Life cycle assessments for biomass derived sustainable biopolymer & energy co-

generation

Dongda Zhang1,2,3*, Ehecatl Antonio del Rio-Chanona1,2, Nilay Shah1,2

1: Centre for Process Systems Engineering, Imperial College London, South Kensington

Campus, London SW7 2AZ, UK

2: Department of Chemical Engineering, Imperial College London, South Kensington

Campus, London SW7 2AZ, UK

3: Centre for Process Integration, School of Chemical Engineering and Analytical Science,

University of Manchester, Oxford Road, Manchester, M1 3BU, UK

*: corresponding author, email: dongda.zhang11@imperial.ac.uk, tel: 44 (0)7543785283.

 Abstract

Sustainable polymers derived from biomass have been considered as promising candidates to

reduce the dependency on fossil based polymers. In this study, a conceptual process design

was conducted for citrus waste derived biopolymer production with energy co-generation,

and its eco-friendliness was evaluated through life cycle assessment by comparison against a

petroleum derived polymer production process. Based on the current research, two original

conclusions were proposed. The first one is that energy-efficient separation techniques are of

critical importance for the design of eco-friendly chemical processes. Only focusing on the

use of sustainable feedstocks with high conversion reactions cannot guarantee an

environmentally-friendly final product. The second one is that biomass should be considered

not only as a raw material, but more importantly, as an energy source for the sustainable

synthesis of biochemicals. In other words, a sustainable process should be designed such that

a portion of biomass is used to provide clean energy for process operation, with the rest

converted for product generation.

Keywords: biomass waste, polylimonene carbonate, energy co-generation, process design,

life cycle assessment, sustainable production

1. Introduction

The excessive consumption of fossil based resources and their consequential environmental
1,2
pollution have brought an urgent global challenge in the recent decades . For example,

because of the continuous growth of population, economic, and societal development, the

worldwide electricity demand derived from fossil fuels e.g. natural gas and coal has been

estimated to increase by 95.8% from 2008 to 2035 3. Meanwhile, the production of other

commodities such as bulk chemicals, cosmetics, and food industries also requires large
4,5
amounts of non-renewable petrochemicals . All of these non-renewable resources based

processes result in emissions of greenhouse gases which cause climate change, global

warming, and health issues 3, severely threatening the current environment. To this end, the

only solution to effectively resolve the challenge is to discover advanced technologies for the

sustainable development and production from eco-friendly biomass feedstock 1,6.

Biomass is a renewable resource derived from solar energy and atmospheric CO 2 through

photosynthesis. To date, two types of biomass resources, namely microorganisms and

biomass wastes, have been widely used for the production of clean energy and sustainable
3,7
commodities . For microorganisms, microalgae and cyanobacteria have been extensively

investigated due to their outstanding advantages such as high solar energy utilisation
8,9
efficiency and rapid growth rate over other plants . They have been applied to produce
10 11
biofuels e.g. biodiesel , biohydrogen through different technologies, for instance
12 13
hydrothermal methods and anaerobic digestion , and food supplements such as

astaxanthin 14, lutein 9,15

, and C-phycocyanin 16,17
. For biomass wastes, a variety of candidates

including citrus waste, agricultural waste, forestry residues, and food waste have been

intensively exploited to produce both energy (e.g. liquid fuels, electricity) 18,19 and sustainable

value-added chemicals (e.g. resins, solvents, surfactants) 20.

So far, it is commonly accepted that regardless of the type of biomass, it is predominantly

used for two purposes. The first one is to generate energy, including biogas, liquid biofuels,

heat, and electricity. For example, both algae biomass and citrus wastes have been used to
21,22
synthesise biogas through anaerobic digestion for heat and electricity co-generation .

Similarly, comprehensive research has been performed to produce different biofuels e.g.

bioethanol, biodiesel, biohydrocarbon, etc. through a number of techniques such as

23,24 25,26
gasification and pyrolysis by utilising microalgae and agricultural biomass wastes.
27,28
The kinetic mechanisms of these reactions have also been well studied , with the aim to

improve process efficiency and conversion. In addition, environmental impacts of these

biomass derived energy generation processes have been analysed with their advantages being

quantified compared to traditional fossil based routes 3,29,30.

The second purpose is to use biomass as a sustainable starting material for the synthesis of

bulk chemicals and high-value products, therefore replacing the petroleum based production

routes. At this moment, biomass has been used to produce different commodities such as

solvents 31, food supplements 17,32

, and industrial materials 33,34
. Amongst these applications,

converting biomass into polymers has been given particular attention within the last few

years because of their large global market demand and diverse use in different areas across

both daily life and industrial development 7. For instance, a number of sustainable monomers

or polymer precursors e.g. limonene, isoprene, 1,4-cyclohexadiene have been produced from

biomass including both biowaste and microalgae 20. Research has been carried out to explore

the reaction kinetics and optimal operating conditions for the polymerisation of these
35,36
biorenewables . Furthermore, key properties of newly proposed biopolymers have been

measured in previous studies 35,37,38.

In spite of the above achievements, however, most of the research uses biomass only as either

an energy resource or a feedstock for chemicals production, with little consideration on the

potential of using biomass for sustainable product & energy co-generation, despite the

growing popularity of the “bioenergy” concept. In our study, we focus on the sustainable

production of polylimonene carbonate (PLC), a newly proposed biopolymer of which the

monomer precursor (limonene) can be directly derived from various biomass resources such
37,39 40,41
as citrus wastes and microalgae . Different synthesis methods from limonene
35,37
oxidation to PLC production have been explored in previous studies , and it is
42
demonstrated that PLC is a perfect candidate to replace polystyrene (PS) , a commercial

fossil based polymer with a large global market demand but causing significant

environmental burden during its manufacturing route 43. Nonetheless, until now little effort

has been paid to the design of environmentally friendly PLC production process.

In our very recent study 44, synthesis routes from limonene oxidation to PLC production were

proposed by adopting a series of reactions that occur under mild conditions (room

temperature and 1 bar) with high conversion and selectivity. Despite the careful selection, our

study concluded that these processes still cause negative environmental impacts due to the

considerable amount of energy consumed in the separation steps, even though the raw

materials for PLC production come from eco-friendly feedstocks (biomass, CO 2) and the only

process by-product is water. However, as biomass can also be utilised for energy production,

it is possible that through biomass energy co-generation, the energy required for PLC

production can be totally supplied from biomass. Thus, the environmental impacts of this

process (PLC & energy co-generation system) can be significantly improved. Therefore, to

test this hypothesis, the current study aims to conduct a life cycle assessment (LCA) by
designing a conceptual PLC production system with energy co-generation, and provide

directions for future generic sustainable bio-based process development.

2. Methodology

2.1 Process design and description

An original process design for polylimonene carbonate (PLC) production was conducted in
44
our previous study , including limonene production from citrus waste, limonene oxide

synthesis via limonene and tert-butyl hydroperoxide (TBHP), PLC synthesis by limonene

oxide and CO2, and TBHP regeneration via tert-butyl alcohol (TBA, product from the

limonene oxide synthesis section) and hydrogen peroxide. The study, however, concluded

that despite the starting materials for PLC production coming from citrus wastes extracted

limonene and CO2, the underlying polymer production route is still not carbon-negative or

carbon-neutral. Moreover, the entire polymer production system designed also results in

negative impacts in several environmental categories e.g. climate change, human toxicity,

and water and fossil resource depletion due to the use of TBHP.

To improve the environmental sustainability of the PLC production process and compare it

against the traditional polystyrene (PS) production route, in this study, two improvements are

addressed. The first modification is the change of the limonene oxide synthesis route via a

direct reaction between limonene and hydrogen peroxide under mild conditions with a more

eco-friendly solvent. This is because the previous study identifies that the use of TBHP is

responsible for a significant proportion of environmental impacts of the original PLC

production process 44. The second improvement is the change of the fate of citrus waste for

energy co-generation. In the original process design, citrus waste after limonene extraction

was sold as cattle feed, and the solar energy fixed inside the biowaste during photosynthesis
was barely used. Therefore, the process designed in the current work includes limonene

production from citrus waste, limonene oxidation, PLC synthesis, and biomass energy

regeneration. Specific modifications from limonene oxidation to PLC production are

presented in Fig. 1.

Figure 1: PLC production process, including limonene oxidation (top section) and PLC

synthesis (bottom section). Terminology: SEP – distillation column, RC – recycle, MIXS –

mixer, PLC-SEP – liquid/solid separator, REA – reactor. MIX – solution mixture, DIS –

solution separated after distillation column, METH – methanol, LIM – limonene, LIMO –

limonene oxide.

2.1.1 Limonene production and energy co-generation

The limonene extraction procedure from citrus wastes used in this work is same as that
44
described in the previous study . The only difference is that biowaste after limonene

extraction is now used for energy generation. Because the limonene content in citrus peels is
around 3.8 wt% (dry weight) 45, it is estimated that to produce 1 kg of limonene, about 25.32

kg of biowaste have to be supplied from the citrus plant. Previous research claimed that a nett

energy of 48 MJ (in form of heat) can be generated from 1 kg of citrus based biowaste
18
through gasification . Therefore, theoretically speaking, for each kilogram of limonene

produced from citrus waste, 1.22 GJ nett energy can be co-generated for heat and electricity

supply.

2.1.2 Limonene oxide synthesis and PLC production

In the current work, direct oxidation of limonene by hydrogen peroxide is selected with the

aim to improve the process sustainability, although a higher conversion efficiency and
42,46
selectivity can be achieved by using TBHP . It is reported that under mild conditions the

highest conversion efficiency and selectivity of this reaction are 78% and 86%, respectively,
46
which happens at 1 bar and 80 °C with ethyl acetate being the solvent . Therefore, this

information is selected in the current study for the re-design of limonene oxide synthesis

section. A schematic of this section (pumps, valves, and reactant recycles are omitted) is

shown in Fig. 2.

From the figure, it is seen that after the reaction, the mixture comprising both products

(limonene oxide and water) and unreacted reactants (hydrogen peroxide and limonene) is sent

to a distillation column (SEP1) for separation. Because of the low heat stability of hydrogen

peroxide 47, this separation is carried out under vacuum conditions with water and solvent

being removed from the top and the rest removed from the bottom. Then, the mixture of

limonene, hydrogen peroxide, and limonene oxide is separated in another distillation column

(SEP3). The distillate which consists of unreacted limonene and hydrogen peroxide is
recycled to the reactor (shown in Fig. 1), and limonene oxide is piped to the PLC production

section.

Figure 2: Schematic of limonene oxide synthesis section. Terminologies are same with Fig. 1.

Meanwhile, ethyl acetate and water are sent to a third column (SEP2) for distillation.

However, because ethyl acetate and water form an azeotrope (boiling point is 70.3 °C at 1

bar, with a composition of 8.5 wt% of water and 91.5% of ethyl acetate) 48, it is not possible

to separate the solvent and water purely in one distillation column. Although in theory this

mixture can be separated completely by adding another distillation column operated at a

different pressure, it is notable that the azeotrope contains a high concentration of ethyl

acetate (>90%) which is recycled in the system as a solvent. Therefore, purifying this

azeotrope is not necessary and may cause an extra process cost. Thus, the azeotrope is

recycled to the reactor and additional water is removed from the system after distillation.

Finally, the polymerisation reaction of CO2 and limonene oxide into PLC is conducted in the

presence of homogeneous, zinc-based catalysts at pressures of ~ 7 bar and at ambient

 37 42
temperature , with single-pass limonene oxide conversions of 50% (Fig. 1). The

experimental conditions for PLC synthesis need to be tightly controlled, because the catalyst

is easily deactivated in presence of water and air traces. After flashing off excess CO 2, PLC is

precipitated from the product mixture through the addition of methanol. Subsequently, the

solvent is removed via distillation and unreacted limonene oxide is passed to a secondary

reaction stage to continue the polymerisation process, followed by renewed PLC precipitation

with methanol. A detailed introduction regarding PLC production section can be found in the

previous work 44.

2.1.3 Polystyrene production process

So far, the LCA of the polystyrene (PS) production process has not been conducted. To

compare the environmental impacts between PLC and PS, it is essential to model the PS

production process in this work. Given that environmental impacts of the industrial styrene

(precursor of PS) synthesis route are available in the database, it is only necessary to design

the styrene polymerisation process. Therefore, this design is presented in Fig. 3 and briefly

described in this section.

Styrene polymerisation for PS production has been well established in industry 49. A solvent

(ethyl benzene) is usually added into the reactor for viscosity control. A series of reactors (3

to 5) are used for polymerisation. For example, when three reactors are used, the operating

temperature is generally controlled at 110 to 130 °C (set as 120 °C in this study) in the first

reactor and 150 to 180 °C (set as 150 °C and 180 °C in the second and third reactor,
49,50
respectively, in this study) in the last two reactors . To keep the reactant and solvent in a

liquid phase, pressures in the reactors are set to be 1 bar, 1.5 bar, and 3 bar in the first,

second, and third reactor, respectively 51. The final conversion is around 90% (set as 87.5% in
this work) 49. After reaction, the product mixture is sent to a vacuum devolatiliser to remove
49,50
solvent and unreacted monomer due to the low heat stability of ethyl benzene . Then, the

reactant mixture is recycled to the reactor and PS is sent for further refining (omitted in this

study for convenience of conceptual process design).

Figure 3: Schematic of polystyrene production process. Terminology: MIX – mixer, PUMP –

pump, HEAT – heat exchanger, REACTOR – reactor, PS-SEP – liquid/solid separator,

STYRE – styrene, EB – ethyl benzene, REAC – reactant, PROD – product, RECYC –

recycle flow, PS – polystyrene.

2.2 Life cycle assessment

Life cycle assessment (LCA) is widely used as a standard modelling tool to investigate the
52
environmental and health impacts of a process for a specific product synthesis . LCA

includes four steps: goal and scope definition, life cycle inventory, life cycle impact

assessment, and interpretation 53.

2.2.1 Goal and scopes

In this study, the goals of LCA are to explore the most influential factors determining the

process environmental and health impacts for further PLC production, and how to improve
the system performance so that the synthesis route of this newly proposed polymer can be

energy-efficient, environmentally sustainable, and carbon-negative (i.e. eliminating GHG

emission during the synthesis route) when taking into account the clean energy co-generated

through this process. The scope of this LCA covers the process from the preparation of the
54
raw materials (production of citrus wastes from orange trees) to the final production of

polymer before it is transported to customers. As a result, a cradle-to-gate analysis is adopted

in this work, as this method focuses on a system boundary from feedstock collection to final

product synthesis 55. As a detailed LCA for the upstream process (i.e. orange tree growth and
54
citrus wastes production) has been carried out in a recent study , the current research

therefore adopted the result obtained from the previous work when considering

environmental impacts of the upstream process. It should be emphasised that the supply chain

of raw materials and transportation of reactants and products are not included in this study

due to the early research stage. However, effects of supply chain will be considered in future

research once detailed process intensification is completed and the productivity of PLC is

increased.

Because PLC has been found to be able to replace the traditionally used PS due to their

similar properties 42, the petroleum derived PS synthesis route is selected as a benchmark to

evaluate the environmental sustainability of the current designed PLC production process.

What is more, the current proposed PLC production process is modified based on our

previous study by embedding energy co-generation from biowaste and re-designing the

limonene oxide synthesis section. As a result, to explore whether the current process can

result in a better environmental impact, the original PLC production process is also chosen as

a benchmark for comparison. The functional unit used in this study is set as producing 21,600
44
tonnes polymer (PLC or PS) per year in a single plant, same as that in our recent study ,
recommended by the previous work where the annual consumption of limonene used for

polymer production should be around 15,000 tonnes 56.

2.2.2 Life cycle inventory

The life cycle inventory (LCI) of the original PLC production process has been presented in
44
our previous work . Essential database including raw material preparation (citrus wastes

production from orange trees), limonene extraction from citrus wastes and PLC synthesis can

be directly used in this work. For biomass energy co-generation, a state-of-the-art heat and

electricity co-generation plant built in Europe was adopted in this study. This is because a

large amount of citrus waste is produced annually in several European countries such as

Spain and Italy. Hence, constructing a PLC production plant in Europe can guarantee the

stability of the raw material supply chain. The energy co-generation plant was originally

designed for energy recovery from agricultural biomass and wood waste and its database can

be found in Ecoinvent 3.2. Due to the lack of existing information, potential deviations

caused by the difference between citrus wastes and agricultural biomass are neglected in this

work, and will be refined in future work after additional data becomes available.

As estimated in a previous work, a nett energy of 48 MJ (in form of heat) can be generated

from 1 kg citrus waste through the same procedure 18.This information is therefore adopted

into in the current work. Energy generated from the plant is in form of steam (heat) which can

be further used for electricity generation. To complete the current LCI, both mass balance and

energy balance have to be calculated. Simulation results of feedstock consumption, energy

balance, and process cost are presented in the Results and discussion section. The full

inventory from raw materials consumption to PLC production can be found in the

Supplementary Information.
2.2.3 Impact assessment methodology

For the current proposed PLC and energy co-generation process as well as the PS production

process, process design and simulation were implemented in Aspen Plus V9. LCA was

conducted in Simapro 8.1, and the Ecoinvent 3.2 LCA database was used in the current

research. The assessment method selected for LCA is ReCiPe because of its wide application
54,57
used in European studies . Different environmental and health categories including

climate change, ozone depletion, human toxicity, ecotoxicity of land and water, agricultural

land occupation, and depletion of water and fossil are applied to identify the best polymer
54,57
synthesis route because they have been commonly used in the literature . As the processes

involved in this study are primarily used for polymer production, an allocation factor of

100% is given to the investigated polymers (PLC or PS).

3. Results and discussion

3.1 Process simulation results

Based on the proposed PLC production process, the modelling results that constitute the

current LCI are listed in Table 1. From the table, it is estimated that the cost for PLC

production from the current re-designed process is 1.15 €/kg, almost same as that of the

original PLC production process, and falls within the range of the current PS market price

(1.0 to 1.4 €/kg) 44. Therefore, from the economic perspective, both the original process and

the current modified process are promising for future PLC industrialisation and replacing PS.

It is, however, important to clarify that the potential profit gained from the co-generated

energy is not included in the economic analysis, given the fact that energy and cattle feed

(original PLC process) are considered as by-products and their price may oscillate frequently.
 Table 1: Simulation result of the current PLC production process

Limonene oxide synthesis section

Limonene H2O2 Limonene oxide H2O
Flow rate
1763.3 kg h-1 440.8 kg h-1 1970.7 kg h-1 233.4 kg h-1
Energy use Heat (steam) 0.127 MW Electricity 84.33 kW
-1
Solvent use Ethyl acetate 275.1 kg h
Capital cost Operating cost Raw material cost
Process cost
4.67 million € 1.50 million €/yr 19.3 million €/yr
PLC production section
Methanol Limonene oxide CO2 PLC
Flow rate -1 -1 -1
851.5 kg h 1970.7 kg h 570.5 kg h 2541.2 kg h-1
Energy use Heat (steam) 1.80 MW Electricity 54.56 kW
Capital cost Operating cost Raw material cost
Process cost
4.69 million € 1.41 million €/yr 1.84 million €/yr

3.2 Comparison of different limonene oxide synthesis routes

As mentioned before, limonene oxidation was identified to be the primary section

contributing environmental burdens in the original process due to the use of tert-butyl

hydroperoxide (TBHP) and its industrial synthesis method 44. Therefore, in the current study,

direct reaction between limonene and hydrogen peroxide under mild conditions is chosen to
46
re-design this section . Hence, to evaluate the improvement of process environmental

sustainability exclusively attributed by the replacement of limonene oxide synthesis section, a

comparison between the current (but without energy co-generation) and the previous PLC

production process is conducted. The results are shown in Fig. 4.

Figure 4: LCA of different polymer production processes. For PLC production, energy co-

generation is excluded here.

From Fig. 4, it can be found that the newly proposed PLC process (without energy co-

generation) indeed shows significant improvements compared to the original process in terms

of human toxicity and ecotoxicity, and also leads to lower climate change impacts. However,

when considering the scope of the entire environmental impacts, its advantages in human

health and climate change are partially offset by its higher consumption of natural resources

(water, fossil, and land) than the original PLC production process, due to the use of additional

solvent (ethyl acetate) in the limonene oxidation section. Nonetheless, when compared

against the PS production process, it is seen that the current proposed process results in a

50% reduction in climate change impacts with similar performance in human toxicity,

ecotoxicity, land occupation and better performance in natural resources depletion (water and

fossil). This indicates that when considering different environmental impact categories, the
current proposed PLC process can cause lower environmental burdens compared to the PS

production process, although this improvement is not significant. In terms of the original PLC

production process, in spite of its better performance in natural resources consumption and

climate change impacts than the PS production process, its severe ecotoxicity and human

toxicity may greatly prevent its further industrial application. As a result, the replacement of

original limonene oxidation section is demonstrated to be essential.

Most important, based on the current comparison result, it is concluded that only using

sustainable feedstocks and high conversion reactions is not sufficient enough to guarantee an

eco-friendly final product. For example, in the current study, the raw materials for polymer

production are CO2 and biowaste derived limonene, and the only by-product is water from

hydrogen peroxide. Meanwhile, both limonene oxidation and PLC production are conducted

under conditions with little energy consumption. However, the climate change impact is

amplified by over 10 times only after two reaction steps from limonene extraction (0.2l kg

CO2 eq. per kg limonene, equivalent to 0.15 kg CO 2 eq. per kg PLC) to PLC production (2.48

kg CO2 eq. per kg PLC). From Fig. 5(a), it is seen that similar to the result obtained in the
44
original process , the limonene oxidation section still causes the majority of the

environmental impacts.
Figure 5: LCA of the current designed PLC production process without energy co-generation.

(a) contribution of environmental impact from each section; (b) contribution of

environmental impact in the limonene oxidation section (limonene is excluded as its impact is

counted in the limonene production section).

In the previous study, it was concluded that such an observation is attributed to the use of

TBHP, a reactant of which the industrial synthesis route is environmentally harmful 44. In the

current research, however, it is found that the solvent selected (ethyl acetate) does not cause

the major environmental impact (Fig. 5(b)). On the contrary, both the use of hydrogen

peroxide and the consumption of heat utility play a significant role in this case. A further

investigation shows that when removing ethyl acetate from the entire PLC production system,

there is negligible change on the LCA result. This strongly suggests that when aiming to

design an eco-friendly chemical synthesis process, it is vital to consider not only from the

reaction and material conversion points of view, but more important from the energy use and

downstream separation perspectives. The heat supplied to the limonene oxidation section is

predominantly consumed by separating hydrogen peroxide, limonene oxide, and limonene

due to their similar boiling point; as well as extra water and ethyl acetate (removing extra

water from the water-ethyl acetate azeotrope). Thus, the amount of CO 2 produced from fossil

resources for energy supply is more than that consumed during PLC production. As a result,

this study concludes that in order to achieve an environmentally sustainability process, an

energy-efficient downstream separation procedure (e.g. easily separated mixtures) has to be

particularly designed, or low carbon heat sources (e.g. hydrogen) used.

3.3 LCA of PLC & energy co-generation process

As introduced in the methodology section, another modification of the current PLC

production process is that biowaste after limonene extraction is sent for energy generation

instead of being sold as cattle feed. Recall that for each 1 kg limonene extracted, 1.22 GJ nett
energy (in form of heat) can be generated for heat (steam) and electricity generation.

Therefore, by taking this factor into account, LCA results of the PLC & energy co-generation

process are presented in Fig. 6.

From Fig. 6(a), it is seen that with energy co-generation, a significant improvement in the

environmental and health impacts of the current PLC production process is achieved. Except

for a marginal impact on water depletion (positive LCA results indicate a negative

environmental impact), the PLC & energy co-generation process shows great positive

impacts to the environment for all the categories included in this study. This clearly

demonstrates the vital role of using biomass for energy generation for future sustainable

process design. It is important to emphasise that the energy released from biomass comes

from solar energy, and through gasification this energy is effectively converted into heat.

Although the majority of CO2 fixed during photosynthesis is released to the environment, the

amount of captured solar energy through biomass gasification can fully support the heat and

electricity required for the entire PLC production process. Thus, no fossil resource is needed

to supply energy for PLC synthesis. Furthermore, due to the fast growth rate of agricultural

plants, the emitted CO2 from biomass gasification can be rapidly fixed by photosynthesis for

the growth of plant and synthesis of useful raw material (e.g. limonene). Therefore,

systematically speaking, this carbon flow cycle eventually results in the co-production of

carbon-negative chemicals and energy.

Figure 6: LCA of the PLC and energy co-generation process. (a): current designed PLC

production process; (b): original PLC production process.

For instance, in the current study, the total energy required for 1 kg PLC production is 3.53

MJ heat eq. (including 2.73 MJ heat and 0.20 MJ electricity; this electricity is equivalent to

0.80 MJ heat, with a thermal to electrical energy conversion of 0.25 21), while that produced

from biowaste is 33.3 MJ, almost 10 times of the energy required for PLC synthesis. Hence,

the energy released from biomass gasification can supply not only the energy consumed in

the polymer production system, but also provide extra heat and electricity for other systems.

Based on the same principle, by changing the fate of biowaste for energy generation, notable

improvements in the environmental impact of the original PLC production are also achieved,

with only mild environmental burdens remaining in terrestrial and freshwater ecotoxicity

(Fig. 6(b)). This clearly demonstrates the essential role of using biomass for energy co-

generation for future sustainable process design. Whilst when comparing with Fig. 6(a), the

current re-designed process is still found to be a better option than the original PLC

production process, given its greater values on most of the environmental categories (except

the marginal water depletion due to the change of limonene oxidation route). Thus, the

current proposed process should be selected for future more detailed PLC production process

design and optimisation.

3.4 Comparison of citrus and algae derived PLC & energy co-generation processes
44
Finally, in the previous study , another process in which limonene is produced from

genetically engineered microalgae mutant was also designed and compared against the citrus

derived PLC production process. In the microalgae derived PLC production process, algal

biomass after limonene synthesis is also sent for electricity generation through anaerobic
digestion. Similarly to the current conclusion, the previous research found that this process

also contributes significant benefits to the environment. Therefore, to identify which

feedstock, algae or citrus waste, could have the best performance for sustainable PLC

production, both the algae based and the citrus based PLC & energy co-generation processes

are compared through LCA. Furthermore, since it is demonstrated that the current proposed

limonene oxide synthesis section is better than the previous designed route, the original algae

derived PLC production process is also modified here by substituting the current limonene

oxidation method for the previous one. The comparison result is shown in Fig. 7.

Figure 7: Comparison of LCA results of citrus based and algae based PLC production process
From Fig. 7, it is seen that for the majority of the environmental and health categories, both

processes show positive impacts (negative LCA values), indicating their promising

environmental performance. Nonetheless, there are three reasons why citrus waste should be

selected as the most suitable feedstock for future PLC production instead of algae. Firstly, the

citrus based PLC production route leads to a much better performance (generally over double

compared to the algae derived route) on most of the environmental categories e.g. human

toxicity, ozone depletion, ecotoxicity, meanwhile guaranteeing a positive impact on climate

change and fossil depletion. Thus, when considering all the potential environmental impacts,

this process demonstrates a greater eco-friendliness. Secondly, particularly to water

depletion, the algae derived system shows a considerable water demand compared to the

citrus based system (negligible water depletion). This is because microalgae biomass has to

be cultivated in a suspended liquid system in which water occupies 99% of the reactor

volume 58. As a result, compared to the plantation of citrus biomass, the algae cultivation

route causes a critical burden on water resources, thus it may not be preferred for industrial

scale PLC production.

Thirdly, from the reality point of view, limonene mass content from citrus waste is 3.8%,

which is over 16 times higher than that from algae (0.23%) 41. This means that to produce the

same amount of limonene, more nutrients (e.g. nitrogen, sulphur, minerals) have to be

consumed for algae cultivation than citrus plants, and the separation and reuse of these

natural resources may become a potential challenge reducing process eco-friendliness and

energy-efficiency. This is one of the reasons why the citrus based PLC production process

yields a better overall performance than the algae based PLC production route in the current

study. In addition, because of the extremely low limonene content synthesised from

microalgae biomass, it is unlikely that the algae derived PLC synthesis route can be applied
to industrial-scale production and meet the global limonene market demand for the use of

polymers and cosmetics. As a result, the citrus based process is more promising and should

be given more emphasis in future study.

Conclusion

Overall, based on the current study, two conclusions are obtained. The first one is that an

energy-efficient separation procedure is of critical importance for the design of sustainable

and eco-friendly chemical production processes. This suggests that when choosing a

synthesis route for the target chemical production, criteria should not be exclusively provided

from the reaction point of view (e.g. green chemistry indices) but also from the separation

perspective (e.g. how easy that the reaction mixture can be separated). Otherwise, energy

consumption during separation, recycle, and resources reuse can result in great environmental

and health burdens and cause the process to be environmentally harmful, even if the synthesis

route is short and the reactants are derived from sustainable resources.

The second conclusion is that when aiming to design an eco-friendly process, it is vital to

consider biomass as both a raw material and an energy source. In other words, compared to

only maximising the material conversion efficiency from feedstock into the target product, it

is more important to optimise the ratio of biomass between being a sustainable feedstock and

being a renewable energy supplier. Based on the current study, it is expected that a carbon-

negative and energy-positive process should be designed in such a way that all the energy

required in the system is provided from part of the biomass feedstock, with the rest being

used for target chemical and energy co-production.

In terms of future work, it is noticed that more comprehensive process design and control has

to be carried to ensure the high performance of PLC polymerisation, as the present

experimental conditions need to be tightly controlled due to the deactivation of catalyst.

Potential environmental impact caused by catalyst reactivation should be also considered. In

particular, similarly to polystyrene synthesis, PLC synthesis yields a solid and brittle polymer

which requires co-solvent to guarantee the high conversion and efficient separation. While

catalysts from the zinc-based family are typically deactivated due to the presence of solvents,

aluminium-based catalysts are typically more “resistant” to the existence of co-solvents 59 and

should be focused for the development of more robust catalyst.

Acknowledgement

This research is supported by the EPSRC project under grant EP/L017393/1, “Sustainable

Polymers”.

References

1. White, A. A. et al. The National Science Foundation’s Investment in Sustainable

Chemistry, Engineering, and Materials. ACS Sustain. Chem. Eng. 1, 871–877 (2013).

2. Gong, J. et al. Sustainable Conversion of Mixed Plastics into Porous Carbon

Nanosheets with High Performances in Uptake of Carbon Dioxide and Storage of

Hydrogen. ACS Sustain. Chem. Eng. 2, 2837–2844 (2014).

3. Gutiérrez-Arriaga, C. G., Serna-González, M., Ponce-Ortega, J. M. & El-Halwagi, M.

M. Sustainable Integration of Algal Biodiesel Production with Steam Electric Power

Plants for Greenhouse Gas Mitigation. ACS Sustain. Chem. Eng. 2, 1388–1403 (2014).

4. Miller, S. A. Sustainable polymers: replacing polymers derived from fossil fuels.

Polym. Chem. 5, 3117 (2014).

5. Capelli, B., Bagchi, D. & Cysewski, G. R. Synthetic astaxanthin is significantly

inferior to algal-based astaxanthin as an antioxidant and may not be suitable as a

human nutraceutical supplement. Nutrafoods 12, 145–152 (2013).

6. Fava, F. et al. Biowaste biorefinery in Europe: opportunities and research &

development needs. N. Biotechnol. 32, 100–108 (2015).

7. Zhang, D., del Rio-Chanona, E. A. & Shah, N. Screening Synthesis Pathways for

Biomass-Derived Sustainable Polymer Production. ACS Sustain. Chem. Eng.

acssuschemeng.7b00429 (2017).

8. Zhang, D., Chanona, E. A. D.-R., Vassiliadis, V. S. & Tamburic, B. Analysis of green

algal growth via dynamic model simulation and process optimization. Biotechnol.

Bioeng. 112, (2015).

9. del Rio-Chanona, E. A., Ahmed, N. rashid, Zhang, D., Lu, Y. & Jing, K. Kinetic

modeling and process analysis for Desmodesmus sp. lutein photo-production. AIChE

J. 63, 2546–2554 (2017).

10. Gnansounou, E. & Raman, J. K. Life cycle assessment of algae biodiesel and its co-

products. Appl. Energy 161, 300–308 (2016).

11. Zhang, D. & Vassiliadis, V. S. Chlamydomonas reinhardtii Metabolic Pathway

Analysis for Biohydrogen Production under Non-Steady-State Operation. Ind. Eng.

Chem. Res. 54, 10593–10605 (2015).

12. Xu, D. & Savage, P. E. Effect of reaction time and algae loading on water-soluble and

insoluble biocrude fractions from hydrothermal liquefaction of algae. Algal Res. 12,

60–67 (2015).

13. Rodriguez, C., Alaswad, A., Mooney, J., Prescott, T. & Olabi, A. G. Pre-treatment

techniques used for anaerobic digestion of algae. Fuel Process. Technol. 138, 765–779

(2015).
14. Wan, M. et al. The effective photoinduction of Haematococcus pluvialis for

accumulating astaxanthin with attached cultivation. Bioresour. Technol. 163, 26–32

(2014).

15. Xie, Y.-P. et al. Simultaneous enhancement of CO2 fixation and lutein production with

thermo-tolerant Desmodesmus sp. F51 using a repeated fed-batch cultivation strategy.

Biochem. Eng. J. 86, 33–40 (2014).

16. Xie, Y. et al. Fed-batch strategy for enhancing cell growth and C-phycocyanin

production of Arthrospira (Spirulina) platensis under phototrophic cultivation.

Bioresour. Technol. 180, 281–287 (2015).

17. del Rio-Chanona, E. A., Zhang, D., Xie, Y., Manirafasha, E. & Jing, K. Dynamic

Simulation and Optimization for Arthrospira platensis Growth and C-Phycocyanin

Production. Ind. Eng. Chem. Res. 54, 10606–10614 (2015).

18. Lanfranchi, M. Economic analysis on the enhancement of citrus waste for energy

production. J. Essent. Oil Res. 24, 583–591 (2012).

19. Yun, Y.-M. et al. Biohydrogen production from food waste: Current status, limitations,

and future perspectives. Bioresour. Technol. (2017).

20. del Rio-Chanona, E. A., Zhang, D. & Shah, N. Sustainable biopolymer synthesis via

superstructure and multiobjective optimization. AIChE J. (2017).

21. Koppar, A. & Pullammanappallil, P. Anaerobic digestion of peel waste and wastewater

for on site energy generation in a citrus processing facility. Energy 60, 62–68 (2013).

22. Ward, A. J., Lewis, D. M. & Green, F. B. Anaerobic digestion of algae biomass: A

review. Algal Res. 5, 204–214 (2014).

23. Azadi, P., Brownbridge, G. P. E., Mosbach, S., Inderwildi, O. R. & Kraft, M.

Production of Biorenewable Hydrogen and Syngas via Algae Gasification: A

Sensitivity Analysis. Energy Procedia 61, 2767–2770 (2014).

24. Li, B. et al. Hydrogen production from agricultural biomass wastes gasification in a

fluidized bed with calcium oxide enhancing. Int. J. Hydrogen Energy 42, 4832–4839

(2017).

25. Ferreira, C. I. A. et al. Comparative valorisation of agricultural and industrial

biowastes by combustion and pyrolysis. Bioresour. Technol. 218, 918–925 (2016).

26. Anand, V., Sunjeev, V. & Vinu, R. Catalytic fast pyrolysis of Arthrospira platensis

(spirulina) algae using zeolites. J. Anal. Appl. Pyrolysis 118, 298–307 (2016).

27. La Villetta, M., Costa, M. & Massarotti, N. Modelling approaches to biomass

gasification: A review with emphasis on the stoichiometric method. Renew. Sustain.

Energy Rev. 74, 71–88 (2017).

28. Anand, V., Sunjeev, V. & Vinu, R. Catalytic fast pyrolysis of Arthrospira platensis

(spirulina) algae using zeolites. J. Anal. Appl. Pyrolysis 118, 298–307 (2016).

29. Steubing, B., Zah, R. & Ludwig, C. Heat, Electricity, or Transportation? The Optimal

Use of Residual and Waste Biomass in Europe from an Environmental Perspective.

Environ. Sci. Technol. 46, 164–171 (2012).

30. Lardon, L., Hélias, A., Sialve, B., Steyer, J.-P. & Bernard, O. Life-Cycle Assessment

of Biodiesel Production from Microalgae. Environ. Sci. Technol. 43, 6475–6481

(2009).

31. Song, J. et al. Biomass-derived γ-valerolactone as an efficient solvent and catalyst for

the transformation of CO2 to formamides. Green Chem. 18, 3956–3961 (2016).

32. Zhang, D. et al. Dynamic modelling of Haematococcus pluvialis photoinduction for

astaxanthin production in both attached and suspended photobioreactors. Algal Res.

13, 69–78 (2016).

33. Arora, P., Hoadley, A. F. A., Mahajani, S. M. & Ganesh, A. Small-Scale Ammonia

Production from Biomass: A Techno-Enviro-Economic Perspective. Ind. Eng. Chem.

 Res. 55, 6422–6434 (2016).

34. del Rio-Chanona, E. A. et al. Optimal Operation Strategy for Biohydrogen Production.

Ind. Eng. Chem. Res. 54, 6334–6343 (2015).

35. Peña Carrodeguas, L., González-Fabra, J., Castro-Gómez, F., Bo, C. & Kleij, A. W. Al

III -Catalysed Formation of Poly(limonene)carbonate: DFT Analysis of the Origin of

Stereoregularity. Chem. - A Eur. J. 21, 6115–6122 (2015).

36. Byrne, C. M., Allen, S. D., Lobkovsky, E. B. & Coates, G. W. Alternating

Copolymerization of Limonene Oxide and Carbon Dioxide. J. Am. Chem. Soc. 126,

11404–11405 (2004).

37. Hauenstein, O., Reiter, M., Agarwal, S., Rieger, B. & Greiner, A. Bio-based

polycarbonate from limonene oxide and CO 2 with high molecular weight, excellent

thermal resistance, hardness and transparency. Green Chem. 18, 760–770 (2016).

38. Winkler, M., Romain, C., Meier, M. A. R. & Williams, C. K. Renewable

polycarbonates and polyesters from 1,4-cyclohexadiene. Green Chem. 17, 300–306

(2015).

39. Zhu, Y., Romain, C. & Williams, C. K. Sustainable polymers from renewable

resources. Nature 540, 354–362 (2016).

40. Jahandideh, A. et al. Life cycle analysis of a large-scale limonene production facility

utilizing filamentous N 2 -fixing cyanobacteria. Algal Res. 23, 1–11 (2017).

41. Davies, F. K., Work, V. H., Beliaev, A. S. & Posewitz, M. C. Engineering Limonene

and Bisabolene Production in Wild Type and a Glycogen-Deficient Mutant of

Synechococcus sp. PCC 7002. Front. Bioeng. Biotechnol. 2, (2014).

42. Dalaeli, J., Fogle, C. & Yang, J. Polymers from Oranges: Design and Feasibility of

Polymer Production from Orange Oil Derivatives. (2005).

43. U.S. Environmental Protection Agency. Global Warming Potentials (GWP) of ODS
 Substitutes. (2016).

44. Zhang, D., del Rio-Chanona, E. A., Wagner, J. L. & Shah, N. Life cycle assessments

of bio-based sustainable polylimonene carbonate production processes. Sustain. Prod.

Consum. (2018). doi:10.1016/j.spc.2018.03.001

45. Ciriminna, R., Lomeli-Rodriguez, M., Demma Carà, P., Lopez-Sanchez, J. A. &

Pagliaro, M. Limonene: a versatile chemical of the bioeconomy. Chem. Commun. 50,

15288–15296 (2014).

46. Bonon, A. J. et al. Limonene epoxidation with H2O2 promoted by Al2O3: Kinetic

study, experimental design. J. Catal. 319, 71–86 (2014).

47. Hurd, C. & Puterbaugh, M. Concentration of Hydrogen Peroxide. (1930).

48. B/R Instrument Corporation. What is an Azeotrope? (2017). Available at:

http://www.solvent--recycling.com/azeotrope_1.html.

49. Odian, G. Principles of Polymerization. (John Wiley & Sons, Inc., 2004).

50. Platzer, N. Design of Continuous and Batch Polymerization Process. Ind. Eng. Chem.

62, 6–20 (1970).

51. Almeida, A. S., Wada, K. & Secchi, A. R. Simulation of styrene polymerization

reactors: kinetic and thermodynamic modeling. Brazilian J. Chem. Eng. 25, 337–349

(2008).

52. Yates, M. R. & Barlow, C. Y. Life cycle assessments of biodegradable, commercial

biopolymers—A critical review. Resour. Conserv. Recycl. 78, 54–66 (2013).

53. Montazeri, M. & Eckelman, M. J. Life Cycle Assessment of Catechols from Lignin

Depolymerization. ACS Sustain. Chem. Eng. 4, 708–718 (2016).

54. Roberts, G. Life Cycle Assessment - Renewable and Sustainable Citrus Oils Final

Report. (2012).

55. von der Assen, N. & Bardow, A. Life cycle assessment of polyols for polyurethane
 production using CO2 as feedstock: insights from an industrial case study. Green

Chem. 16, 3272 (2014).

56. Kong, Q. & Shah, N. An optimisation-based framework for the conceptual design of

reaction-separation processes. Chem. Eng. Res. Des. 113, 206–222 (2016).

57. Keller, H., Rettenmaier, N. & Reinhardt, G. A. Integrated life cycle sustainability

assessment – A practical approach applied to biorefineries. Appl. Energy 154, 1072–

1081 (2015).

58. Liu, T. et al. Attached cultivation technology of microalgae for efficient biomass

feedstock production. Bioresour. Technol. 127, 216–222 (2013).

59. Carrodeguas, L. P. et al. AlIII‐Catalysed Formation of Poly(limonene)carbonate: DFT

Analysis of the Origin of Stereoregularity. Chem. Eur J. 21, 6115–6122 (2015).

 Life cycle impact of the current PLC & energy co-production process

LCA for limonene production per 1,000 kg (ReCiPe) Environmental impact

Climate change 207 kg CO2-eq
Water depletion 0.75 m3
Fossil depletion 51.9 kg oil-eq
Terrestrial acidification 0.83 kg SO2-eq
Freshwater eutrophication 4.84 × 10-2 kg P-eq
Marine eutrophication 0.28 kg N-eq
Terrestrial ecotoxicity 0.006 kg 1,4-DB-eq
Freshwater ecotoxicity 0.468 kg 1,4-DB-eq
Marine ecotoxicity 0.54 kg 1,4-DB-eq
Human toxicity 50.0 kg 1,4-DB-eq
Ozone depletion 9.42 × 10-6 kg CFC-eq
Photo-chemical oxidant formation 0.81 kg NMVOC
Raw materials for PLC production process Annual consumption
Limonene 15 kt/year
Hydrogen peroxide 3.7 kt/year
Ethyl acetate 2.3 kt/year
Water generated from PLC production process 2.0 kt/year
Methanol 7.1 kt/year
CO2 required for PLC synthesis 5.0 kt/year
Total PLC production 21.6 kt/year
Total heat required for PLC production 5.9 × 107 MJ/year
Total electricity required for PLC production 4.3 × 106 MJ/year

For citrus derived limonene production process, the life cycle inventory was not directly

provided in the previous study 1, whilst the LCA results were provided and therefore added

into the current database. LCA in the previous study was implemented through the same

method as the current study (ReCiPe Midpoint method). A detailed introduction of this

process can be found in the published report 1.

References

1. Roberts G. Life Cycle Assessment - Renewable and Sustainable Citrus Oils Final

Report. Chicago; 2012.