financially than landfilling.8 It can accept mixed plastics but produces carcinogenic
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8 49 products and releases environmental pollutions.9 For these reasons, the total amount of waste
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10 50 incinerated is only 12% to date.2
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51 Mechanical recycling is a widely used recycling method.10 However, it has limited
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15 52 applications because it usually causes polymer degradation and cannot handle mixed plastics
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17 53 because of the immiscibility of polymer blends.11 Furthermore, mechanical recycling usually
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54 requires washing and drying, which are energy-intensive processes.12
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22 55 Pyrolysis is an emerging technology to reduce the plastic waste. It can convert mixed
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24 56 plastics (except Type 3, PVC) to fuels. However, pyrolysis of plastic waste typically occurs at high
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26 57 temperatures (450-800°C).9, 13 It has low oil yields without catalysts and the oil produced needs
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29 58 upgrading for fuel applications, resulting in a high processing cost.9, 14 This is a key reason that the
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31 59 plastic fuel industries are not economically competitive when the crude oil price is relatively low.
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33 60 Hydrothermal processing using subcritical or supercritical water to convert feedstocks into
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61 liquid products is called hydrothermal liquefaction (HTL). HTL is a thermochemical
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38 62 depolymerization process in an enclosed reactor, where water can serve as a solvent, catalyst, or
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40 63 reactant.15 HTL usually requires moderate temperatures (280–380°C) and pressures (7-30 MPa).15
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64 As the reaction condition approaches the critical point of water, its properties such as dielectric
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45 65 constant, ionic strength, density, and heat/mass transport coefficients are changed rapidly for both
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47 66 subcritical and supercritical water. Especially, the rapid change of density correlates with other
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49 67 macroscopic properties to reflect changes at the molecular level such as solvation power,
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52 68 molecular diffusivity, and viscosity.15 These significant changes enable the subcritical or
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54 69 supercritical water to bring about fast, selective, and efficient reactions to convert organic wastes
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58 3
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3 70 to crude oil, as compared to conventional thermochemical conversion methods such as pyrolysis
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6 71 and gasification.14, 16, 17
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8 72 Because HTL can process wet feedstocks with organic contaminants without the need of
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10 73 washing and drying, HTL has been extensively studied for converting wet biomass into biocrude
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74 oil.15, 18-22 Furthermore, the hydrogen-donating ability of subcritical and supercritical water has
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15 75 been used to upgrade heavy crude oil derived from petroleum and biomass,23-26 or to desulfurize
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17 76 crude oil.27-29 However, the feedstocks of these studies typically were too complex to develop
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77 comprehensive reaction pathways, unless model compounds were used.21, 30, 31 Instead of
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22 78 studying how the chemical structure of hydrocarbons may affect the reactions under supercritical
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24 79 water, previous studies primarily focused on how to improve and engineer the fuel properties of
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26 80 heavy crude oils.23-29
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29 81 Few studies have focused on using supercritical water to liquefy polyolefins into oil or
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31 82 gas products. Only two studies have been reported on the conversion of polyethylene into oil.
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33 83 Watanabe et al (1998) used supercritical water for the liquefaction of low-density polyethylene
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84 (LDPE).32, 33 The oil yield was only 30% because of a relatively low temperature (400°C) and a
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38 85 short reaction time (0.5 hr). Moriya and Enomoto (1999) used supercritical water for converting
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40 86 high-density polyethylene (HDPE) into oil, but no kinetic data were reported.32, 33 Only limited
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87 reaction conditions were tested in both studies.32, 33 The products (oil, gas, post-SWL water, and
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45 88 solid) were not analyzed in detail, and the application of the oil products remained unclear. No
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47 89 comprehensive pathways for the conversion of PE in supercritical water were reported
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49 90 previously.
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52 91 The use of supercritical water for converting polypropylene (PP) into useful products has
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54 92 not been explored previously. There has been only one study using steam cracking for converting
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3 93 PP into oil.34 Since the pressure was below the critical pressure, water vapor (instead of
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6 94 supercritical water), was used for the conversion. Steam cracking required more energy than
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8 95 SWL since a phase change was involved.15 Only one reaction condition was tested and no
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10 96 detailed characterization was carried out to explore the potential applications of the various
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97 products. A second study using subcritical water for converting PP into wax for use as a solid
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15 98 fuel was reported recently.30 None of these two studies reported any kinetic data or proposed a
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17 99 pathway for the conversion.
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100 Recently, polyolefin waste has been studied as a co-feed for coal or biomass
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22 101 conversion.35, 36 However, these studies focused mainly on the conversion efficiency of coal or
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24 102 biomass. The purpose of co-feeding plastic with coal or biomass was to enhance the quality or
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26 103 the quantity of the oils. Understanding the kinetics or the reaction pathways of polyolefin
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29 104 conversion was not the focus. In short, there was no literature study exploring the use of
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31 105 supercritical water to produce various useful products from PP. No kinetic data or reaction
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33 106 pathways for the conversion of PP in supercritical water have been reported. In particular,
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107 whether the branching structure of PP affects the reactivity or selectivity of intermediates in
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38 108 supercritical water has not been reported in the literature.
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40 109 The long-term objective of this study is to develop efficient methods to convert PP waste
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110 to oils, which can be used as feedstocks for fuels or other chemicals. It is important to understand
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45 111 first how a model PP is converted into oils. This study is focused on the use of supercritical water
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47 112 for the liquefaction (SWL) of PP. The effects of reaction temperature and reaction time were
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49 113 investigated because they are the major factors affecting hydrothermal processing of organic
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52 114 waste.20, 32, 37 To evaluate the potential of the oil product for fuel applications, the analyses for
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54 115 elemental composition, boiling point distribution, and fuel specification (viscosity, density, surface
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3 116 tension, and heating values) were carried out. Chemical compositions of oil and gas products were
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6 117 characterized using GC-MS. The thermal degradation behavior and molecular weight distribution
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8 118 of the solid residue were also analyzed. Potential reaction pathways for SWL of PP were proposed.
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10 119 Furthermore, the energy demand, energy efficiency, and greenhouse gas emissions (GHG) were
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120 estimated and compared to those for incineration, mechanical recycling, pyrolysis, and solvent
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15 121 extraction.
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17 122 This is the first study using supercritical water, without the need of catalyst or hydrogen,
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123 to convert PP into oil with high yields (91 wt.%). The pathways for the conversion of PP in
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22 124 supercritical water were developed for the first time based on the analysis of the reaction
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24 125 intermediates. No comprehensive pathways for the conversion of PE in supercritical water were
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26 126 reported previously. Comparison of the reaction intermediates between SWL of PP and PE
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29 127 indicated that the branching of PP affects significantly the selectivity of the intermediates and the
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31 128 reaction pathways. More energy is needed to break the C-C bonds in the backbone than to break
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33 129 the C-CH3 bonds in PP, resulting in mostly olefins in the oil and gas intermediates in PP
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130 conversion, instead of mostly paraffins in PE conversion. The olefins in the oils derived from PP
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38 131 lead to the formation of cyclics and aromatics, which were not observed or reported previously for
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40 132 PE conversion.
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133 The oils derived from PP have a similar boiling point range, heating value, H/C and O/C
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45 134 ratios, carbon numbers, density, viscosity, and surface tension as gasoline. The oils have
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47 135 potential to be used as gasoline blendstocks, without upgrading processes such as cracking or
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49 136 distillation. Furthermore, it is expected that SWL is a net-energy positive process and has higher
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52 137 energy efficiency and lower greenhouse gas (GHG) emissions than incineration and mechanical
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54 138 recycling.
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3 139 MATERIALS AND METHODS
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6 140 Feedstocks. The polymer used in this study was polypropylene (PP) from Sigma-Aldrich
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8 141 (St. Louis, MO) with a density of 0.9 g/mL at 25°C. The number-average molecular weight (Mn)
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10 142 was about 67,000 (g/mol) and the weight-average molecular weight (Mw) was about 250,000
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143 (g/mol). The polydispersity (Mw/Mn) was 3.73. All chemicals and reagents used were from
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15 144 Fischer Scientific (Waltham, MA) and used as received.
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17 145 Supercritical Water Liquefaction (SWL). The SWL experiments were conducted with
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146 a batch reactor similar to that of previous studies.37-39 The reactor parts, fittings, and accessories
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22 147 were purchased from Swagelok (Solon, OH). The hydrothermal reactors used in the study were
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24 148 made of a stainless-steel tubing, a stainless-steel capillary, and a high-pressure valve with an
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26 149 operating volume of 35 mL. SWL reactors were heated with a tubular furnace (Thermo
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29 150 Scientific, Lindberg Blue M Muffle Furnace). The schematic diagram of the experimental set-up
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31 151 is available in the Supporting Information (Fig. S1).
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33 152 SWL reactions were carried out at temperatures from 380 to 500°C with a reaction time
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153 from 0.5 to 6 hr. Each SWL test used 1 gram of polymeric feedstock and proper amounts of
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38 154 deionized water to achieve supercritical water conditions with a reaction pressure of 23 MPa
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40 155 (3400 psi). The reactor was subsequently assembled and the headspace was purged with nitrogen
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156 three times to remove the residual air. Nitrogen gas was again added to the reactor to build up to
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45 157 a 0.62 MPa (90 psi) gauge pressure prior to the start of the SWL reactions. Initial and final
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47 158 pressures were recorded before and after the reactions. For each condition, at least two
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49 159 independent SWL tests (n≥2) were carried out. The average value and the standard deviation
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52 160 were reported. After each test, the reactors were cooled down to room temperature within 0.5 hr.
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3 161 The tubular heaters used in this study took about 11 minutes to reach 450°C. The reaction time
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6 162 reported in this study did not include the heating time to reach the target temperature.
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8 163 Product Separation and Yield Calculation. The SWL product separation procedure is
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10 164 available in the Supporting Information (Fig. S2). The gas pressure was measured with a gauge
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165 attached for determining the gas yield calculated based on the ideal gas law and the analyzed gas
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15 166 composition of the gaseous product.19-21, 40 More details about this protocol were also available in
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17 167 previous studies converting wet biowaste into biocrude oil via HTL.19-21, 34, 40 In addition, the gas
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168 yield calculated from the ideal gas law was checked by measuring the weight difference of the
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22 169 reactor and the reactor contents before and after the experiment. The gas yield and oil yield
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24 170 calculated accordingly from these two methods agree closely. Detail can be found in the
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26 171 Supporting Information (Fig. S3).
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29 172 After the reaction, the needle valve was opened and a sample of the gas was collected for
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31 173 further analysis. The contents in the reactor were poured into glass vials. For TGA and elemental
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33 174 analysis, the oil product, which was naturally separated from the water, was collected for the
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175 analyses. For GC-MS analysis of the oil sample, dichloromethane (DCM) was poured to the
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38 176 reactor, and the reactor was shaken on a vortex mixer (Fisher Scientific, Hampton, NH) for 5 s.
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40 177 Then the reactor was rinsed using 10 mL of DCM 3 times. All the rinsing solvent was collected
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178 and mixed with the oil products in the same vial. The collected products with DCM were filtered
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45 179 through a vacuum filtration apparatus with pre-weighed filter paper to separate the liquid and
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47 180 solid products. The solid product along with the filter paper was placed in the hood for overnight
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49 181 drying. The separation of the aqueous phase and the DCM phase was carried out by a separatory
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52 182 funnel.
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54 183 For each SWL test, yields of solid residue, gas, and oil products were determined by
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56 184 Equations 1-3 (based on dry weight, d.w.), which were used in previous HTL studies.14, 19-21, 34
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3 Wresidue
4 Solid residue yield (d.w.%) = × 100 (1)
5 WFeedstock
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8 Based on the ideal gas law method and verified
9 Gas product yield (d.w%) = (2)
10 using the weight difference method
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Oil product yield (d.w.%) = 100 - (solid residue + gas) (3)
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17 185 Analysis of oil and post-SWL water. After the SWL reaction, the oil product was naturally
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19 186 separated with the post-SWL water. There was no solvent evaporation or rinsing with DCM before
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21 187 the analyses.
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188 Carbon and hydrogen analyses were performed via combustion at 990°C with an elemental
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26 189 analyzer (Exeter Analytical, Inc., North Chelmsford, MA). Duplicate analyses were conducted for
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28 190 each sample and the average value was reported. The higher heating value (HHV) of oil was
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191 calculated using the Dulong formula based on the elemental composition: HHV (MJ/kg) = 0.3383
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33 192 × C+1.422 × (H–O/8), where C, H, and O are the carbon, hydrogen, and oxygen mass
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35 193 percentages of the oil products.18, 19 Oxygen was calculated by the difference (i.e., O (wt.%) = 100
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37 194 –C (wt.%)–H (wt.%)).
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40 195 The chemical compositions of the oil and post-SWL water were analyzed using GC-MS
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42 196 (Shimadzu QP-2010 GC-MS). More details can be found in the literature.18-21, 39, 41 The MS is an
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44 197 electron ionization single quadrupole instrument. Gas chromatography was performed on a DB-
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198 5MS column (Agilent, Santa Clara, CA) with an injection temperature of 300°C and an ion
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49 199 source temperature of 260°C. The temperature program was performed in ~5 min at 30-60°C,
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51 200 followed by an oven temperature ramp of 5°C/min to 300-325°C for a final ~10 min. The mass
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201 spectrometer was operated in positive electron impact mode in m/z 40-500 scan range. The
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56 202 spectra of all chromatogram peaks were compared with an electron impact mass spectrum from
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3 203 NIST Mass Spectral Database (NIST05). In addition to using a DB-5MS column to analyze the
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6 204 post-SWL water, another column, a ZB-WAX column, which is commonly used for analyzing
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8 205 oxygenated compounds under GC-MS,18-21, 40 was also used for analyzing the post-SWL water.
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10 206 Thermogravimetric analysis (TGA) of the PP-derived oil was performed on a Q50 TGA
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207 (TA Instruments, Schaumburg, IL) from room temperature to 550ºC in 60.0 mL/min N2 at
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15 208 10ºC/min to estimate the boiling point distribution.
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17 209 Analysis of gas products. The chemical compositions of the gas products were analyzed
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210 using another GC-MS (Agilent Technologies, Santa Clara, CA), which has been reported in
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22 211 previous studies.18-21, 39, 41 Gas chromatography was performed on a 15 m GS-GASPRO column
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24 212 with 0.32 mm inner diameter (Agilent Technologies, Santa Clara, CA) with an injection
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26 213 temperature of 200°C, an MSD transfer line of 200°C, and an ion source adjusted to 230°C. The
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29 214 temperature program was 2 min at 35°C, followed by an oven temperature ramp of 3°C/min to
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31 215 160°C for a final 2 min. The mass spectrometer was operated in positive EI in m/z 25-300 scan
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33 216 range. The spectra of all chromatogram peaks were compared with electron impact mass spectra
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217 from NIST Mass Spectral Database (NIST08) and W8N08 library (John Wiley & Sons, Inc.,
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38 218 Hoboken, NJ).
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40 219 Analysis of solid products. The molecular weight distribution of solid products after SWL
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220 reactions was evaluated by matrix-assisted laser desorption ionization (MALDI) time-of-flight
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45 221 (TOF) MS. Spectra were obtained on a Voyager-DE PRO MALDI-TOF instrument (Applied
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47 222 Biosystems, Framingham, MA). Mass spectra were acquired in positive ion linear mode with an
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49 223 accelerating voltage of 25,000 V. Anthracene and CHCA were used as matrices. One microliter of
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52 224 matrix was mixed with one microliter of sample and spotted on the plate.
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3 225 Fuel specification analysis of oil products. The fuel specifications including viscosity,
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6 226 density, and surface tension of oil were measured. The characterizations of fuel specification were
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8 227 conducted by ASTM standards (ASTM D445) or previously reported methods.42
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10 228 RESULTS AND DISCUSSION
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229 SWL Product Yields from Model Polypropylene (PP). In order to study the effects of
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15 230 reaction temperature and time on the liquefaction of PP, the conversion was carried out at a
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17 231 range of reaction conditions, 380-450°C for 0.5-4 hr (Fig. 1). The highest oil yield (91%) was
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232 obtained at 425°C with a 2-4 hr reaction time or 450°C with a 0.5-1 hr reaction time. At 380°C,
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22 233 very little PP was converted to oil (Fig. 1a). As the reaction temperature increased to 425°C, the
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24 234 oil yield increased with increasing reaction time (Figs. 1b and 1c). At 450°C, the oil yield (90-
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26 235 91%) was the highest at 0.5-1 hr. Further increase in reaction time resulted in a lower oil yield
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29 236 because more PP was converted into gas (Fig. 1d). The gas yield was increased from 10% to
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31 237 17% when the reaction time was increased from 4 hr to 6 hr at 425°C (see Supporting
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33 238 Information, Fig. S4). The gas yield was even higher (28%) at 500°C with a short reaction time
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239 (0.5 hr, see Supporting Information, Fig. S5). Very little black char was generated under all the
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38 240 conditions tested, because supercritical water stabilized certain radicals to minimize coke
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40 241 formation.15, 32
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58 11
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4 100 (a) 380°C 100 (b) 400°C
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6 80 80
Yield (wt.%)
Yield (wt.%)
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8 60 60
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10 40 40 Oil
Oil Gas
11 Gas Solid
12 20 Solid
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0 0
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15 0.5hr 1hr 2hr 4hr 0.5hr 1hr 2hr 4hr
16 100 425°C 100
17 (c) (d) 450°C
18 80 80
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Yield (wt.%)
Yield (wt.%)
20 60 60
21 Oil
22 Oil Gas
40 Gas 40 Solid
23 Solid
24 20 20
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0 0
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28 0.5hr 1hr 2hr 4hr 0.5hr 1hr 2hr 4hr
29 242
30 243 Fig. 1. SWL product yields from model PP with reaction time of 0.5-4 hr via SWL at (a) 380°C,
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244 (b) 400°C, (c) 425°C, and (d) 450°C (n ≥ 2).
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34 245 Elemental Analysis and Higher Heating Values (HHVs) of Oil Products. The oil
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36 246 products generated under high yield conditions were analyzed for the elemental composition.
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38 247 The HHVs and the carbon, hydrogen, and oxygen contents of oil products are compared with
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248 those of transportation fuels (Fig. 2a). The standard deviation of the elemental analysis was also
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43 249 included in Fig. 2a.
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45 250 All the oil products have a similar HHV (with the range of 46.3-49.3 MJ/kg) as gasoline
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47 251 (47.7 MJ/kg). In particular, the oil products converted at 425°C with a 2-4 hr reaction time or at
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50 252 450°C with a 0.5-1 hr reaction time have similar or higher HHVs than that of gasoline. This is
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52 253 mainly attributed to higher hydrogen contents of the oil products.
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58 12
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3 254 Fig. 2a indicates that increasing the reaction time reduces the HHVs of the oil products
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6 255 due to the lower hydrogen contents in the oils. When the reaction time increased from 0.5 hr to 4
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8 256 hr at 450°C, the hydrogen contents of the oils decreased from 14 wt.% to 12 wt.%. Increasing the
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10 257 reaction temperature from 425°C to 450°C with the same reaction time (4 hr) also reduced the
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258 hydrogen content and the HHV of the oil. The results suggested that more hydrogen of the oil
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15 259 was converted into hydrogen gas at a higher temperature or a longer reaction time.
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17 260 Furthermore, the Van Krevelen diagram (Fig. 2b) shows that SWL can produce oils with
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261 similar H/C and O/C ratios as gasoline, diesel, or jet fuel, depending on the reaction conditions.
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22 262 The oils derived from PP liquefaction had much higher HHV (48-49 MJ/kg) than the bio-oils
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24 263 derived from biomass liquefaction (30-36 MJ/kg), mainly because their oxygen contents (<0.6
25
26 264 wt.%) were much less than those of the bio-oils (~10-20 wt.%).15
27
28
29 265
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58 13
59
1
2
3 (a)
4
5 Carbon Hydrogen Oxygen HHV
6
100 50
7 425°C 450°C
8
Elemental Compositions (wt.%)
9
10 80
11 49
12
13
HHV (MJ/kg)
14 60
15
16 48
17
18 40
19
20
21
47
20
22
23
24
25 0 46
26 2hr 4hr 0.5hr 1hr 2hr 4hr Gasoline Diesel Jet Fuel
27
28 (b)
29 2.1
30
31
32
33 2.0
34
35
425°C, 2hr
H/C atomic ratio
36 1.9
37 425°C, 4hr
38 450°C, 0.5hr
39
40 1.8 450°C, 1hr
41 450°C, 2hr
42
450°C, 4hr
43 1.7
44 Gasoline
45 Diesel
46
47 1.6 Jet Fuel
48 Biodiesel
49
50 0.0 0.2 0.4
51
52 O/C atomic ratio
53
54
266 Fig. 2. Elemental compositions of the oil (n=2): (a) HHV, carbon, hydrogen, and oxygen
55 267 contents of oil; and (b) the Van Krevelen diagram of the oil obtained at various reaction
56 268 conditions.
57
58 14
59
1
2
3 269 TG Analysis of Oil. Thermogravimetric analysis (TGA), which can be considered as a
4
5
6 270 miniature “distillation”,20 was carried out to investigate the boiling point distribution and
7
8 271 potential applications of the oil products (Fig. 3). The weight percentage of the oil distilled over
9
10 272 TGA temperature of 25-550°C was available in the Supporting Information (Fig. S6). The fuel
11
12
13
273 fractions with the boiling point range of 25-200°C, 200-300°C, and 300-550°C were defined as
14
15 274 naphtha (or gasoline), (jet fuel + light diesel), and (diesel + lubricant), respectively. The naphtha
16
17 275 yield was defined as the naphtha fraction in the oil multiplied by the oil yield at a specific
18
19
276 reaction condition.
20
21
22 277 When the reaction time increased from 2 hr to 6 hr at 425°C, the naphtha fraction
23
24 278 increased from 73% to 94% while the heavier fractions ((jet fuel + light diesel) and (diesel +
25
26 279 lubricant)) decreased accordingly. This result indicates that the heavier fractions were cracked
27
28
29 280 into naphtha as the reaction time increased. A similar trend was also observed as the reaction
30
31 281 time extended from 0.5 hr to 1 hr at 450°C. Since the majority (94%) of the oil is in the naphtha
32
33 282 range, the oil products could be directly used as gasoline blendstocks. The naphtha-like products
34
35
36
283 also could be converted into specialty solvents and other chemicals using existing refining
37
38 284 infrastructures.43
39
40 285 Cracking of the heavier fractions into naphtha required more than 4 hr at 425°C.
41
42
286 Although the naphtha fraction remained relatively constant as the reaction temperature increased
43
44
45 287 from 450°C to 500°C, the naphtha yields decreased because the oil yields decreased (Fig. 3).
46
47 288 Higher temperature favors gasification rather than liquefaction. The highest naphtha yield was
48
49 289 achieved at 425°C and 4 hr or 450°C and 1 hr.
50
51
52
53
54
55
56
57
58 15
59
1
2
3
4 Naphtha Jet Fuel + Light Diesel
5 Diesel + Lubricant Naphtha Yield
6
7 425°C 450°C 500°C 100
8
100
Fractions in Oil (wt.% of Oil)
Naphtha Yield (wt.% of PP)

9
10
11 80 80
12
13
14
15
60 60
16
17
18 40 40
19
20
21
22 20 20
23
24
25 0 0
26
27
2hr 4hr 6hr 0.5hr 1hr 2hr 4hr 0.5hr
28
29 290
30 291 Fig. 3. Fractions of various products in the oil and the naphtha yields at different reaction
31 292 conditions.
32
33
34
293 GC-MS Analysis of Oil. In order to understand the conversion of PP and construct the
35
36 294 reaction pathways of the major intermediates, GC-MS analysis was conducted for selected
37
38 295 samples. Previous analyses have demonstrated that 425°C can lead to high naphtha fraction and
39
40 296 yield (Fig. 3). At this temperature, the oil yield was the highest at 2 hr (Fig. 1). Therefore, the oil
41
42
43 297 samples obtained from various reaction time at 425°C (Fig. 4a) or with different reaction
44
45 298 temperatures with a 2 hr reaction time (Fig. 4b) were selected for GC-MS analysis. The spectra
46
47 299 and the identified chemicals of the oil were available in the Supporting Information (Figs. S7-S8
48
49
50 300 and Tables S1-S2). Compounds characterized by GC-MS were categorized into several groups,
51
52 301 including saturated aliphatics (C6-C11 paraffins), unsaturated aliphatics (C6-C13 olefins),
53
54 302 cyclics (C6-C15), and aromatics (C8-C9). The hydrocarbons in the oil products of this study
55
56
57
58 16
59
1
2
3 303 typically have similar GC-MS response factors.44, 45 Therefore, it is reasonable to estimate the
4
5
6 304 major chemical compositions of the oil based on the peak areas. The percentages attributed to
7
8 305 different chemical groups were summarized in Fig. 4. The percentage of the C5-C10 compounds,
9
10 306 which is in the gasoline range,41 in the oil samples was also shown in Fig. 4.
11
12
13
307 With a reaction time of 0.5 hr at 425°C (Fig. 4a), the majority (93%) of the oil was the
14
15 308 unsaturated aliphatics (mostly C9-C12 olefins) and a small amount of saturated aliphatics (7%
16
17 309 paraffins). The C-C bond (348 kJ/mol) is a weaker bond (as compared to the C-H bond, 413
18
19
310 kJ/mol) in the PP structure so the degradation of PP under SWL likely starts from chain scission.
20
21
22 311 In order to stabilize the radicals generated during the polymer degradation process, carbon
23
24 312 double bonds (C=C) would be formed in addition to the production of alkanes (paraffins).
25
26 313 Similar findings were reported when converting single PP into oil using water vapor at a high
27
28
29 314 temperature (500°C with 18 MPa).34
30
31 315 As the reaction time increased from 0.5 hr to 4 hr, the percentage of unsaturated
32
33 316 aliphatics (olefins) reduced from 93% to 49%, while the percentage of cyclics (C6-C15)
34
35
36
317 increased from 0% to 35%, indicating that a majority of the unsaturated aliphatics (olefins) was
37
38 318 converted into cyclics in 3.5 hr. The percentages of saturated aliphatics (C6-C11 paraffins) and
39
40 319 aromatics (C8-C9) increased from 7% to 11% and from 0% to 3% in 3.5 hr, respectively. The
41
42
320 saturated aliphatics (paraffins) likely came from the conversion of unsaturated aliphatics
43
44
45 321 (olefins). The aromatics likely came from the cyclics (see Supporting Information, Section 7).
46
47 322 Compared to saturated aliphatics (paraffins) and aromatics, cyclics and unsaturated
48
49 323 aliphatics (olefins) share the same chemical formula. Therefore, cyclization was favored over
50
51
52 324 saturation and aromatization. Meanwhile, the percentage of C5-C10 (gasoline range) increased
53
54
55
56
57
58 17
59
1
2
3 325 from 64% to 97% when the reaction time increased from 0.5 hr to 4 hr. This result also explains
4
5
6 326 why the naphtha fractions increased with increasing reaction time at 425°C (Fig. 3).
7
8 327 In addition to studying the effects of reaction time, the effects of reaction temperature on
9
10 328 chemical compositions were also investigated (Fig. 4b). Similar to the results shown in Fig. 4a,
11
12
13
329 as the reaction temperature increased, the percentage of unsaturated aliphatics (olefins) reduced
14
15 330 while those of cyclics, saturated aliphatics (paraffins) and aromatics increased. Higher reaction
16
17 331 temperatures also resulted in gas formation from unsaturated or saturated aliphatics. In particular,
18
19
332 the aromatics (e.g., xylene found in this study, see Table S2 in Supporting Information), grew to
20
21
22 333 15% at 450°C. Aromatics have a major use as chemical feedstocks. For instance, xylene is
23
24 334 widely utilized in the plastic industry (e.g., to manufacture plasticizers).34, 46 By finely tuning the
25
26 335 SWL conditions, various products and chemicals can be converted from PP.
27
28
29 336
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58 18
59
1
2
3 (a)
4
5 100
6
7 Percentage of Total Identified Area (%)
8 Total C5-C10
9 80
10
11 Unsaturated Aliphatics
12 60 (C6-C13)
13
14
15
16 40 Cyclics (C6-C15)
17
18
19 Saturated Aliphatics
20 20
(C6-C11)
21
22
23
0
Aromatics
24 (C8-C9)
25
26 0.5 hr 1 hr 2 hr 4 hr
27
28 Reaction Time (hr)
29 (b)
30
31 100
32 Total C5-C10
33
Percentage of Total Identified Area (%)
34 80
35
36
37 Unsaturated Aliphatics
38 60
(C6-C13)
39
40 Cyclis
41 40 (C6-C15)
42
43
44 Aromatics
45 20
(C8-C9)
46
47
Saturated Aliphatics
48 0
49 (C6-C11)
50
51 380°C 400°C 425°C 450°C
52 Reaction Temperature (°C)
53
54 337 Fig. 4. Chemical compositions of the oil products converted at (a) various reaction times and
55 338 425°C and (b) various reaction temperatures and a 2 hr reaction time.
56
57
58 19
59
1
2
3 339 Analysis of the Gas Products. In addition to characterizing the oil products, the gas
4
5
6 340 products were also analyzed because the gas yields could be as high as 20-28% at higher reaction
7
8 341 temperatures (450-500°C) or longer reaction times (4-6 hr). GC-MS analysis was also carried out
9
10 342 to investigate the chemical compositions in the gas samples from various reaction conditions.
11
12
13
343 The spectra and the identified chemicals of the gas products were listed in the Supporting
14
15 344 Information (Figs. S9-S10 and Tables S3-S4). The compositions of gas products at 425°C
16
17 345 obtained from 0.5-4 hr were shown in Fig. 5a. The y-axis was the individual peak areas
18
19
346 normalized by the total peak area of the gas products at 4 hr. The major compounds in the gas
20
21
22 347 included ethane, propane, propene, butane, and pentane (Table S3 in Supporting Information).
23
24 348 The hydrocarbons in the gas products generally have similar response factors under GC-MS and
25
26 349 therefore the chemical compositions of the gas products can be estimated based on the peak
27
28
29 350 areas.44, 45 As Fig. 5a shows, the amounts of the major compounds in the gas products increased
30
31 351 as the reaction time increased. The dominant products in the gas phase were C3 and the majority
32
33 352 of C3 was propene. Propene may come from the cracking of the oil products, which is an
34
35
36
353 endothermic reaction.47 Increasing the reaction time would provide more energy and increase the
37
38 354 production of C3.
39
40 355 The gas products at different reaction temperatures with a 2 hr reaction time were also
41
42
356 analyzed by GC-MS (Fig. 5b). Because PP was barely converted into either oil or gas at 380°C,
43
44
45 357 the gas produced at 380°C with a 2 hr reaction time was not analyzed. As the reaction
46
47 358 temperature increased from 400°C to 450°C, the amounts of C3 increased significantly. This
48
49 359 could be related to the structure of PP, which is composed of propene monomers. With an
50
51
52 360 increasing reaction temperature, more energy was supplied to crack PP and the oil into C3.
53
54 361 Moreover, the amounts of C4 also increased with increasing reaction temperature.
55
56
57
58 20
59
1
2
3 362 A very small amount of CO2 was detected (which made up less than 1% of gas products
4
5
6 363 under all the reaction conditions tested, Table S3 in Supporting Information). The oxygen
7
8 364 content in the oil was less than 0.6 wt.% (See Fig. 2). These findings plus the mass balance of
9
10 365 oxygen (in Supporting Information, Fig. S11) suggest that little water participated in the
11
12
13
366 reactions under all the conditions tested.
14
15 367 The C2 and C3 are monomers for polyolefin synthesis, and C4 and C5 can be used as
16
17 368 special chemicals or blended into gasoline. Propane and propene can be used to synthesize PP,
18
19
369 ethane is the major feedstock to manufacture polyethylene, and pentane is one of the blowing
20
21
22 370 agents to produce polystyrene foams.48 The recovery of C2 to C5 could help promote a circular
23
24 371 economy.
25
26 372
27
28
29 373
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58 21
59
1
2
3 (a)
4
5
6 50 C3
7
8
9 40
10 % of Maximum Peak Area
11
12 30
13
14 C4
15 20
16 C5
17
18 10
19 C2
20 C6
21 0
22
23
0.5 hr 1 hr 2 hr 4 hr
24
25 Reaction Time (hr)
26
27
28 (b)
29
30
31 50
32 C3
33
34
40
% of Maximum Peak Area
35
36
37
38 30
39
40 C4
41
42 20
43
44 C5
45 10
46 C2
47
48 C6
49 0
50
51
52 400°C 425°C 450°C
53 Reaction Temperature (°C)
54
55 374 Fig. 5. Chemical compositions of the gas products converted from (a) various reaction times at
56 375 425°C and (b) various reaction temperatures with a 2 hr reaction time.
57
58 22
59
1
2
3 376 Analysis of the Solid Residue. The amounts of solid residue remaining after SWL
4
5
6 377 reactions were only significant (>50%) at lower reaction temperatures (≤400°C) and shorter
7
8 378 reaction times (≤1hr). In order to explore if there are any potential applications of the solid
9
10 379 residue, TGA was carried out to understand their thermal degradation behavior in the TGA
11
12
13
380 temperature of 25-550°C (Fig. S12). The solid residue sampled at various reaction temperatures
14
15 381 with a 2 hr reaction time were analyzed to study the effect of reaction temperature. The solid
16
17 382 residue sampled at 425°C with various reaction times were also analyzed to investigate how the
18
19
383 reaction time may affect the thermal degradation behavior of the solid residue. The results from
20
21
22 384 TGA indicate that the solid residues had a similar thermal degradation behavior as PP,
23
24 385 suggesting that the solid residue could still be polymers.
25
26 386 Although the thermal degradation behavior of PP and the solid residue was not
27
28
29 387 significantly different, further analysis was carried out to examine if there is any difference
30
31 388 between their molecular weight distributions. MALDI-TOF-MS analysis was conducted to
32
33 389 investigate the molecular weight distribution, the number average and the weight average
34
35
36
390 molecular weights of the solid residue.49 The solid residue sampled at 425°C with a 2 hr reaction
37
38 391 time (2 wt.%) was subjected to MALDI-TOF-MS analysis because their thermal degradation
39
40 392 behavior changed the most under TGA (see Supporting Information, Fig. S12). The acquisition
41
42
393 mass range was from 1,000 to 22,000 (g/mol). The PP feedstock has a number average molecular
43
44
45 394 weight (Mn) of 67,000 (g/mol) and a weight average molecular weight (Mw) of 250,000 (g/mol).
46
47 395 The molecular weight of the solid residue obtained via SWL was reduced with a Mn of 5,100
48
49 396 (g/mol) and a Mw of 7,993 (g/mol) (see Supporting Information, Fig. S13). Pyrolysis of PP at the
50
51
52 397 same reaction condition (at 425°C with a 2 hr reaction time) was also conducted to obtain the
53
54 398 solid residue for MALDI-TOF-MS analysis. Under these reaction conditions, only about 50% PP
55
56
57
58 23
59
1
2
3 399 was converted into oil via pyrolysis (by contrast, 91% of PP was converted into oil via SWL).
4
5
6 400 The solid residue obtained via pyrolysis could not be dissolved in the solvents for MALDI-TOF-
7
8 401 MS analysis. This finding indicates that the average molecular weight of the solid residue
9
10 402 obtained via pyrolysis was larger than that via SWL.
11
12
13
403 Analysis of the post-SWL Water. The post-SWL water was also analyzed to find any
14
15 404 products partitioned into the water phase. GC-MS analysis was carried out with the post-SWL
16
17 405 water at 425°C with a 4 hr reaction time (Supporting Information, Fig. S14). Only a small
18
19
406 amount of one oxygen-containing compound (hydroxyisobutyric acid) was found in the post-
20
21
22 407 SWL water. The mass balances of carbon, hydrogen, and oxygen also indicate that little oxygen
23
24 408 or hydrogen from water (<0.2%) was incorporated into the oil or gas products (Supporting
25
26 409 Information, Fig. S11). Most of the carbon and hydrogen in PP feedstock were recovered in the
27
28
29 410 oil (70-90%) and gas (5-30%) products, while the majority of the added water (>99.8%) was
30
31 411 recovered in the post-SWL water.
32
33 412 Potential Reaction Pathways for SWL of PP. Based on the analyses of the products in
34
35
36
413 different phases under a range of reaction times and temperatures (Figs. 4-5), potential reaction
37
38 414 pathways of major intermediates in the conversion of PP are summarized in Fig. 6. More
39
40 415 detailed mechanisms for the major reaction pathways are proposed in Fig. S15 in the Supporting
41
42
416 Information. The proposed reaction pathways were based on the results of GC-MS analyses of
43
44
45 417 the major intermediates and they may not represent all the reactions taking place under
46
47 418 supercritical water conditions.
48
49 419 First, the reaction temperature should be at least 425°C to have significant liquefaction
50
51
52 420 products. At this temperature, PP was quickly depolymerized into oligomers at short times (<0.5
53
54 421 hr). When the reaction time further increased (from 0.5 hr to 4 hr), a majority of the unsaturated
55
56
57
58 24
59
1
2
3 422 aliphatics would be transformed into cyclics via cyclization. During the same time period, small
4
5
6 423 amounts of unsaturated aliphatics (olefins) may become saturated aliphatics (paraffins) and
7
8 424 aromatics. Theoretically, aromatization can occur by either dehydrogenation of cyclics or
9
10 425 cyclotrimetization of unsaturated aliphatics (olefins).46, 50 Fig. 4 showed that the oil products at a
11
12
13
426 lower temperature and a longer reaction time (e.g. 425°C, 4 hr) were similar to those at a higher
14
15 427 temperature and a shorter reaction time (e.g. 450°C, 2 hr). The results suggest that the reactions
16
17 428 followed similar pathways but the reaction rate was faster at a higher temperature.
18
19
20 Plastic Oligomer Products
21 Feedstock
22
23
24
25
26
27
28
Cyclics
29 Unsaturated d (C6-C15)
a b
30 Aliphatics
31
(C6-C13) g
32 e
33 n-x
34 c Aromatics
35 c (C8-C9)
36 f
37 Saturated
38 Gas
Aliphatics f
39 (C2-C6)
40 (C6-C11)
41
42
43
44
45
46 429
47 430 Fig. 6. A potential reaction scheme of converting PP via SWL: (a) depolymerization, (b)
48 431 cracking, (c) hydrogenation/saturation, (d) cyclization, (e) aromatization, (f) gasification, and (g)
49 432 dehydrogenation. A green box represents oil phase products and a red box denotes gas products.
50
51 433 The thickness of arrows represents the relative amounts of products.
52
53 434 Comparison to Similar Technologies. It was observed in this study that the conversion
54
55 435 of PP in SWL has significantly different kinetics, pathways, oil yield, and product composition,
56
57
58 25
59
1
2
3 436 compared to pyrolysis (Table S5). Without any catalyst, pyrolysis of PP has a lower oil yield
4
5
6 437 (67-82 wt. %) than SWL (81-91 wt.%) and a higher yield of coke/char (1-27 wt.%) than SWL
7
8 438 (<<1 wt.%).51-54 The pyrolysis oil has a wider hydrocarbon distribution, covering the gasoline
9
10 439 range (C4-C12), the diesel range (C13-C16), and the lubricant range (C17+), whereas the SWL
11
12
13
440 PP oil has 90% of the hydrocarbons in the gasoline range (C4-C12).51-54 The SWL oil has more
14
15 441 cyclics and aromatics than the PP pyrolysis oil.51-54 The results of this study also indicate that the
16
17 442 reactions of PP in SWL are more selective and more controllable than those in pyrolysis.
18
19
443 Furthermore, the kinetics, pathways, and products of the conversion of biomass into
20
21
22 444 biocrude oil are significantly different from those for the conversion of PP into oil using
23
24 445 supercritical water. For instance, biomass generally favors a lower reaction temperature
25
26 446 (typically from 250-350°C) and a shorter reaction time (15-60 min) than plastics to achieve the
27
28
29 447 highest biocrude oil yield.19, 20, 22, 25, 41 Biomass generally contains heteroatoms such as oxygen
30
31 448 and nitrogen. Thus, their reaction pathways are very different from those of PP, which are
32
33 449 composed of only hydrocarbons. Catalysts are required in biomass conversion to reduce the
34
35
36
450 oxygen or nitrogen contents in the oil products to increase the calorific values of the biocrude
37
38 451 oil.21, 40 Furthermore, most of the biocrude oil still requires catalytic upgrading (e.g.,
39
40 452 deoxygenation or denitrogenation) to further reduce the oxygen or nitrogen contents in the oil for
41
42
453 their use as transportation fuels.25 In contrast, it was found in this study that the oils from PP
43
44
45 454 have little oxygen-containing products and much higher calorific values than the biocrude oil.
46
47 455 Therefore, the PP-derived oil has the potential to be used as gasoline blendstocks without further
48
49 456 upgrading.
50
51
52
53
457 Overall, the characterization results for the different products in SWL show that SWL can
54
55 458 be a versatile technology to help achieve a circular economy. If oil products are preferred, the
56
57
58 26
59
1
2
3 459 best conditions to achieve high oil yields are 425°C and 2-4 hr or 450°C and 0.5-1 hr. The oil
4
5
6 460 products obtained from this specific reaction condition have the potential to be used as
7
8 461 alternative fuels or feedstocks for other chemicals.
9
10 462 Roles of Water. In neat pyrolysis, depolymerization of polymers occurs in a viscous
11
12
13
463 polymer phase. By contrast, in SWL, supercritical water causes partial dissolution of the molten
14
15 464 polymer phase. The dilution of the polymer phase promotes polymer dissociation and
16
17 465 unimolecular reactions (e.g., β-scission), instead of higher order reactions of the intermediates.55,
18
19 56
466 As a result, the reactions involving coke formation, polycondensation, and gas formation are
20
21
22 467 suppressed.55, 56 Therefore, supercritical water can shift the selectivity away from the formation
23
24 468 of high molecular weight species, which can form in significant quantities for the pyrolysis of
25
26 469 hydrocarbons and polymers. Supercritical water can shift the selectivity from biomolecular
27
28
29 470 reactions to unimolecular reactions.56, 57 Furthermore, the branching structure of PP reduced the
30
31 471 bond energy of CH3-CH.56, 57 Hemolytic dissociation of the side chains produced radicals that
32
33 472 could form olefins via β-scission. As a result, olefins are the major products of PP derived oils
34
35
36
473 and gases (Supporting Information, Section 7).
37
38 474 In addition to the role of water as an effective reaction medium, water could be a catalyst
39
40 475 in the SWL of PP. However, more research is needed to verify which specific reactions are
41
42
476 catalyzed by water. Furthermore, very little oxygenated products were found in the gas products
43
44
45 477 or the post-SWL water. The weight of water before and after SWL water remained the same. The
46
47 478 results indicated that little water participated as a reactant or as a product in the conversion of PP.
48
49 479 Differences between SWL of PP and PE. To further understand if the branching of PP
50
51
52 480 may differentiate its reactivity from PE in SWL, the chemical compositions of oil and gas
53
54 481 converted from pure PP and PE were compared (Table S6). As shown in this table, n-alkanes
55
56
57
58 27
59
1
2
3 482 (paraffins) are dominant in the oils and gases converted from PE, whereas alkenes (olefins) are
4
5
6 483 dominant in the oils and gases converted from PP. The gas products converted from PE are
7
8 484 mainly methane and alkanes (paraffins),58, 59 whereas those from PP are propene and other
9
10 485 alkenes (olefins). No cyclics or aromatics were reported previously in the oils or gases derived
11
12
13
486 from PE.32 This result is consistent with Fig. S15. The Eq. S1 and S2 in Fig. S15 suggest that
14
15 487 most of the olefins result from the dissociation of the C-CH3 bonds in PP. Since PE does not
16
17 488 have the branching structure, it is expected from Fig. S15 that little olefins, cyclics, or aromatics
18
19
489 should be present in the products derived from PE.
20
21
22 490 The Potential of Using the Oil Converted from PP via SWL as Alternative Fuels.
23
24 491 Fuel specification analysis of the oil converted from PP via SWL was carried out to evaluate the
25
26 492 potential of using the oil as fuel blendstocks (see Supporting Information, Table S7). The oil
27
28
29 493 converted from PP via SWL shows a similar heating value, density, viscosity, boiling point
30
31 494 distribution, surface tension, and carbon number as gasoline and jet fuels. As of 2015, about 90
32
33 495 million tons of virgin PP were produced annually. If a similar amount of PP waste is generated
34
35
36
496 annually and can be converted at 91% yield into gasoline blendstocks using SWL, about 80
37
38 497 million tons of oil can be obtained. This approach has the potential to meet 2% of the global
39
40 498 gasoline demand per year60 and reduce the PP waste accumulation.
41
42
499 SWL of PP waste. In order to test if the screened condition obtained from the model
43
44
45 500 system can work for real-world plastic waste, an additional SWL test was carried out using a
46
47 501 waste container made of PP. The best conditions to achieve high oil yields and quality (425°C
48
49 502 for a 4 hr reaction time) were tested. The screened condition obtained from the model system
50
51
52 503 worked well for the conversion of the PP waste (see Fig. S16). A similar oil yield (90 wt.%) was
53
54 504 obtained.
55
56
57
58 28
59
1
2
3 505 Energy Demand, Energy Efficiency (Eout/Ein) and Greenhouse Gas (GHG)
4
5
6 506 Emissions of Hydrothermal Liquefaction (HTL) and Other Plastic Recycling Methods.
7
8 507 SWL processing of PP is an emerging technology. There is no pilot scale data for reliable
9
10 508 estimates of energy demand, energy efficiency or GHG emissions. However, it is expected that
11
12
13
509 SWL processing has similar values as HTL. HTL typically uses subcritical or near-critical water
14
15 510 as its reaction medium. Preliminary estimates based on pilot-scale HTL data for biomass
16
17 511 liquefaction and comparison with other plastic recycling methods are shown in Table 1 (detailed
18
19
512 assumptions are listed in Supporting Information, Table S8). The estimates for producing virgin
20
21
22 513 polymer and gasoline were also included in Table 1. HTL has 10 times lower process energy
23
24 514 input than producing virgin PP from petroleum crude.61, 62 It also has a lower energy input and
25
26 515 higher energy efficiency than mechanical recycling because HTL does not require washing and
27
28
29 516 drying.11, 12, 63, 64 Although HTL has a higher energy input than incineration, its energy efficiency
30
31 517 is much higher and its GHG emissions are much lower.8 Solvent extraction potentially has a
32
33 518 lower process energy input, the highest energy efficiency, and the lowest GHG emissions.51, 65
34
35
36
519 However, limited studies have been reported only for single polymers.
37
38 520
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58 29
59
1
2
3 521 Table 1 Preliminary estimates of energy demand, energy efficiency (Eout/Ein), and greenhouse
4
5
522 gas emissions (GHG) for the production of virgin polymers, gasoline, and different plastic
6 523 recycling methods.8, 19, 20, 41, 51, 61-69
7 524
8
Process Energy Energy GHG (kg CO2/kg
9 Product
10 Input (MJ/kg) Efficiency product)
11
12 Virgin Polymer 40 1.2 1.8 PP
13
14 Gasoline 4.6 10 1.9 Fuel
15
16 Incineration 0.02-0.03 3.7 3.2 Energy
17
18 Mechanical
19 9 5.3 0.6 PP
Recycling
20
21 Solvent
22 1.8 26.7 0.5 PP
23 Extraction
24
25 Pyrolysis 3.6 11.7 N/A Oil
26
27
28 HTL 2.8 12.0 0.2-0.6 Naphtha
29
30 525
31
32
33
526 In summary, SWL can effectively convert PP into oil. SWL reaction temperatures (380-
34
35 527 500°C) and reaction times (0.5-6 hr) have been explored. The highest oil yield (91 wt.%) was
36
37 528 achieved at 425°C and 2-4 hr or at 450°C and 0.5-1 hr. The highest naphtha yield (~80 wt.%)
38
39
529 was obtained at 425°C and 4 hr or at 450°C and 1 hr. These conditions produced the oils with an
40
41
42 530 HHV of 48 MJ/kg. GC-MS and fuel specification analyses indicate this oil product potentially
43
44 531 can be used as gasoline blendstocks. The chemical compositions of oil included aliphatic, cyclic,
45
46 532 and aromatic hydrocarbons. However, higher reaction temperature (>450°C) or longer reaction
47
48
49 533 time (>4 hr) were not favorable because they led to more gas products. Major reaction pathways
50
51 534 of converting PP into oil via SWL were also proposed. SWL is expected to have a lower process
52
53 535 energy input and higher energy efficiency than mechanical recycling or producing virgin PP
54
55
56
536 from petroleum crude. Furthermore, SWL potentially has 5-16 times lower GHG emissions than
57
58 30
59
1
2
3 537 incineration. Overall, this study demonstrates that SWL is a robust, versatile, and net-energy
4
5
6 538 positive process, which has the potential for converting PP into various useful products and to
7
8 539 reduce the plastic waste accumulation.
9
10 540 ASSOCIATED CONTENT
11
12
13 541 Supporting Information.
14
15 542 The experimental set-up of SWL reaction (Section 1); Separation process of SWL
16
17
18
543 products (Section 2); Characterization of oil and gas products (Section 3); Mass balances of
19
20 544 SWL of PP (Section 4); Characterization of solid residue (Section 5); Characterization of post-
21
22 545 SWL water (Section 6); Detailed major reaction pathways of SWL of PP (Section 7);
23
24
546 Comparison of the oil products obtained via SWL and pyrolysis (Section 8); Comparison of the
25
26
27 547 oil and gas converted from pure PP to PE via SWL (Section 9); Fuel specification analysis
28
29 548 (Section 10); SWL of PP waste (Section 11); and the preliminary estimates of energy demand,
30
31 549 energy efficiency, and greenhouse gas emissions for the production of virgin polymers, gasoline
32
33
34 550 and different plastic recycling methods (Section 12). This material is available free of charge via
35
36 551 the Internet at http://pubs.acs.org.
37
38 552 AUTHOR INFORMATION
39
40
41 553 Corresponding Author
42
43
44 554 *Prof. Nien-Hwa Linda Wang. 480 W. Stadium Avenue, West Lafayette, IN 47907; phone: +1-
45
46 555 765-494-4081; fax: +1-765-494-0805; email: wangn@ecn.purdue.edu
47
48
49
556 ACKNOWLEDGEMENTS
50
51 557 The authors appreciate the financial support from the Davidson School of Chemical Engineering
52
53 558 at Purdue University and the Trask Innovation Fund from the Purdue Research Foundation.
54
55
559
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58 31
59
1
2
3 560 REFERENCES
4
5
6 561 1. Jambeck, J. R.; Geyer, R.; Wilcox, C.; Siegler, T. R.; Perryman, M.; Andrady, A.;
7 562 Narayan, R.; Law, K. L., Plastic waste inputs from land into the ocean. Science 2015, 347
8 563 (6223), 768-771, DOI 10.1126/science.1260352
9 564 2. Geyer, R.; Jambeck, J. R.; Law, K. L., Production, use, and fate of all plastics ever made.
10 565 Sci. Adv. 2017, 3 (7), DOI 10.1126/sciadv.1700782
11
566 3. Rochman, C. M., Microplastics research—from sink to source. Science 2018, 360 (6384),
12
13
567 28-29, DOI 10.1126/science.aar7734
14 568 4. MacArthur, E., Beyond plastic waste. Science 2017, 358 (6365), 843, DOI
15 569 10.1126/science.aao6749
16 570 5. Lavers, J. L.; Bond, A. L., Exceptional and rapid accumulation of anthropogenic debris
17 571 on one of the world’s most remote and pristine islands. Proc. Natl. Acad. Sci. 2017, 114
18 572 (23), 6052-6055, DOI 10.1073/pnas.1619818114
19
573 6. Horton, A. A.; Walton, A.; Spurgeon, D. J.; Lahive, E.; Svendsen, C., Microplastics in
20
21 574 freshwater and terrestrial environments: Evaluating the current understanding to identify
22 575 the knowledge gaps and future research priorities. Sci. Total Environ. 2017, 586
23 576 (Supplement C), 127-141, DOI 10.1016/j.scitotenv.2017.01.190
24 577 7. Rochman, C. M.; Browne, M. A.; Halpern, B. S.; Hentschel, B. T.; Hoh, E.;
25 578 Karapanagioti, H. K.; Rios-Mendoza, L. M.; Takada, H.; Teh, S.; Thompson, R. C.,
26 579 Policy: Classify plastic waste as hazardous. Nature 2013, 494 (7436), 169-171, DOI
27
28
580 10.1038/494169a
29 581 8. Nabavi-Pelesaraei, A.; Bayat, R.; Hosseinzadeh-Bandbafha, H.; Afrasyabi, H.; Chau,
30 582 K.-w., Modeling of energy consumption and environmental life cycle assessment for
31 583 incineration and landfill systems of municipal solid waste management - A case study in
32 584 Tehran Metropolis of Iran. J. Clean Prod. 2017, 148, 427-440, DOI
33 585 10.1016/j.jclepro.2017.01.172
34
586 9. Baytekin, B.; Baytekin, H. T.; Grzybowski, B. A., Retrieving and converting energy
35
36
587 from polymers: deployable technologies and emerging concepts. Energy Environ. Sci.
37 588 2013, 6 (12), 3467-3482, DOI 10.1039/c3ee41360h
38 589 10. Garcia, J. M.; Robertson, M. L., The future of plastics recycling. Science 2017, 358
39 590 (6365), 870-872, DOI 10.1126/science.aaq0324
40 591 11. Hopewell, J.; Dvorak, R.; Kosior, E., Plastics recycling: challenges and opportunities.
41 592 Philos. Trans. Royal Soc. B 2009, 364 (1526), 2115-2126, DOI 10.1098/rstb.2008.0311
42
593 12. Ragaert, K.; Delva, L.; Van Geem, K., Mechanical and chemical recycling of solid
43
44 594 plastic waste. Waste Manag. 2017, 69, 24-58, DOI 10.1016/j.wasman.2017.07.044
45 595 13. Kunwar, B.; Cheng, H.; Chandrashekaran, S. R.; Sharma, B. K., Plastics to fuel: a
46 596 review. Renew. Sust. Energ. Rev. 2016, 54, 421-428, DOI 10.1016/j.rser.2015.10.015
47 597 14. Wang, Y.; Zhang, F.-S., Degradation of brominated flame retardant in computer housing
48 598 plastic by supercritical fluids. J. Hazard. Mater. 2012, 205, 156-163, DOI
49 599 10.1016/j.jhazmat.2011.12.055
50
51
600 15. Peterson, A. A.; Vogel, F.; Lachance, R. P.; Fröling, M.; Antal Jr, M. J.; Tester, J. W.,
52 601 Thermochemical biofuel production in hydrothermal media: a review of sub-and
53 602 supercritical water technologies. Energy Environ. Sci. 2008, 1 (1), 32-65, DOI
54 603 10.1039/B810100K
55
56
57
58 32
59
1
2
3 604 16. Savage, P. E., A perspective on catalysis in sub-and supercritical water. J. Supercrit.
4
5
605 Fluids 2009, 47 (3), 407-414, DOI 10.1016/j.supflu.2008.09.007
6 606 17. Kraft, S.; Vogel, F., Estimation of Binary Diffusion Coefficients in Supercritical Water:
7 607 Mini Review. Ind. Eng. Chem. Res. 2017, 56 (16), 4847-4855, DOI
8 608 10.1021/acs.iecr.7b00382
9 609 18. Chen, W.-T.; Tang, L.; Qian, W.; Scheppe, K.; Nair, K.; Wu, Z.; Gai, C.; Zhang, P.;
10 610 Zhang, Y., Extract Nitrogen-Containing Compounds in Biocrude Oil Converted from
11
611 Wet Biowaste via Hydrothermal Liquefaction. ACS Sustain. Chem. Eng. 2016, DOI
12
13
612 10.1021/acssuschemeng.5b01645
14 613 19. Chen, W.-T.; Zhang, Y.; Zhang, J.; Schideman, L.; Yu, G.; Zhang, P.; Minarick, M.,
15 614 Co-liquefaction of swine manure and mixed-culture algal biomass from a wastewater
16 615 treatment system to produce bio-crude oil. Appl. Energy 2014, 128 (0), 209-216, DOI
17 616 10.1016/j.apenergy.2014.04.068
18 617 20. Chen, W.-T.; Zhang, Y.; Zhang, J.; Yu, G.; Schideman, L. C.; Zhang, P.; Minarick,
19
618 M., Hydrothermal liquefaction of mixed-culture algal biomass from wastewater treatment
20
21 619 system into bio-crude oil. Bioresour. Technol. 2014, 152 (0), 130-139, DOI
22 620 10.1016/j.biortech.2013.10.111
23 621 21. Chen, W.-T.; Qian, W.; Zhang, Y.; Mazur, Z.; Kuo, C.-T.; Scheppe, K.; Schideman,
24 622 L. C.; Sharma, B. K., Effect of ash on hydrothermal liquefaction of high-ash content algal
25 623 biomass. Algal Res. 2017, 25, 297-306, DOI j.algal.2017.05.010
26 624 22. Zhang, Y.; Chen, W. T., 5 - Hydrothermal liquefaction of protein-containing feedstocks
27
28
625 A2 - Rosendahl, Lasse. Direct Thermochemical Liquefaction for Energy Applications
29 626 2018, 127-168, DOI 10.1016/B978-0-08-101029-7.00004-7
30 627 23. Canıaz, R. O.; Erkey, C., Process intensification for heavy oil upgrading using
31 628 supercritical water. Chem. Eng. Res. Des. 2014, 92 (10), 1845-1863, DOI
32 629 10.1016/j.cherd.2014.06.007
33 630 24. Caniaz, R. O.; Simsek, S.; Arca, S.; Sarayloo, E.; Kavakli, I. H.; Erkey, C., Upgrading
34
631 blends of microalgae feedstocks and heavy oils in supercritical water. J. Supercrit. Fluids
35
36
632 2018, 133, 674-682, DOI 10.1016/j.supflu.2017.09.002
37 633 25. Chen, W.-T. Upgrading hydrothermal liquefaction biocrude oil from wet biowaste into
38 634 transportation fuel. University of Illinois at Urbana-Champaign, 2017.
39 635 26. Duan, P.; Savage, P. E., Catalytic treatment of crude algal bio-oil in supercritical water:
40 636 optimization studies. Energy Environ. Sci. 2011, 4 (4), 1447-1456, DOI
41 637 10.1039/c0ee00343c
42
638 27. Kida, Y.; Carr, A. G.; Green, W. H., Cleavage of side chains on thiophenic compounds
43
44 639 by supercritical water treatment of crude oil quantified by two-dimensional gas
45 640 chromatography with sulfur chemiluminescence detection. Energy Fuels, 2014, 28 (10),
46 641 6589-6595, DOI 10.1021/ef5015956
47 642 28. Kida, Y.; Class, C. A.; Concepcion, A. J.; Timko, M. T.; Green, W. H., Combining
48 643 experiment and theory to elucidate the role of supercritical water in sulfide
49 644 decomposition. PCCP 2014, 16 (20), 9220-9228, DOI 10.1039/C4CP00711E
50
51
645 29. Patwardhan, P. R.; Timko, M. T.; Class, C. A.; Bonomi, R. E.; Kida, Y.; Hernandez,
52 646 H. H.; Tester, J. W.; Green, W. H., Supercritical water desulfurization of organic
53 647 sulfides is consistent with free-radical kinetics. Energy Fuels 2013, 27 (10), 6108-6117,
54 648 DOI 10.1021/ef401150w
55
56
57
58 33
59
1
2
3 649 30. Duan, P.; Savage, P. E., Catalytic hydrothermal hydrodenitrogenation of pyridine. Appl.
4
5
650 Catal. B 2011, 108, 54-60, DOI 10.1016/j.apcatb.2011.08.007
6 651 31. Fu, J.; Lu, X.; Savage, P. E., Catalytic hydrothermal deoxygenation of palmitic acid.
7 652 Energy Environ. Sci. 2010, 3 (3), 311-317, DOI 10.1039/B923198F
8 653 32. Moriya, T.; Enomoto, H., Characteristics of polyethylene cracking in supercritical water
9 654 compared to thermal cracking. Polym. Degrad. Stab. 1999, 65 (3), 373-386, DOI
10 655 10.1016/S0141-3910(99)00026-9
11
656 33. Watanabe, M.; Hirakoso, H.; Sawamoto, S.; Adschiri, T.; Arai, K., Polyethylene
12
13
657 conversion in supercritical water. J. Supercrit. Fluids 1998, 13 (1-3), 247-252, DOI
14 658 10.1016/S0896-8446(98)00058-8
15 659 34. Williams, P. T.; Slaney, E., Analysis of products from the pyrolysis and liquefaction of
16 660 single plastics and waste plastic mixtures. Resour. Conserv. Recycl. 2007, 51 (4), 754-
17 661 769, DOI 10.1016/j.resconrec.2006.12.002
18 662 35. Shen, Y.; Wu, H.; Pan, Z., Co-liquefaction of coal and polypropylene or polystyrene in
19
663 hot compressed water at 360–430°C. Fuel Process. Technol. 2012, 104, 281-286, DOI
20
21 664 10.1016/j.fuproc.2012.05.023
22 665 36. Wu, X.; Liang, J.; Wu, Y.; Hu, H.; Huang, S.; Wu, K., Co-liquefaction of microalgae
23 666 and polypropylene in sub-/super-critical water. RSC Adv. 2017, 7 (23), 13768-13776,
24 667 DOI 10.1039/C7RA01030C
25 668 37. Brown, T. M.; Duan, P.; Savage, P. E., Hydrothermal Liquefaction and Gasification of
26 669 Nannochloropsis sp. Energy Fuels 2010, 24 (6), 3639-3646, DOI 10.1021/ef100203u
27
28
670 38. Waldner, M. H.; Vogel, F., Renewable Production of Methane from Woody Biomass by
29 671 Catalytic Hydrothermal Gasification. Ind. Eng. Chem. Res. 2005, 44 (13), 4543-4551,
30 672 DOI 10.1021/ie050161h
31 673 39. Watson, J.; Si, B.; Li, H.; Liu, Z.; Zhang, Y., Influence of catalysts on hydrogen
32 674 production from wastewater generated from the HTL of human feces via catalytic
33 675 hydrothermal gasification. Int. J. Hydrogen Energy 2017, 42 (32), 20503-20511, DOI
34
676 10.1016/j.ijhydene.2017.05.083
35
36
677 40. Yu, G.; Zhang, Y.; Guo, B.; Funk, T.; Schideman, L., Nutrient Flows and Quality of
37 678 Bio-crude Produced via Catalytic Hydrothermal Liquefaction of Low-Lipid
38 679 Microalgae. BioEnergy Res. 2014, 1-12, DOI 10.1007/s12155-014-9471-3
39 680 41. Gai, C.; Zhang, Y.; Chen, W.-T.; Zhang, P.; Dong, Y., Energy and nutrient recovery
40 681 efficiencies in biocrude oil produced via hydrothermal liquefaction of Chlorella
41 682 pyrenoidosa. RSC Adv. 2014, 4 (33), 16958-16967, DOI 10.1039/C3RA46607H
42
683 42. Chung, J.; Boudouris, B. W.; Franses, E. I., Surface tension behavior of aqueous
43
44 684 solutions of a propoxylated surfactant and interfacial tension behavior against a crude oil.
45 685 Colloids Surf., A 2018, 537, 163-172, DOI 10.1016/j.colsurfa.2017.10.011
46 686 43. Speight, J. G., The Chemistry and Technology of Petroleum, Fifth Edition. Taylor &
47 687 Francis: 2014.
48 688 44. Göröcs, N.; Mudri, D.; Mátyási, J.; Balla, J., The Determination of GC–MS Relative
49 689 Molar Responses of Some n-Alkanes and their Halogenated Analogs. J. Chromatogr. Sci.
50
51
690 2013, 51 (2), 138-145, DOI 10.1093/chromsci/bms118
52 691 45. Matisova, E., Quantitative analysis of aromatic hydrocarbons in complex hydrocarbon
53 692 mixtures by high resolution capillary gas chromatography. Chem. Listy 1998, 92, 870-
54 693 874.
55
56
57
58 34
59
1
2
3 694 46. Franck, H. G.; Stadelhofer, J. W., Industrial Aromatic Chemistry: Raw Materials ·
4
5
695 Processes · Products. Springer Berlin Heidelberg: 2012.
6 696 47. Watson, J.; Zhang, Y.; Si, B.; Chen, W.-T.; de Souza, R., Gasification of biowaste: A
7 697 critical review and outlooks. Renew. Sust. Energ. Rev. 2018, 83, 1-17, DOI
8 698 10.1016/j.rser.2017.10.003
9 699 48. Rapra, S., Blowing Agents and Foaming Processes 2014. Smithers Information Limited:
10 700 2014.
11
701 49. Zhu, H.; Yalcin, T.; Li, L., Analysis of the Accuracy of Determining Average Molecular
12
13
702 Weights of Narrow Polydispersity Polymers by Matrix-Assisted Laser Desorption
14 703 Ionization Time-of-Flight Mass Spectrometry. J. Am. Soc. Mass Spectrom. 1998, 9 (4),
15 704 275-281, DOI 10.1016/S1044-0305(97)00292-4
16 705 50. Walter, R.; Otto, S.; Karl, K.; Tim, T., Cyclisierende Polymerisation von Acetylen I
17 706 Über Cyclooctatetraen. Liebigs Ann. 1948, 560 (1), 1-92, DOI 10.1002/jlac.19485600102
18 707 51. Achilias, D. S.; Roupakias, C.; Megalokonomos, P.; Lappas, A. A.; Antonakou, Ε. V.,
19
708 Chemical recycling of plastic wastes made from polyethylene (LDPE and HDPE) and
20
21 709 polypropylene (PP). J. Hazard. Mater. 2007, 149 (3), 536-542, DOI
22 710 10.1016/j.jhazmat.2007.06.076
23 711 52. Ahmad, I.; Khan, M. I.; Khan, H.; Ishaq, M.; Tariq, R.; Gul, K.; Ahmad, W., Pyrolysis
24 712 Study of Polypropylene and Polyethylene Into Premium Oil Products. Int. J. Green
25 713 Energy 2015, 12 (7), 663-671, DOI 10.1080/15435075.2014.880146
26 714 53. FakhrHoseini, S. M.; Dastanian, M., Predicting Pyrolysis Products of PE, PP, and PET
27
28
715 Using NRTL Activity Coefficient Model. J. Chem. 2013, 2013, 5, DOI
29 716 10.1155/2013/487676
30 717 54. Sakata, Y.; Uddin, M. A.; Muto, A., Degradation of polyethylene and polypropylene into
31 718 fuel oil by using solid acid and non-acid catalysts. J. Anal. Appl. Pyrolysis 1999, 51 (1),
32 719 135-155, DOI 10.1016/S0165-2370(99)00013-3
33 720 55. Savage, P. E.; Gopalan, S.; Mizan, T. I.; Martino, C. J.; Brock, E. E., Reactions at
34
721 supercritical conditions: applications and fundamentals. AIChE J. 1995, 41 (7), 1723-
35
36
722 1778, DOI 10.1002/aic.690410712
37 723 56. Akiya, N.; Savage, P. E., Roles of Water for Chemical Reactions in High-Temperature
38 724 Water. Chem. Rev. 2002, 102 (8), 2725-2750, DOI 10.1021/cr000668w
39 725 57. Savage, P. E., Mechanisms and kinetics models for hydrocarbon pyrolysis. J. Anal. Appl.
40 726 Pyrolysis 2000, 54 (1), 109-126, DOI 10.1016/S0165-2370(99)00084-4
41 727 58. Su, X.; Zhao, Y.; Zhang, R.; Bi, J., Investigation on degradation of polyethylene to oils
42
728 in supercritical water. Fuel Process. Technol. 2004, 85 (8), 1249-1258, DOI
43
44 729 10.1016/j.fuproc.2003.11.044
45 730 59. Wong, S. L.; Ngadi, N.; Amin, N. A. S.; Abdullah, T. A. T.; Inuwa, I. M., Pyrolysis of
46 731 low density polyethylene waste in subcritical water optimized by response surface
47 732 methodology. Environ. Technol. 2016, 37 (2), 245-254, DOI
48 733 10.1080/09593330.2015.1068376
49 734 60. (USEIA), U. S. E. I. A. U.S. Energy Information Administration. https://www.eia.gov/
50
51
735 (accessed 07/25).
52 736 61. Hammond, G.; Jones, C.; Lowrie, F.; Tse, P., Inventory of carbon & energy: ICE.
53 737 Sustainable Energy Research Team, Department of Mechanical Engineering, University
54 738 of Bath Bath: 2008; Vol. 5.
55
56
57
58 35
59
1
2
3 739 62. Oyler, J. National Alliance for Advance Biofuels and Bio-Products Final Technical
4
5
740 Report Addendum Hydrothermal Processing Pilot System; Donald Danforth Plant
6 741 Science Center.
7 742 63. Associates, F. Life Cycle Inventory of 100% Postconsumer HDPE and PET Recycled
8 743 Resin from Postconsumer Containers and Packaging; Kansas: Prairie Village, 2011.
9 744 64. Kreiger, M. A.; Mulder, M. L.; Glover, A. G.; Pearce, J. M., Life cycle analysis of
10 745 distributed recycling of post-consumer high density polyethylene for 3-D printing
11
746 filament. J. Clean. Prod. 2014, 70, 90-96, DOI 10.1016/j.jclepro.2014.02.009
12
13
747 65. Weeden, G. S.; Soepriatna, N. H.; Wang, N. H. L., Method for efficient recovery of
14 748 high-purity polycarbonates from electronic waste. Environ. Sci. Technol. 2015, 49 (4),
15 749 2425-2433, DOI 10.1021/es5055786
16 750 66. Kunwar, B.; Moser, B. R.; Chandrasekaran, S. R.; Rajagopalan, N.; Sharma, B. K.,
17 751 Catalytic and thermal depolymerization of low value post-consumer high density
18 752 polyethylene plastic. Energy 2016, 111, 884-892, DOI 10.1016/j.energy.2016.06.024
19
753 67. Tzanetis, K. F.; Posada, J. A.; Ramirez, A., Analysis of biomass hydrothermal
20
21 754 liquefaction and biocrude-oil upgrading for renewable jet fuel production: The impact of
22 755 reaction conditions on production costs and GHG emissions performance. Renew. Energ.
23 756 2017, 113, 1388-1398, DOI 10.1016/j.renene.2017.06.104
24 757 68. Wang, M.; Wu, M.; Huo, H., Life-cycle energy and greenhouse gas emission impacts of
25 758 different corn ethanol plant types. Environ. Res. Lett. 2007, 2 (2), 024001, DOI
26 759 10.1088/1748-9326/2/2/024001
27
28
760 69. Chen, W.-T.; Zhang, Y.; Lee, T. H.; Wu, Z.; Si, B.; Lee, C.-F. F.; Lin, A.; Sharma, B.
29 761 K., Renewable diesel blendstocks produced by hydrothermal liquefaction of wet
30 762 biowaste. Nat. Sustain. 2018, 1 (11), 702-710, DOI 10.1038/s41893-018-0172-3
31
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10 1021@acssuschemeng 8b03841

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is published by the American Chemical Society. 1155 Sixteenth Street N.W.,

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