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Sub- and supercritical water for chemical recycling of plastic waste

Alex Queiroz, Giovanni B. Pedroso, Sergio N. Kuriyama, Antonio A. Fidalgo-Neto

PII: S2452-2236(20)30053-5
DOI: https://doi.org/10.1016/j.cogsc.2020.100364
Reference: COGSC 100364

To appear in: Current Opinion in Green and Sustainable Chemistry

Received Date: 31 March 2020

Revised Date: 14 May 2020
Accepted Date: 19 May 2020

Please cite this article as: A. Queiroz, G.B. Pedroso, S.N. Kuriyama, A.A. Fidalgo-Neto, Sub- and
supercritical water for chemical recycling of plastic waste, Current Opinion in Green and Sustainable
Chemistry, https://doi.org/10.1016/j.cogsc.2020.100364.

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 1 Sub- and supercritical water for chemical recycling of plastic waste
2

3 Special Issue on South America of Current Opinion in Green and Sustainable Chemistry
4

5 Alex Queiroza, Giovanni B. Pedrosoa, Sergio N. Kuriyamaa, Antonio A. Fidalgo-

6 Netoa*

a
8 SENAI Innovation Institute for Green Chemistry, RJ, 20271-030, Brazil.

10 *Corresponding author: SENAI Innovation Institute for Green Chemistry

11 Morais e Silva st, 53, Block 9, Rio de Janeiro, RJ, 20271-030, Brazil.

12 Phone: +55 21 3978 6101

13 E-mail address: aaneto@firjan.com.br

14

15
 1 Abstract
2 The use of plastic in daily life is growing at expressive rates. Due to its inherent
3 characteristics, such as chemical resistance and low biodegradability, plastic waste is
4 already a global issue. Traditionally used methods for plastic conversion, like
5 incineration, cause some environmental concerns, besides not being economically
6 attractive. Sub- and supercritical water provide a strongly oxidant environment, which
7 can deal with this waste by allowing the obtention of high-added value products from
8 waste of synthetic polymers. These processes, when carefully optimized using
9 chemometric methods, produce fuels and even the initial monomers that can be
10 employed for polymer synthesis, reducing the direct demand for fossil raw materials in
11 a circular economy approach.
12

13 Keywords

14 • Environmental issues
15 • Circular economy
16 • Synthetic polymers
17 • Chemometric support
18 • Cost-benefit evaluation

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 1 1. Introduction

2 Recently, environmental issues related to plastics have emerged as an important

3 topic of global discussion and concern, while production of plastic materials for

4 different uses has grown: 1.7 million metric tons in 1950, 310 million metric tons in

5 2014, with estimates to reach 1800 metric tons in 2050 (Fig.1) [1-3].

7 Fig. 1: The global plastic production and its geopolitical feature, adapted from [2].

9 Due to its global spread, chemical and mechanical resistance and the presence of

10 additives in its composition, plastic waste represents a significant threat to the

11 environment [4]. As a result of the slow and gradual breakdown of the polymer chains

12 into micro and nanoplastics, these compounds enter the food chain and impact the

13 composition of soil and water [2,5]. Recent studies [6] point out that the oceans already

14 contain more than 170 million metric tons of plastics, most of them as microplastics

15 (particles with less than 5 mm), adding up to more than 5 trillion fragments floating on

16 its surface [2]. This amount accounts for only 3% of the disposal, while 76% is

17 landfilled in terrestrial ecosystems, 12% is incinerated and 9% is recycled [4,5,7].

18 Currently, two main processes are used for plastic waste conversion at relevant

19 scales: incineration and mechanical recycling. Although incineration is reasonably

20 efficient in eliminating these materials and able to process non-segregated plastic

21 wastes, it is not financially desirable (due to the high CAPEX for implementation of

22 industrial plants and high operational costs), responsible for the liberation of

23 carcinogenic substances [7], and clearly not environmental friendly. Mechanical

24 recycling, on the other hand, is not able to deal with polymer mixtures and requires
 1 energy-consuming washing and drying steps [7,8], without achieving performance

2 similar to the original material. Although not being able to process high amounts of

3 waste, pyrolysis [47] and depolymerization by solvolysis [48] are mature technologies

4 that can be used as alternative conversion techniques.

5 Economic aspects must also be considered, since this commodity has an annual

6 growth of U$ 600 billion, with projections of U$ 720 billion in 2025 [1,9], which

7 guarantees exponential growth in production and, of course, it affects the continuous

8 generation of this waste above the capacity of landfills, incinerators and recyclers. In

9 this scenario, plastic waste must be seen not as a problem to be solved, but as an

10 opportunity. Recycling of this type of waste can generate compounds that may be

11 employed to compose new polymeric chains, or even as alternative fuels, in a circular

12 economy approach that minimizes the direct use of fossil raw materials [10]. The

13 development of new and more efficient processes for conversion of plastic waste

14 becomes increasingly important, while the demand for these processes to use greener

15 solvents grows in the same proportion. Thus, the use of sub- and supercritical solvents

16 for plastic waste conversion can be a viable option, being water one of the most suitable

17 candidates for such applications.

18

19 2. Sub- and supercritical Water: a tool to solve the world’s plastic problem?

20 Supercritical solvents are compounds that, at temperature and pressure above

21 their critical point, exhibit intermediate properties between liquids and gases. While

22 their density, solvent strength and viscosity are liquid-like, they behave like a gas in

23 terms of compressibility and diffusivity, and those characteristics bring advantages for

24 many different purposes [11,12]. Supercritical water (SCW), for example, which exists
 1 in temperatures above 375 ºC and pressures above 217 atm, can be completely miscible

2 with nonpolar gases [13], and has been claimed as a solvent with unique properties for

3 advanced oxidation processes [14], including degradation of plastic waste [15].

4 Although physical-chemical properties change significantly at the vicinity of the critical

5 point [16], sub-critical water has also been investigated for thermochemical conversion

6 of plastic waste, given the desirable milder operating conditions.

7 Water is the most abundant substance on Earth’s surface, naturally the

8 environmental solvent par excellence. However, incorporating its use under

9 supercritical state into industrial processes is not trivial and there are many challenges

10 involved. Among these challenges, reducing the cost of the equipment and operation,

11 improving the operation with highly concentrated solid suspensions, implementing

12 downstream processes to achieve marketable products [17] and reducing the corrosive

13 effects of supercritical water on the apparatus [18] are aspects that need to be

14 considered.

15 Sub- or supercritical water processes eliminate problems arising from the low

16 thermal conductivity of polymers, manage to deal with common additives on these

17 matrices, like flame retardants or stabilizers and, as already demonstrated [19-21], can

18 lead to high added-value products, after careful optimization and operation. Depending

19 on the chemical structure of the polymeric materials, it may be possible to recover the

20 monomers and use them for the production of new plastic materials, obtain useful raw

21 materials for chemical syntheses, or even obtain fuels and derivatives [7] as an

22 alternative to the primary use of fossil sources. Currently, it is already possible to find

23 companies that explore the SCW conversion for treatment of plastic waste in industrial

24 scale, e.g. RenerELP (https://renewelp.co.uk/technology/).

 1 According to several authors [7,20-26], increasing temperature and reaction time

2 of SCW transformation processes applied to plastic materials can lead to higher

3 conversion yields and reaction rates, and a higher amount of gas products, like CO2,

4 CH4 and H2. By the other hand, increasing pressure usually tends to have little effect on

5 the reaction rates. Also, water acts both as oxidizing and solubilizing agent, dissolving

6 components releasing during the crack of polymeric chains. Once the ratio between

7 plastic feedstock and water increases, the dispersibility of macromolecular free-radical

8 fragments decreases, reducing reaction rates [46]. A conceptual representation can be

9 seen in Fig. 2, which highlights that gaseous, liquid and solid fractions are always

10 present, although their composition differ remarkably in response of process conditions.

11

12 Fig.2. Conceptual representation of major products of supercritical water treatment at different

13 process conditions (PAHs: Polycyclic aromatic hydrocarbons).

14

15 In the view of the particularities of each polymeric class, polymers synthesized

16 by step-growth or chain growth mechanism have been extensively studied, in order to

17 establish optimized thermodynamic parameters for the obtention of different

18 compounds from recycling using sub- and supercritical water.

19

20 2.1. Step-growth polymerization

21 Polymers formed by step-growth mechanism are often referred to as

22 condensation polymers, although there is a large but not total overlap between these

23 terms [27]. Normally, this mechanism involves the liberation of small molecules, such

24 as water or methanol, during the reaction. The process happens in steps, with the
 1 conversion of monomers to dimers, and then to lower molecular weight oligomers; as

2 the reaction nears its completion, significant amounts of higher molecular chain material

3 can be formed, as demonstrated [28]. Usually, these polymers have ether, ester or amide

4 bonds, which can be targets for depolymerization by solvolysis [29]. Most of them are

5 polyamides, like nylon-6; or polyesters, like polyethylene terephthalate (PET).

6 Chemical recycling of polyethylene terephthalate (PET) was performed in

7 autoclave reactor using sub-critical water, and the results showed the possibility of

8 obtaining up to 80% of the original terephthalic acid (TPA), and 60% of the ethylene

9 glycol (EG), at 300ºC for 30 min [26]. It was possible to increase this recovery yield to

10 90.5% in terms of TPA, using zinc acetate as a catalyst, at 240ºC for the same reaction

11 time, in a fused-silica capillary reactor [30]. Also, employing seawater and higher

12 temperatures, the gasification was demonstrated [23] with yield of 98% of the PET

13 material, using SCW conversion.

14 For SCW conversion of nylon-6, the recovery yield of the monomer, ε-

15 caprolactam, was close to 78% under 300 ºC for 85 min of residence time, with 3% of

16 the original plastic material being converted to polycyclic aromatic hydrocarbons [31].

17 For polyurethane, the monomers diaminotoluene and the polyol could be recovered, as

18 described [32], using subcritical water, with and yield of 72%, under 250 ºC for 30 min.

19 Several authors have investigated the effect of process parameters on the SCW

20 conversion of polycarbonate (PC). Using sub- critical water, bisphenol-A was the only

21 product detected on the liquid phase, while CO2 was the only gas product. The

22 hydrolysis yield, was close to 100% after 50 min of reaction. This reaction was also

23 studied using seawater for PC microplastics conversion [33], and some of the alkali

24 metal salts present on the water phase (KCl, CaCl2, NaHCO3) had a significant catalytic
 1 effect on the gasification, effect previously described by Kawasaki et al. (2007) [34].

2 The presence of chemical additives also impacts the conversion of plastics. The flame

3 retardant decabromodiphenyl ether (deca-BDE) accelerated the hydrolysis of PC on

4 sub-critical water, while the addition of the plasticizer di-n-octyl phthalate (DnOP) had

5 the opposite effect, and both reduced the yield of conversion of PC into bisphenol-A

6 [25].

8 2.2. Chain-growth polymerization

9 Chain-growth polymerization occurs by the sequential addition of a monomer to

10 a growing chain, with polymeric chains being formed in the first moments after the

11 reaction starts [27]. Normally, the monomer is unsaturated, almost always an ethene or

12 a substituted ethene, and chain propagation can happen through anionic, cationic, free-

13 radical, or coordination catalyst-based mechanisms [35]. Examples of this class include

14 polyolefins, polystyrene (PS), polyvinyl chloride (PVC) and polytetrafluoroethylene

15 (PTFE). Given the absence of polar groups, chain-growth polymers tend to be less

16 susceptible to biodegradation when compared to step-growth polymers. Thus, the

17 development of new solutions to recycle waste containing these compounds becomes

18 more urgent. Due to the absence of heteroatoms, it becomes difficult to obtain the

19 respective monomers after SCW treatment, as described by an increasing number of

20 authors [7, 36-39] that had previously studied the impact of process conditions on the

21 relative amount of solid, liquid and gas products.

22 Conversion of polyolefins to naphtha is one of the most desired applications,

23 given that it can be easily cracked to ethylene and propylene in existing petrochemical

24 plants, in an circular economy approach [49]. Degradation of both polyethylene (PE)

 1 and polypropylene (PP) was evaluated under SCW conditions. For PE, the highest

2 conversion yield into oil was described [22], which was above 90 wt. %, obtained at

3 460 ºC, with a reaction time of 1 min, and water/PE ratio of 6. PP showed a very similar

4 degradation profile, with up to 91% of the material being converted to oil under 425 ºC

5 for 2-4 h, or under 450 ºC for 0.5-1 h. About 80-90% of the oil components (saturated

6 and unsaturated aliphatic, cyclic and aromatic compounds) had the same boiling point

7 as naphtha (25-200 ºC), according to [7]. The results showed that increasing

8 temperature and residence time of the materials on the reactor tends to decrease the oil

9 yield, while the amount of the gas fraction increases. The ratio between water and

10 polymer affect both the yield of the products and the composition of the oil products in

11 both cases. For PP, [36] related that higher temperatures (750 ºC) provided conversion

12 of 79.9% of the carbon content to gas products in 60 min.

13 SCW conversion of polystyrene (PS) led to a very different product composition

14 when compared to polyolefins. In this case, toluene and ethylbenzene were the major

15 products, with styrene dimers and trimers were also formed. Using subcritical water, at

16 370ºC, equilibrium conversion was around 80% after 5 min; while in supercritical

17 water, at 390ºC, the equilibrium conversion reached 100% after 3 min, according to

18 [37]. For high impact polystyrene, the maximum carbon liquefaction yield performed by

19 [38] was 77 wt.%, at 490 ºC, six times higher than conventional pyrolysis. For both

20 cases, increasing temperature also promoted the transformation processes, although

21 some traces of polycyclic aromatic hydrocarbons were produced.

22

23 2.3. Chemometrics for process optimization

 1 In fact, subcritical or supercritical water properties can be useful to perform

2 conversion of plastic waste in a selective, fast and efficient way, producing oil and gas

3 fractions. However, these processes might be complex, and several variables can

4 influence the conversion yield, and therefore the economic viability. The synthetic

5 polymer residues composition, moisture content, temperature, pressure, reaction time,

6 water salinity and the use of catalysts are a few of these variables [7,11,39]. Some of

7 these variables might have unique effects, but there is also the possibility of some

8 synergic interaction between them. In this context, chemometrics can be helpful to fully

9 comprehend a given system, aiming to reach significant results with less costs [40-42].

10 Using chemometric techniques [43,44], it is possible to evaluate the influence of

11 each variable on the conversion yield, aiming to maximize the obteention of a specific

12 product. Surprisingly, there is a lack of studies that systematically employ multivariate

13 strategies [45]. Moreover, most of the authors explore the operational variables in a

14 basic manner, as mentioned by Bai et al. [39], or by changing each factor univariately,

15 as well as, by adjusting just a few variables in detriment of many other synergic ones.

16 The main drawback is, surely, the lack of confidence about optimal operational

17 conditions.

18

19 3. Conclusions

20 The strong features of sub- and supercritical water processes for conversion of

21 plastic waste lie in the knowledge produced by abundant research on this topic, which

22 shows promising results either in lab or pilot scale, with good conversion yields. There

23 are some weak features involved, like high processing cost, in addition to some

24 operational problems, which require further research.

 1 Besides solving a problem of plastic waste disposal, it might be possible to

2 obtain high added-value products from polymers waste. Step-growth polymers can be

3 converted to its initial monomers, while chain-growth polymers can be converted to

4 distinct products, like naphtha, or feedstocks. In general, operation at high temperatures

5 could mean fast reaction kinetics, which could allow extremely fast processes to be

6 developed. But these conditions usually promote gasification (converting the original

7 material to CO2, CH4, H2, among others) or formation of solid residues, such as

8 polycyclic aromatic hydrocarbons. By carefully optimizing thermodynamic parameters

9 of the processes or residence time of the plastic material on the reactor, it might be

10 possible to adjust the composition of the products.

11 Chemometric approaches can be applied in process optimization, aiming to

12 maximize the conversion yield and adjust the composition of the products, while saving

13 energy and operation time. Thus, SCW processes are potential tools for recycling plastic

14 waste at a near future.

15

16

17 Declarations of interest: none

18 Funding

19 This work was supported by the SENAI Innovation Institute for Green Chemistry.

20
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4
Highlights

• Growing research efforts in SCW process lead to deep process

knowledge
• Reaction kinetics should be considered in order to reach a specific
product
• Process optimization beyond univariate experiments might allow better
efficiencies
• SCW processes are potential tools for recycling and reuse of polymer
wastes
Declaration of interests

☒ The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.

☐The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests: