Top Curr Chem (Z) (2018) 376:3https://doi.org/10.1007/s41061-017-0182-z

1 3

REVIEW

Green and Sustainable Separation of Natural Products from Agro‑Industrial Waste: Challenges, Potentialities, and Perspectives on Emerging Approaches

Vânia G. Zuin1,2  · Luize Z. Ramin1

Received: 30 August 2017 / Accepted: 26 December 2017 / Published online: 17 January 2018 © The Author(s) 2018. This article is an open access publication

Abstract New generations of biorefinery combine innovative biomass waste resources from different origins, chemical extraction and/or synthesis of biomate-rials, biofuels, and bioenergy via green and sustainable processes. From the very beginning, identifying and evaluating all potentially high value-added chemicals that could be removed from available renewable feedstocks requires robust, efficient, selective, reproducible, and benign analytical approaches. With this in mind, green and sustainable separation of natural products from agro-industrial waste is clearly attractive considering both socio-environmental and economic aspects. In this paper, the concepts of green and sustainable separation of natural products will be dis-cussed, highlighting the main studies conducted on this topic over the last 10 years. The principal analytical techniques (such as solvent, microwave, ultrasound, and supercritical treatments), by-products (e.g., citrus, coffee, corn, and sugarcane waste) and target compounds (polyphenols, proteins, essential oils, etc.) will be pre-sented, including the emerging green and sustainable separation approaches towards bioeconomy and circular economy contexts.

Keywords Green and sustainable extraction · Sustainable separation · Green analytical techniques · Biomass waste · Biorefinery · Bioeconomy and circular economy

This article is part of the Topical Collection“Chemistry and Chemical Technologies in Waste Valorization”; editedby Carol Sze Ki Lin.

* Vânia G. Zuin vaniaz@ufscar.br; vania.zuin@york.ac.uk

1 Department of Chemistry, Federal University of São Carlos, Rod. Washington Luís, km 235, São Carlos 13565-905, Brazil

2 Green Chemistry Centre of Excellence, University of York, North Yorkshire YO10 5DD, UK

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1 Introduction

Currently, it can be observed that global sustainability challenges are all closely interconnected, such as pollution, climate change, biodiversity loss, poverty, energy, and food security. As stated by Liu et al. [1], only holistic and disruptive approaches integrating various components of human and natural systems are effective in iden-tifying and proposing suitable solutions for these challenges, especially those related to research, development, and innovation (RD&I) in interdisciplinary and transdisci-plinary studies. To exemplify this systemic view, Fig. 1 illustrates the Earth surface that, based on the “Dymaxion map” (the Fuller Projection Map), shows the planet as a continuum without splitting any continents, seas, and oceans, where cycles are integrated through flows of matter, energy, and information [1, 2]. Here, Bra-zil, China, the Caribbean, and Africa interact across space, time, and organizational levels in many ways. For instance, the expansion of soybean production aggravates deforestation in Brazil, but also provides food and feedstock to China. The food trade between both countries also affects other areas, including the Caribbean and Africa. Dust particles from the Sahara Desert, also increased due to unbalanced agricultural practices, can reach the Caribbean and have an impact on coral reefs and soil fertility, diminishing tourism in this region. In addition, nutrient-rich particles from Africa can reach Brazil, improving its forest productivity.

According to the Director-General of the Food and Agriculture Organization (FAO) of the United Nations [3], after years of progress, world hunger has increased since 2015. Around 60% of the world’s starving people are from countries affected by conflict and climate change, including northeast Nigeria, Somalia, South Sudan, and Yemen with 20 million people, often suffering extreme climatic events such as droughts and floods. Not surprisingly, some of the FAO’s top priorities for the next

Fig. 1 Representation of an integrated planetary flow system based on the Dymaxion map, emphasizing some coupled cycles related to food production and socio-environmental impacts among (1) Brazil, (2) China, (3) the Caribbean, and (4) the Sahara Desert. Adapted from [1]

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2 years include topics such as sustainable agriculture, climate change mitigation and adaptation, water scarcity and support of subsistence rural practices, and fisheries and forestry [3, 4]. The challenges related to this demanding context can be intensi-fied and better understood when taking into account that the world population is expected to increase by about 30% over the next 35 years, reaching more than 9.5 billion people in 2050 and 11.2 billion in 2100 [5].

As pointed out by Xia et al. [6], the global food waste of approximately 1.3 bil-lion tons per year is shocking in this context and, although it should be avoided or minimized, it cannot be completely prevented nowadays. Primary and secondary processing generates unpreventable food supply chain waste. This can be due to a number of factors along the supply chain, differing by the commodity and country in question. In general terms, developing countries such as some African countries suffer the greatest loss during the early, upstream part of the primary processing, corresponding to 75% of food losses during production and postharvest. Various ini-tiatives, e.g., building better infrastructure through knowledge transfer (more effi-cient storage and transport technologies) and improving collaboration and market opportunities in the food supply chain could have a positive role. In industrialized countries, waste occurs especially in the consumption stage, accounting for 50% of overall loss of crops in some countries of North America, Europe, and Oceania. In this case, together with educational and cultural actions, other aspects such as developing legislation to make date labels more user-friendly for consumers (sell-by, best-before, and consume-by), redesigning packaging characteristics (avoiding the “buy 1 get 2” offers) and retailer marketing strategies should be considered [7].

It is estimated that around 140 billion tons of biomass from the agricultural sec-tor are generated every year in the world [8, 9], and a considerable part is recog-nized as waste and not conflicting with food availability, e.g., leaves, roots, stalks, bark, bagasse, straw residues, seeds, wood and animal residues. Using alternative strategies to avoid additional losses and produce several high value-added chemicals could minimize the volume of non-renewable materials used today (i.e., roughly 50 billion tons of fossil fuels), enough to greatly reduce greenhouse gas emissions and dependence on non-sustainable resources. Therefore, considering their available vol-ume and practically low costs locally and globally, associated to rich function, struc-ture and chemical heterogeneity, all agro-industrial waste should also be considered for their chemical and material potential, as well as a source of energy [10–13].

An important proposal related to waste hierarchy as a framework for residue man-agement can be seen in Fig.  2 [14, 15], which was reformulated to include agro-industrial waste. In this case, the agro-industrial waste hierarchy has a different meaning from top to bottom, since all biomass is valued as raw material. ‘Preven-tion’ is an intrinsic part of optimized processes, avoiding overproduction. There-fore, the least probable option is ‘disposal’ as the supply chain is designed to attend sustainable consumption, using all bio-based material generated. Here, sustainable production also includes eco-efficiency, cleaner and green productivity, whereas sustainable consumption allows greener choices to be made by individuals based on eco-procurement, supply chain management, waste minimization, recycling, and resource efficiency measures. Both sustainable production and consumption comprises ‘life-cycle thinking’, aiming at preventing problems shifting from one

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life-cycle stage to another, one geographical area or environmental compartment to another.

One of the most important and cited references highlighting the advances in genetics, biotechnology, process chemistry, and engineering that has helped estab-lish a new manufacturing concept to convert renewable biomass into valuable fuels and products, known as biorefinery, was published by Ragauskas and collaborators in the mid-2000s [16]. According to these authors and other researchers [16, 17], integrating biomass and biorefinery technologies has the potential to develop sus-tainable bio-based energy and materials leading to a new manufacturing paradigm (Fig. 3).

In fact, this paradigm is currently connected to other strong concepts, i.e., bio-economy and circular economy; the latter is described as an industrial system that is restorative by intention and design. This idea replaces the end-of-life notion with regeneration, focusing on the use of renewable energy, elimination of toxic chemi-cals, reutilization, return and eradication of “waste through the superior design of materials, products, systems, and business models” [18, 19].

As can be noted, new generations of biorefinery combine innovative biomass resources from different origins, chemical extraction and purification and/or syn-thesis of biomaterials, biofuels and bioenergy via benign processes. From the very beginning, the identification and quantification of all potentially high value-added

Fig. 2 The agro-industrial waste hierarchy modified from [15]. The main idea is to promote sustainable production and consumption systems through zero-waste biorefinery

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compounds that could be removed from the available renewable feedstocks requires another analytical approach, also connected to green chemistry [20, 21].

2 From Green to Sustainable Separation: Towards Holistic, Flexible, and Zero‑Waste Biorefineries

More recently, green extraction and purification have been presented as methods based on establishing processes that reduce energy consumption, using solvents and renewable materials, as well as ensuring a safe and high-quality fraction/product [22]. The aim of their application is to obtain natural products from industrial waste, which is considered a highly attractive initiative [23].

However, a more adequate term for such extraction and purification processes towards vanguard biorefineries could be sustainable separation, adding to the pre-vious green definition, the notion of innovation across all sectors that allows for

Fig. 3 Holistic biorefinery model integrating biomass, biofuel, biomaterials and bioenergy cycle, based on green and sustainable technologies in the scope of bioeconomy and circular economy. Updated and expanded from [16, 17]

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increased value in a wide sense, enhancing human and environment benefits and providing economically accessible technologies also advantageous to industry and large scale processing systems. It includes another dimension related to the genera-tion of more creative and healthy jobs, contributing to the construction of a positive long-term sustainability agenda, encompassing bio-circular economy, environmental and social justice [24–27].

Sustainable separation can be defined as a holistic approach grounded on the cir-cular and flexible design and application of renewable benign materials and aux-iliaries (including bio-derived solvents, solid phases, membranes) and processes [rooted on green analytical techniques and sustainability metrics and indices, e.g., life cycle analysis (LCA), chemometrics, and other interdisciplinary indicators]. The aim is to optimize the tuneable use of energy, time, reagents, devices, scale, yield and number of steps to extract, fractionate, purify or even modify the components of interest from bio-derived waste during these in situ processes, ensuring analytical reproducibility, efficiency, selectivity robustness and scalability, with online evalu-ation regarding measurable objectives to create safer, healthier, and more efficient products, processes, and services under fair conditions, commercially available at accessible and just prices [28–30].

Natural products are among the most attractive value-added chemicals to be con-sidered, which can be classified as organic compounds formed by living systems divided into three main categories: (1) compounds that occur in all cells and have a central role in their metabolism and reproduction (nucleic acids, amino acids, and sugars), also known as primary metabolites; (2) high-molecular polymeric materials which form cellular structures (cellulose, lignins, and proteins) and; (3) chemicals which are characteristic of a limited number of species, called secondary metabo-lites [22, 30]. Many of these bioactive compounds (e.g., alkaloids, terpenoids, and phenols) have been extensively used as medicine, nutraceuticals, flavors, fragrances, cosmetics, food additives, antimicrobials, bio-pesticides, etc. However, among the biggest challenges for biomass utilization is establishing benign methods to separate, purify and modify it into chemicals, fuels, and new materials. This is partially due to, with rare exceptions, the small amounts which are lower than 0.01% of the dry weight of vegetal, associated to possible product inhibition issues, large raw material variability, feed detoxification (when necessary), instability of the target compound (or fractions) and its presence in a complex mixture [23, 30].

It is well known that the separation steps, especially extraction, correspond up to 40–80% of the total costs of most common chemical processes currently used. From the point of view of a holistic biorefinery, separation has attracted more and more attention [31]. For instance, for natural products, solvent-based extraction is one of the best options nowadays considering the nature of many bio-based chem-icals and matrices, and also the fact that other separation methods, such as those based on chromatography or membranes, do not have the same advantages taking into account commercial scales [32].

It is expected that high value-added components from biomass waste such as essential oils, polyphenols, and other food or medicinal-related products are extracted first, followed by polysaccharides, lignocelluloses or waxes via advanced separation and depolymerization processes. Among them, green solvents in general,

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supercritical CO2, subcritical water, microwave (MW)-assisted acidolysis and gas-expanded liquids have been mentioned [33]. Green solvents offer important separa-tion advantages, including near-supercritical or supercritical fluids, which have out-standing mass transport properties, polarity, and easiness of solvent removal after extracting the compound of interest [34]. Another interesting solvent is water, but the range of compounds that are soluble in this medium is quite limited. Never-theless, the use of subcritical water has been demonstrated to be advantageous for organic modification to depolymerize, hydrolyze, gasify, and carbonize biomass to produce bioactive compounds, sugars, biogas, and other valuable solids [16, 35].

Integrating two or more green techniques combining different strategies has played an important role in overcoming the main drawbacks of a single technique towards sustainable separation. For instance, for high-pressure solvent extraction in which the extractants do not reach supercritical conditions, the temperature, time, and solvent consumed can be dramatically reduced associating ultrasound-assisted treatment [28, 36]. In fact, more attention has been paid to green extraction, puri-fication, or modification of natural products derived from agro-industrial waste nowadays, opening up new opportunities for sustainable approaches designed for bioeconomy and circular economy models. The aim of this paper is to present an overview of the design and application of green and sustainable separation of natu-ral products for vanguard zero-waste biorefineries. The main analytical techniques and procedures described over the last 10 years will be described in detail, showing the potentialities, challenges, and perspectives in this topical and emergent scenario.

3 High Value‑Added Approaches for Green and Sustainable Separation of Natural Products from Waste: What can be Observed from the Literature?

More recently, trends in green and sustainable extraction, fractionation and purifi-cation techniques have largely focused on minimizing the use of solvents, energy and materials that are intrinsically benign to human health and the environment [37]. In order to analyze the status quo and perspectives related to natural product separation from waste, a systematic literature review was conducted using the ISIS Web of Knowledge platform (reviews and papers) from 2006 to 2017, combining the descriptors “natural product” and “green extraction/separation” (or “sustainable extraction/separation” or “eco-friendly extraction/separation”) and “waste” (or “resi-due”). Figure  4 shows the number of publications during this period. There were more than 160 research papers and reviews that, to the best of our knowledge, are reasonably representative to show the strongest tendencies in this field over the last decade. It can be clearly observed that there has been an increase in the number of manuscripts over the last 10 years, covering the principles, advances, and applica-tions of these green methods.

The obtained data reflect the growing interest and potential of green and sustain-able methods to separate natural products from waste. One tendency observed in particular was the innovative ways to remove (integrating extraction, purification and/or modification in the same integrated system) and use such compounds in more

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contemporary sectors, promoting human and environmental health instead of gen-eral and old-fashioned remediation [19, 38]. As a result, new applications for food, nutraceutical, and agricultural sectors have been further explored, based on their advantageous properties as natural colorants, flavors, aromas, antioxidants, antifun-gals, bioformulations (bio-pesticides) or simply their use as precursors to generate other compounds for similar uses. Some details related to patents, (non-) clinical trials, sustainable indicators, scaling-up, regulatory, agro-industrial variability and availability, traceability, seasonality, good laboratory and manufacturing practices, additional economical and marketing issues have also been discussed.

Table  1 presents the research papers and reviews published during this period, highlighting their main focus, the green or sustainable techniques/approaches adopted, raw materials (mostly agro-industrial waste) and target compounds stud-ied. The most common raw materials described as chemical feedstocks were waste derived from plants, for instance, food, mainly fruits (citrus, mango, papaya, grape, passiflora, banana, tomato, olive), grains (corn, soybean, sunflower, coffee) and other abundant materials (sugarcane bagasse, tea, wood bark, rice and wheat straw). Additional issues that affect the quality of the final products were also discussed, namely the procedure used for waste collection, selection, storage, drying, matrix characteristics (particle size, shape, specific surface area and porosity). The lat-ter aspects play an important role in extraction efficiency due to the mass and heat transfer processes. Understanding the nature of raw material is crucial to avoid nega-tive influences impacting the quality and yield during the removal of the target com-pounds, e.g., caused by co-extracted contaminants or due to the presence of some

Fig. 4 Number of publications per year focusing on green and sustainable separation (extraction, frac-tionation and purification) of natural products from waste (ISIS Web of Knowledge, January 2006 to December 2017)

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Tabl

e 1

Res

earc

h pa

pers

and

revi

ews f

ocus

ing

on g

reen

and

sust

aina

ble

sepa

ratio

n of

nat

ural

pro

duct

s fro

m a

gro-

indu

stria

l was

te p

ublis

hed

from

Janu

ary

2006

to D

ecem

-be

r 201

7 (I

SIS

Web

of K

now

ledg

e)

Year

Cro

pW

aste

stre

amTa

rget

com

poun

dsG

eogr

aphi

cal l

ocat

ion

Gre

en o

r sus

tain

able

sepa

ratio

n ap

proa

chRe

fere

nces

2017

Oliv

esO

live

kern

els

Phen

olic

com

poun

ds a

nd o

ilFr

ance

and

Spa

inA

queo

us li

quid

solid

ext

ract

ion

(LSE

), m

echa

nica

l exp

ress

ion

(ME)

, sup

ercr

itica

l CO

2 (SC

-CO

2) a

nd g

as-a

ssist

ed m

echa

ni-

cal e

xpre

ssio

n (G

AM

E)

Gas

-ass

isted

mec

hani

cal e

xpre

ssio

n (G

AM

E) fo

r the

sele

ctiv

e re

cove

ry

of li

poph

ilic

and

hydr

ophi

lic c

om-

poun

ds fr

om o

live

kern

el [1

45]

2017

Figs

Leav

esB

ioac

tive

com

poun

dsC

hina

Dee

p eu

tect

ic so

lven

t with

mic

ro-

wav

e an

d ul

traso

und

extra

ctio

nTi

me:

10 

min

(MW

) and

60 

min

(U

S)Te

mpe

ratu

re: 4

0–80

 °CPo

wer

: 250

 W (M

W) a

nd 7

00 W

(U

S)

Enha

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and

gre

en e

xtra

ctio

n po

ly-

phen

ols a

nd fu

rano

coum

arin

s fro

m

Fig

(Fic

us c

aric

a L.

) lea

ves u

sing

de

ep e

utec

tic so

lven

ts [1

36]

2017

Poly

gonu

m m

ulti-

floru

mH

erba

l raw

mat

eria

lsSt

ilben

e gl

ycos

ide

and

anth

raqu

inon

esC

hina

Ioni

c liq

uids

with

ultr

ason

ic

extra

ctor

Tim

e: 1

–120

 min

Pow

er: 4

0–12

0 W

Sequ

entia

l ext

ract

ion

and

sepa

ratio

n us

ing

ioni

c liq

uids

for s

tilbe

ne

glyc

osid

e an

d an

thra

quin

ones

in

Poly

gonu

m m

ultifl

orum

[131

]20

17Se

vera

l sou

rces

Not

defi

ned

Mos

tly b

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poun

dsSp

ain

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al o

verv

iew

abo

ut th

e gr

eenn

ess o

f wat

er a

s ext

ract

ion

solv

ent

Wat

er a

s gre

en e

xtra

ctio

n so

lven

t: Pr

inci

ples

and

reas

ons f

or it

s use

[1

46]

2017

Pom

elo

Flav

edo

Esse

ntia

l oil

Chi

naM

icro

wav

e irr

adia

tion

Pow

er: 2

40–7

00 W

Tim

e: 2

4 m

in

A p

roce

ss to

pre

serv

e va

luab

le

com

poun

ds a

nd a

cqui

re e

ssen

tial

oils

from

pom

elo

flave

do u

sing

a

mic

row

ave

irrad

iatio

n tre

atm

ent

[52]

2017

Sela

gine

lla d

oede

r-le

inii

Not

defi

ned

Bifl

avon

oids

Chi

naIo

nic

liqui

ds a

nd m

icro

wav

e-as

siste

d ex

tract

ion

Pow

er: 3

00–7

00 W

Tim

e: 3

0–50

 min

Tem

pera

ture

: 40–

60 °C

Opt

imiz

atio

n of

ioni

c liq

uid-

assi

sted

extra

ctio

n of

bifl

avon

oids

from

Se

lagi

nella

doe

derle

inii

and

eval

uatio

n of

its a

ntio

xida

nt a

nd

antit

umor

act

ivity

[132

]

Top Curr Chem (Z) (2018) 376:3

1 3

3 Page 10 of 54

Tabl

e 1

(con

tinue

d)

Year

Cro

pW

aste

stre

amTa

rget

com

poun

dsG

eogr

aphi

cal l

ocat

ion

Gre

en o

r sus

tain

able

sepa

ratio

n ap

proa

chRe

fere

nces

2017

Pogo

stem

on c

ablin

Leav

esEs

sent

ial o

ilsIn

done

sia

Mic

row

ave-

assi

sted

hydr

odist

illa-

tion

(MA

HD

) and

solv

ent-f

ree

mic

row

ave

extra

ctio

n (S

FME)

Pow

er: 6

00 W

(MA

HD

) and

26

4 W

(SFM

E)Ti

me:

66 

min

(MA

HD

) and

45 

min

(S

FME)

; sol

vent

: wat

er

Com

paris

on o

f con

vent

iona

l and

m

icro

wav

e-as

siste

d di

stilla

tion

of

esse

ntia

l oil

from

Pog

oste

mon

cab

-lin

leav

es: a

naly

sis a

nd m

odel

ing

of

heat

and

mas

s tra

nsfe

r [14

7]

2017

Jugl

ans r

egia

L.

Fres

h m

ale

flow

ers a

nd

unrip

e w

alnu

t see

dsPh

enol

ic c

onte

nt a

nd w

ater

-so

lubl

e po

lyph

enol

sIta

lyM

icro

wav

e-as

siste

d ex

tract

ion

Freq

uenc

y: 2

.45 

GH

zM

ax. p

ower

: 500

 WSo

lven

t: et

hano

l/wat

erTe

mpe

ratu

re: 6

0–10

0 °C

Tim

e: 6

–30 

min

Proc

ess i

nten

sific

atio

n by

ex

perim

enta

l des

ign

appl

icat

ion

to

mic

row

ave-

assi

sted

extra

ctio

n of

ph

enol

ic c

ompo

unds

from

Jug

lans

re

gia

L. [1

48]

2017

Wal

nuts

Wal

nut d

e-pe

llicl

eFl

avon

oids

Chi

naM

acro

poro

us re

sins

Pret

reat

ed w

ith 5

% H

Cl a

nd 5

%

NaO

H so

lutio

ns

Reco

very

of fl

avon

oids

from

wal

nuts

de

-pel

licle

was

tew

ater

with

m

acro

poro

us re

sins

and

eva

luat

ion

of a

ntio

xida

nt a

ctiv

ities

in v

itro

[149

]20

17G

inse

ngRo

ots

Bio

activ

e co

mpo

unds

Bra

zil

Sequ

entia

l ext

ract

ion

syste

m u

sing

et

hano

l fol

low

ed b

y w

ater

Tem

pera

ture

: 333

 KTi

me:

5–2

40 m

in

Tech

no-e

cono

mic

eva

luat

ion

of

obta

inin

g B

razi

lian

gins

eng

extra

cts i

n po

tent

ial p

rodu

ctio

n sc

enar

ios [

150]

2017

Food

ingr

edie

nts a

nd

natu

ral p

rodu

cts

Not

defi

ned

Nut

race

utic

s, co

smet

ic,

phar

mac

eutic

al, a

nd

bioe

nerg

y ap

plic

atio

ns

Fran

ceRe

view

curr

ent k

now

ledg

e on

ultr

asou

nd-

assi

sted

extra

ctio

n

Ultr

asou

nd-a

ssist

ed e

xtra

ctio

n of

fo

od a

nd n

atur

al p

rodu

cts.

Mec

ha-

nism

s, te

chni

ques

, com

bina

tions

, pr

otoc

ols a

nd a

pplic

atio

ns. A

re

view

[151

]

1 3

Top Curr Chem (Z) (2018) 376:3 Page 11 of 54 3

Tabl

e 1

(con

tinue

d)

Year

Cro

pW

aste

stre

amTa

rget

com

poun

dsG

eogr

aphi

cal l

ocat

ion

Gre

en o

r sus

tain

able

sepa

ratio

n ap

proa

chRe

fere

nces

2017

Coff

eeC

offee

cha

ffA

ntio

xida

nts

Portu

gal

Solid

–liq

uid

extra

ctio

n an

d m

ulti-

freq

uenc

y m

ultim

ode

mod

ulat

ed

(MM

M)

Freq

uenc

y: 1

9.8 

kHz

Pow

er: 2

50 a

nd 5

00 W

Tim

e: 6

0–60

0 s

Mul

ti-fr

eque

ncy

mul

timod

e m

odu-

late

d te

chno

logy

as a

cle

an, f

ast,

and

sust

aina

ble

proc

ess t

o re

cove

r an

tioxi

dant

s fro

m a

coff

ee b

y-pr

oduc

t [15

2]

2017

App

les

Wild

app

le fr

uit d

ust

Bio

activ

e co

mpo

unds

, pol

y-ph

enol

ic a

ntio

xida

nts

Serb

iaM

icro

wav

e-as

siste

d ex

tract

ion

Tim

e: 1

5–35

 min

Etha

nol c

onc.

: 40–

80%

Irra

diat

ion

pow

er: 4

00–8

00 W

Mic

row

ave-

assi

sted

extra

ctio

n of

w

ild a

pple

frui

t dus

t pro

duct

ion

of

poly

phen

ol-r

ich

extra

cts f

rom

filte

r te

a fa

ctor

y by

-pro

duct

s [15

3]20

17W

ood

Woo

d bi

omas

sLi

gnin

olig

omer

sC

hina

Mic

row

ave-

assi

sted

treat

men

t with

de

ep e

utec

tic so

lven

tSo

lven

t: ch

olin

e ch

lorid

e an

d ox

alic

aci

d de

hydr

ate

Tem

pera

ture

: 80 

°CPo

wer

: 800

 WTi

me:

3 m

in

Effici

ent c

leav

age

of li

gnin

-car

bo-

hydr

ate

com

plex

es a

nd u

ltraf

ast

extra

ctio

n of

lign

in o

ligom

ers f

rom

w

ood

biom

ass b

y m

icro

wav

e-as

siste

d tre

atm

ent w

ith d

eep

eute

ctic

solv

ent [

137]

2017

Woo

dO

ak w

ood

from

coo

per-

age

by-p

rodu

cts

Fura

nic

com

poun

ds, c

is- a

nd

trans

- B-m

ethy

l-y-o

cta-

lact

ones

, ter

pene

s and

no

risop

reno

ids,

benz

enic

co

mpo

unds

Spai

nPr

essu

rized

liqu

id e

xtra

ctio

nSo

lven

t: w

ater

, eth

anol

/wat

er

(80:

20) a

nd e

thyl

lact

ate

Tem

pera

ture

: 60–

120 

°CPr

essu

re: 1

0.34

 MPa

Flus

h vo

lum

e: 6

0%Pu

rgin

g tim

e: 8

0 s

Extra

ctio

n of

nat

ural

flav

orin

gs w

ith

antio

xida

nt c

apac

ity fr

om c

oope

r-ag

e by

-pro

duct

s by

gree

n ex

tract

ion

proc

edur

e w

ith su

bcrit

ical

flui

ds

[154

]

2017

P. a

rmen

iaca

, P. p

er-

sica

, P. d

omes

tica,

Tr

iticu

m a

esat

ivum

Frui

t and

veg

etab

les

seed

s and

pee

lsPh

enol

ic c

ompo

unds

Paki

stan

Ultr

ason

ic w

ater

bat

hSo

lven

t: 65

% (v

/v) e

than

ol (m

etha

-no

l and

ace

tone

)Ex

tract

ion

time:

30 

min

Tem

pera

ture

: 50 

°C

Extra

ctio

n an

d qu

antifi

catio

n of

ph

enol

ic c

ompo

unds

from

Pru

nus

arm

enia

ca se

ed a

nd th

eir r

ole

in

biot

rans

form

atio

n of

xen

obio

tic

com

poun

ds [7

1]

Top Curr Chem (Z) (2018) 376:3

1 3

3 Page 12 of 54

Tabl

e 1

(con

tinue

d)

Year

Cro

pW

aste

stre

amTa

rget

com

poun

dsG

eogr

aphi

cal l

ocat

ion

Gre

en o

r sus

tain

able

sepa

ratio

n ap

proa

chRe

fere

nces

2017

Lign

ocel

lulo

se

mat

eria

lsLi

gnoc

ellu

losi

c bi

omas

s su

ch a

s cro

ps o

r fo

restr

y re

sidu

es

Hig

h va

lue-

adde

d bi

o-ba

sed

prod

ucts

(e.g

., bi

oeth

anol

, bi

ogas

, ace

tic a

cid,

ace

tic

acid

, or a

ctiv

ated

car

bon)

Mex

ico

and

Paki

stan

Revi

ewFo

cus o

n tra

nsfo

rmat

ion

base

d on

sy

ngas

pla

tform

(the

rmoc

hem

i-ca

l pla

tform

) and

suga

r pla

tform

(b

ioch

emic

al p

latfo

rm)

Lign

ocel

lulo

se: a

sust

aina

ble

mat

eria

l to

pro

duce

val

ue-a

dded

pro

duct

s w

ith z

ero-

was

te a

ppro

ach

[155

]

2017

Oliv

esO

live

by-p

rodu

ct (p

até)

Fatty

aci

ds a

nd p

heno

lic

com

poun

dsSp

ain

and

Italy

Soxh

let e

xtra

ctio

n (p

erco

latio

n w

ith p

etro

leum

eth

er, u

nder

re

flux)

Mac

ro a

nd m

icro

func

tiona

l co

mpo

nent

s of a

spre

adab

le o

live

by-p

rodu

ct (p

ate)

gen

erat

ed b

y ne

w c

once

pt o

f tw

o-ph

ase

deca

nter

[1

56]

2017

Tucu

mã

palm

frui

tTu

cum

ã’s e

ndoc

arp

Cel

lulo

seB

razi

l and

USA

Alk

alin

e ex

tract

ion

(135

 °C,

auto

clav

e, 2

 bar

, 2 m

in, 2

0% o

f aq

ueou

s NaO

H, 1

:30

straw

to

liquo

r (g/

ml),

30 

min

)

New

app

roac

h fo

r ext

ract

ion

of c

el-

lulo

se fr

om tu

cum

a’s e

ndoc

arp

and

its st

ruct

ural

cha

ract

eriz

atio

n [1

15]

2017

Gra

pes

Seed

sRe

sver

atro

lC

hina

Subc

ritic

al w

ater

ext

ract

ion

Pres

sure

: 0.5

–1.5

 MPa

Tim

e: 2

0–30

 min

Tem

pera

ture

: 130

–170

 °C

Opt

imiz

atio

n of

subc

ritic

al w

ater

ex

tract

ion

of re

sver

atro

l fro

m g

rape

se

eds b

y re

spon

se su

rface

met

hod-

olog

y [1

00]

2017

Man

go, r

ambu

tan,

sa

ntol

Peel

sA

ntio

xida

nt a

ctiv

ityTh

aila

ndSo

lid–l

iqui

d ex

tract

ion

Etha

nol (

95%

)St

udy

effec

t of n

atur

al e

xtra

cts o

n th

e an

tioxi

dant

act

ivity

in p

ork

balls

[157

]20

17To

mat

oes

Peric

arps

with

out s

eeds

Nut

rient

-ric

h an

tioxi

dant

in

gred

ient

sPo

rtuga

l, Sp

ain,

Ir

elan

dM

icro

wav

e ex

tract

ion

(600

 rpm

, 20

0 W

)Ti

me:

0–2

0 m

inTe

mpe

ratu

re: 6

0–18

0 °C

Etha

nol c

onc.

: 0–1

00%

Solid

/liqu

id ra

tio: 5

–45 

g/l

Valo

rizat

ion

of to

mat

o w

aste

s for

de

velo

pmen

t of n

utrie

nt-r

ich

antio

xida

nt in

gred

ient

s: a

sust

ain-

able

app

roac

h to

war

ds th

e ne

eds o

f to

day’

s soc

iety

[158

]

1 3

Top Curr Chem (Z) (2018) 376:3 Page 13 of 54 3

Tabl

e 1

(con

tinue

d)

Year

Cro

pW

aste

stre

amTa

rget

com

poun

dsG

eogr

aphi

cal l

ocat

ion

Gre

en o

r sus

tain

able

sepa

ratio

n ap

proa

chRe

fere

nces

2017

Citr

us la

tifol

ia,

Rubu

s sp.

, O

riga

num

vul

gare

an

d H

eter

othe

ca

inul

oide

s

Peel

and

bro

ken

dow

n ve

geta

ble

mat

eria

lFa

tty a

cids

and

ant

ioxi

dant

s co

mpo

unds

Mex

ico,

Bel

gium

SC-C

O2

Extra

ctio

n tim

e: 1

 hFl

ow: 2

5 g/

min

Pres

sure

: 10–

40 M

PaTe

mpe

ratu

re: 3

5–60

 °CC

o-so

l.: 0

–8 g

/min

Perc

ent fl

ow: 0

–32%

Ther

mod

ynam

ics a

nd st

atist

ical

co

rrel

atio

n be

twee

n su

perc

ritic

al

CO2 fl

uid

extra

ctio

n an

d bi

oact

ivity

pr

ofile

of l

ocal

ly av

aila

ble

Mex

ican

pl

ant e

xtra

cts [

159]

2017

Pom

egra

nate

sPe

els

Car

oten

oids

Gre

ece

Ultr

asou

nd-a

ssist

ed e

xtra

ctio

n (1

39 W

, 20 

kHz)

; sol

vent

s:

vege

tabl

e oi

lsEx

tract

ion

time:

10–

60 m

inTe

mpe

ratu

re: 2

0–60

 °C

Gre

en u

ltras

ound

-ass

isted

ext

ract

ion

of c

arot

enoi

ds fr

om p

omeg

rana

te

was

tes u

sing

veg

etab

le o

ils [7

2]

2017

Pom

egra

nate

sB

oth

edib

le a

nd n

on-

edib

le p

arts

Poly

phen

ols

Gre

ece

Sem

i-aut

omat

ic e

xtra

ctor

Solv

ents

: H2O

, β-C

D, H

P-β-

CD

Extra

ctio

n tim

e: 3

63 m

inTe

mpe

ratu

re: 2

5 °C

Gre

en e

xtra

ctio

n of

pol

yphe

nols

from

w

hole

pom

egra

nate

frui

t usi

ng

cycl

odex

trins

[121

]

2016

Qui

nce

Leav

esN

atur

al d

yes a

nd b

ioac

tive

com

poun

dsRo

man

iaA

queo

us e

xtra

ctio

nEx

tract

ion

time:

60–

240 

min

Tem

pera

ture

: 4–1

00 °C

Dye

ing

and

antib

acte

rial p

rope

rties

of

aqu

eous

ext

ract

s fro

m q

uinc

e (C

ydon

ia o

blon

ga) l

eave

s [16

0]20

16C

orn

Stee

p liq

uor

Vani

llic

acid

, p-c

oum

aric

ac

id, f

erul

ic a

cid,

sina

pic

acid

and

que

rcet

in

Spai

n, P

ortu

gal,

and

Italy

Liqu

id–l

iqui

d ex

tract

ion

Solv

ents

: chl

orof

orm

(56 

°C,

60 m

in)

Ethy

l ace

tate

(25 

°C, 4

5 m

in)

A m

ultif

unct

iona

l ext

ract

from

co

rn st

eep

liquo

r: an

tioxi

dant

and

su

rfact

ant a

ctiv

ities

[161

]

2016

Palm

Oil

palm

em

pty

frui

t bu

nche

sC

ellu

lose

with

pol

ypro

-py

lene

as b

ioco

mpo

site

m

ater

ial

Mal

aysi

a, P

akist

anU

ltras

onic

trea

tmen

t (40

 kH

z)so

lven

t: hy

drog

en p

erox

ide

Extra

ctio

n tim

e: 1

–3 h

Room

tem

pera

ture

Aut

ocla

ve a

nd u

ltra-

soni

catio

n tre

atm

ents

of o

il pa

lm e

mpt

y fr

uit b

unch

fibe

rs fo

r cel

lulo

se

extra

ctio

n an

d its

pol

ypro

pyle

ne

com

posi

te p

rope

rties

[73]

2016

Tom

atoe

sSe

eds a

nd p

eels

Car

oten

oids

/pro

tein

sTu

nisi

a an

d G

erm

any

Supe

rcrit

ical

CO

2 ext

ract

ion

80 °C

, 400

 bar

, 4 g

CO

2/min

for 2

 hB

iore

finer

y ca

scad

e pr

oces

sing

for

crea

ting

adde

d va

lue

on to

mat

o in

dustr

ial b

y-pr

oduc

ts fr

om T

unis

ia

[82]

Top Curr Chem (Z) (2018) 376:3

1 3

3 Page 14 of 54

Tabl

e 1

(con

tinue

d)

Year

Cro

pW

aste

stre

amTa

rget

com

poun

dsG

eogr

aphi

cal l

ocat

ion

Gre

en o

r sus

tain

able

sepa

ratio

n ap

proa

chRe

fere

nces

2016

Bla

ck te

aB

lack

tea

proc

essi

ng

was

teA

ntio

xida

nt a

nd a

ntim

icro

-bi

al p

heno

lic c

ompo

unds

Turk

ey a

nd U

SASo

lven

t ext

ract

ion

Solv

ents

: H2O

, eth

anol

Extra

ctio

n tim

e: 2

 hTe

mpe

ratu

re: 7

0 °C

Bla

ck te

a pr

oces

sing

was

te a

s a

sour

ce o

f ant

ioxi

dant

and

ant

imi-

crob

ial p

heno

lic c

ompo

unds

[46]

2016

Rap

esee

dR

apes

eed

oil c

akes

Prot

ein-

and

lign

in-r

ich

frac

tions

Fran

ceU

ltrafi

ne m

iffing

and

ele

ctro

stat

ic

sepa

ratio

nSo

lven

ts: N

aOH

, die

thyl

ethe

r, he

xane

Extra

ctio

n tim

e: 5

 hTe

mpe

ratu

re: 6

0 °C

Che

mic

al- a

nd so

lven

t-fre

e m

echa

no-

phys

ical

frac

tiona

tion

of b

iom

ass

indu

ced

by tr

ibo-

elec

trost

atic

ch

argi

ng: s

epar

atio

n of

pro

tein

s an

d lig

nin

[139

]

2016

Sunfl

ower

Seed

sSu

nflow

er p

rote

in-b

ased

in

gred

ient

sU

SARe

view

Gre

en p

igm

enta

tion

asso

ciat

ed

with

the

inte

ract

ion

of su

nflow

er

prot

ein

and

oxid

ized

chl

orog

enic

ac

id (C

GA

) by

outli

ning

the

sunfl

ower

oil

and

prot

ein

mea

l m

arke

t, C

GA

reac

tions

con

tribu

t-in

g to

gre

enin

g, m

etho

ds fo

r C

GA

ext

ract

ion,

and

the

effec

t of

proc

essi

ng o

n su

nflow

er p

rote

in

qual

ity a

nd th

e gr

eeni

ng re

actio

n

Chl

orog

enic

aci

d ox

idat

ion

and

its

reac

tion

with

sunfl

ower

pro

tein

s to

form

 gre

en-c

olor

ed c

ompl

exes

[1

62]

2016

Pass

ion

frui

tPe

els

Pect

inM

alay

sia

Aci

dic

and

enzy

mat

ic e

xtra

ctio

nC

itric

solu

tion,

cel

lucl

ast

Extra

ctio

n tim

e: 3

0–12

0 m

inTe

mpe

ratu

re: 3

5–85

 °C

Com

paris

on o

f aci

dic

and

enzy

mat

ic

pect

in e

xtra

ctio

n fro

m p

assi

on fr

uit

peel

s and

its g

el p

rope

rties

[107

]

2016

Red

grap

ePo

mac

ePo

lyph

enol

s and

ant

hocy

a-ni

n pi

gmen

tsG

reec

eU

ltras

ound

-ass

isted

ext

ract

ion

(140

 W, 3

7 kH

z)So

lven

t: aq

ueou

s gly

cero

lEx

tract

ion

time:

60 

min

Tem

pera

ture

: 45 

°C

Dev

elop

men

t of a

gre

en p

roce

ss fo

r th

e pr

epar

atio

n of

ant

ioxi

dant

and

pi

gmen

t-enr

iche

d ex

tract

s fro

m

win

ery

solid

was

tes u

sing

resp

onse

su

rface

met

hodo

logy

and

kin

etic

s [7

4]

1 3

Top Curr Chem (Z) (2018) 376:3 Page 15 of 54 3

Tabl

e 1

(con

tinue

d)

Year

Cro

pW

aste

stre

amTa

rget

com

poun

dsG

eogr

aphi

cal l

ocat

ion

Gre

en o

r sus

tain

able

sepa

ratio

n ap

proa

chRe

fere

nces

2016

Ora

nge

and

lem

onFr

esh

and

was

te p

eel

Pect

in a

nd d

-lim

onen

ePo

rtuga

l and

Ital

yM

icro

wav

eSo

lven

t: w

ater

Extra

ctio

n tim

e: 1

 hTe

mpe

ratu

re: 8

0 °C

Eco-

frie

ndly

ext

ract

ion

of p

ectin

an

d es

sent

ial o

ils fr

om o

rang

e an

d le

mon

pee

ls [5

3]

2016

Coff

eeSp

ent c

offee

gro

unds

Oil

Chi

naU

ltras

onic

atio

n ex

tract

ion

Solv

ent:

hexa

neEx

tract

ion

time:

15–

75 m

in

Effec

t of o

il ex

tract

ion

on p

rope

rties

of

spen

t coff

ee g

roun

ds-p

lasti

c co

mpo

site

s [98

]20

16To

mat

oW

aste

of t

omat

o pa

ste

plan

tsLy

cope

neIr

an a

nd C

anad

aM

icro

emul

sion

tech

niqu

e (M

ET)

Solv

ents

: wat

er, s

apon

in: g

lyce

rol,

surfa

ctan

t: ly

cope

neEx

tract

ion

time:

30 

min

Tem

pera

ture

: 25 

°C

Enha

nced

lyco

pene

ext

ract

ion

from

to

mat

o in

dustr

ial w

aste

usi

ng

mic

roem

ulsi

on te

chni

que:

opt

imi-

zatio

n of

enz

ymat

ic a

nd u

ltras

ound

pr

e-tre

atm

ents

[163

]20

16Re

d ca

psic

um (C

ap-

sicu

m a

nnuu

m)

Proc

essi

ng re

sidu

eC

arot

enoi

dsIn

dia

Enzy

mat

ic li

quef

actio

nPe

ctin

ase,

vis

cozy

me

L, c

ellu

lose

ex

tract

ion

Tim

e: 1

 hTe

mpe

ratu

re: 6

0 °C

Enzy

me-

assi

sted

extra

ctio

n of

ca

rote

noid

-ric

h ex

tract

from

red

caps

icum

(Cap

sicu

m a

nnuu

m)

[108

]

2016

Ric

eH

usk

Cel

lulo

seIn

dia

Eco-

frie

ndly

met

hod

mon

tmor

illon

ite, L

iOH

, H2O

2Ex

tract

ion

time:

6 h

Tem

pera

ture

: 80 

°C

Extra

ctio

n of

cel

lulo

se fr

om a

gric

ul-

tura

l was

te u

sing

mon

tmor

illon

ite

K-1

0/Li

OH

and

its c

onve

rsio

n to

re

new

able

ene

rgy:

bio

fuel

by

usin

g M

yrot

heci

um g

ram

ineu

m [1

22]

2016

Tea

(yar

row

and

rose

hi

p)B

y-pr

oduc

ts fr

om fi

lter-

tea

fact

ory

Chl

orop

hylls

and

car

ot-

enoi

dsSe

rbia

Supe

rcrit

ical

flui

d ex

tract

ion

Extra

ctio

n tim

e: 5

 hTe

mpe

ratu

re: 4

0 an

d 60

 °CPr

essu

re: 1

00–3

00 b

arCO

2 flow

rate

: 0.1

94 h

k/h

Extra

ctio

n of

min

or c

ompo

unds

(c

hlor

ophy

lls a

nd c

arot

enoi

ds)

from

yar

row

-rose

hip

mix

ture

s by

tradi

tiona

l ver

sus g

reen

tech

niqu

e [8

3]

Top Curr Chem (Z) (2018) 376:3

1 3

3 Page 16 of 54

Tabl

e 1

(con

tinue

d)

Year

Cro

pW

aste

stre

amTa

rget

com

poun

dsG

eogr

aphi

cal l

ocat

ion

Gre

en o

r sus

tain

able

sepa

ratio

n ap

proa

chRe

fere

nces

2016

Cor

n, su

garc

ane,

so

rghu

m, p

earl

mill

et, g

reen

gra

m,

grou

ndnu

t ses

ame

Bag

asse

, sto

ver,

stal

k an

d sh

ell

Para

-cou

mar

ic a

cid

(pCA

)In

dia

and

USA

Alk

alin

e hy

drol

ysis

pH 3

, alk

ali c

onc.

: 0.5

–4 M

Hyd

roly

sis d

urat

ion:

4–2

4 h

Suga

ring-

out f

or se

para

tion

of p

CA

from

hyd

roly

sate

Extra

ctio

n of

p-c

oum

aric

aci

d fro

m

agric

ultu

ral r

esid

ues a

nd se

para

tion

usin

g ‘s

ugar

ing

out’

[116

]

2016

Win

ery

Gra

pe w

aste

s and

by-

prod

ucts

Ant

ioxi

dant

com

poun

ds a

nd

poly

phen

ols

Den

mar

k, C

hina

, Fr

ance

and

Bra

zil

Revi

ewC

onve

ntio

nal (

solid

liqu

id e

xtra

c-tio

n, h

eatin

g, g

rindi

ng, e

tc.)

and

non-

conv

entio

nal (

puls

ed e

lect

ric

field

s, hi

gh v

olta

ge e

lect

rical

dis

-ch

arge

s, pu

lsed

ohm

ic h

eatin

g,

ultra

soun

ds, m

icro

wav

e-as

siste

d ex

tract

ions

, sub

- and

supe

rcrit

i-ca

l flui

d ex

tract

ions

, as w

ell a

s pr

essu

rized

liqu

id e

xtra

ctio

n)

met

hods

Gre

en a

ltern

ativ

e m

etho

ds fo

r the

ex

tract

ion

of a

ntio

xida

nt b

ioac

tive

com

poun

ds fr

om w

iner

y w

aste

s an

d by

-pro

duct

s: a

revi

ew [1

64]

2016

1st t

o 3r

d ge

nera

tion

biod

iese

l fee

d-sto

cks

Mos

tly m

icro

alga

eB

iodi

esel

Mal

aysi

a an

d Ja

pan

Revi

ewIn

tegr

atio

n of

enz

ymat

ic re

acto

rs

with

supe

rcrit

ical

flui

d te

chno

l-og

y

Gre

en b

iodi

esel

pro

duct

ion:

a re

view

on

feed

stock

, cat

alys

t, m

onol

ithic

re

acto

r, an

d su

perc

ritic

al fl

uid

tech

nolo

gy [8

4]20

16Ja

troph

a cu

rcas

, oil

palm

Seed

s, em

pty

frui

t bu

nch

Bio

-oil

Mal

aysi

aM

icro

wav

e ex

tract

ion

Solv

ent:

wat

erEx

tract

ion

time:

60–

140 

min

Pow

er: 2

00–7

00 W

Gre

en b

io-o

il ex

tract

ion

for o

il cr

ops

[54]

2016

Gre

en te

aG

reen

tea

resi

due

Prot

ein

The

Net

herla

nds

Alk

alin

e pr

otei

n ex

tract

ion

Solv

ent:

NaO

HEx

tract

ion

time:

2 h

Tem

pera

ture

: 95 

°C

Impr

ovin

g yi

eld

and

com

posi

tion

of

prot

ein

conc

entra

tes f

rom

gre

en

tea

resi

due

in a

n ag

ri-fo

od su

pply

ch

ain:

effe

ct o

f pre

-trea

tmen

t [11

7]

1 3

Top Curr Chem (Z) (2018) 376:3 Page 17 of 54 3

Tabl

e 1

(con

tinue

d)

Year

Cro

pW

aste

stre

amTa

rget

com

poun

dsG

eogr

aphi

cal l

ocat

ion

Gre

en o

r sus

tain

able

sepa

ratio

n ap

proa

chRe

fere

nces

2016

Euca

lypt

us w

ood

Euca

lypt

us c

hips

Hem

icel

lulo

ses

Uru

guay

Gre

en li

quor

ext

ract

ion

Solv

ents

: wat

er a

nd g

reen

liqu

or

(Na 2

CO3,

Na 2

S, a

nd N

aOH

)ex

tract

ion

time:

30–

150 

min

tem

pera

ture

: 100

–160

 °C

Inte

grat

ed fo

rest

bior

efine

ries:

gre

en

liquo

r ext

ract

ion

in e

ucal

yptu

s w

ood

prio

r to

kraf

t pul

ping

[123

]

2016

Wat

erm

elon

sJu

ice

Lyco

pene

Bra

zil

Mic

rofil

tratio

n, d

iafil

tratio

n,

reve

rse

osm

osis

α-A

l 2O3 m

embr

anes

T1-

70 (3

5 °C

)Po

lyam

ide

com

posi

te m

embr

anes

(3

5 °C

, 60 

bar)

Inte

grat

ed m

embr

ane

sepa

ratio

n pr

o-ce

sses

aim

ing

to c

once

ntra

te a

nd

purif

y ly

cope

ne fr

om w

ater

mel

on

juic

e [1

40]

2016

Larc

h w

ood

Sapw

ood,

hea

rtwoo

d,

bark

and

bra

nche

sPh

enol

ic c

ompo

unds

Slov

enia

Pres

suriz

ed h

ot w

ater

Extra

ctio

n tim

e: 3

0 m

inTe

mpe

ratu

re: 1

00 °C

Isol

atio

n of

phe

nolic

com

poun

ds

from

larc

h w

ood

was

te u

sing

pr

essu

rized

hot

wat

er: e

xtra

ctio

n,

anal

ysis

and

eco

nom

ic e

valu

atio

n [1

65]

2016

Tom

atoe

sPo

mac

eLy

cope

neIr

anM

icro

emul

sion

tech

niqu

eH

2O a

nd su

rfact

ants

Extra

ctio

n tim

e: 3

0 m

inTe

mpe

ratu

re: 3

5 °C

Mic

roem

ulsi

on-b

ased

lyco

pene

ex

tract

ion:

effe

ct o

f sur

fact

ants

, co

-sur

fact

ants

, and

pre

treat

men

ts

[166

]20

16M

elon

sR

ind

Car

bohy

drat

es, p

heno

lic

com

poun

ds, a

nd fa

tty

acid

s

Spai

nSo

lven

t ext

ract

ion

Solv

ent:

cycl

ohex

ane,

eth

anol

Extra

ctio

n tim

e: 2

 hM

icro

wav

e ra

diat

ion:

190

 °C,

20 m

in, 2

00 W

Mic

row

ave

heat

ing

for t

he c

atal

ytic

co

nver

sion

of m

elon

rind

was

te

into

bio

fuel

pre

curs

ors [

167]

2016

Tom

atoe

s,fu

ngus

Bla

kesl

ea

tris

pora

Proc

essi

ng w

aste

Lyco

pene

Gre

ece

Revi

ewEm

phas

is o

n fin

al p

rodu

ct sa

fety

an

d ec

ofrie

ndly

pro

cess

ing

(sol

vent

ext

ract

ion,

SFE

, MA

E,

high

-pre

ssur

e pr

oces

sing

, ultr

a-so

und,

ele

ctric

al m

etho

ds)

Nat

ural

orig

in ly

cope

ne a

nd it

s “g

reen

” do

wns

tream

pro

cess

ing

[168

]

Top Curr Chem (Z) (2018) 376:3

1 3

3 Page 18 of 54

Tabl

e 1

(con

tinue

d)

Year

Cro

pW

aste

stre

amTa

rget

com

poun

dsG

eogr

aphi

cal l

ocat

ion

Gre

en o

r sus

tain

able

sepa

ratio

n ap

proa

chRe

fere

nces

2016

Ora

nges

Peel

Pect

inIta

lyC

onve

ntio

nal h

ydro

disti

llatio

n,

MA

E, U

SSo

lven

ts: w

ater

Extra

ctio

n tim

e: 5

–155

 min

Tem

pera

ture

: 90–

333 

°C

Nov

el c

onfig

urat

ions

for a

citr

us

was

te b

ased

bio

refin

ery:

from

sol-

vent

less

to si

mul

tane

ous u

ltras

ound

an

d m

icro

wav

e-as

siste

d ex

tract

ion

[55]

2016

Lem

ons,

oliv

es,

onio

n, re

d gr

ape,

co

ffee,

and

whe

at

Peel

, lea

ves,

solid

w

aste

s, po

mac

e, sp

ent

filte

r and

bra

n

Poly

phen

olic

com

poun

dsG

reec

eU

ltras

ound

ext

ract

ion

(140

 W,

37 k

Hz)

eut

ectic

mix

ture

sEx

tract

ion

time:

90 

min

Tem

pera

ture

: 80 

°C

Nov

el g

lyce

rol-b

ased

nat

ural

eut

ectic

m

ixtu

res a

nd th

eir e

ffici

ency

in th

e ul

traso

und-

assi

sted

extra

ctio

n of

an

tioxi

dant

pol

yphe

nols

from

agr

i-fo

od w

aste

bio

mas

s [75

]20

16Po

tato

esPe

els

Poly

phen

olic

ant

ioxi

dant

sG

reec

eU

ltras

ound

ext

ract

ion

(140

 W,

37 k

Hz)

Solv

ents

: eth

anol

and

gly

cero

lEx

tract

ion

time:

90 

min

Extra

ctio

n te

mpe

ratu

re: 5

0–80

 °C

Opt

imiz

atio

n of

a g

reen

ultr

asou

nd-

assi

sted

extra

ctio

n pr

oces

s for

po

tato

pee

l (So

lanu

m tu

bero

sum

) po

lyph

enol

s usi

ng b

io-s

olve

nts a

nd

resp

onse

surfa

ce m

etho

dolo

gy [7

6]20

16G

rape

sSe

eds

Gra

pe se

ed o

ilC

roat

iaSu

perc

ritic

al C

O2

Extra

ctio

n tim

e: 9

0 m

inTe

mpe

ratu

re: 3

5–64

 °CPr

essu

re: 1

58–4

41 b

arCO

2 flow

rate

: 1.9

4 kg

/h

Opt

imiz

atio

n of

supe

rcrit

ical

CO

2 ex

tract

ion 

of g

rape

seed

oil

usin

g re

spon

se su

rface

met

hodo

logy

[85]

2016

Cro

cus s

ativ

usPe

tals

(und

erut

ilize

d bu

lk a

gro-

was

te)

Phen

olic

com

poun

dsIr

anSu

bcrit

ical

wat

er e

xtra

ctio

nEx

tract

ion

time:

20–

60 m

inTe

mpe

ratu

re: 1

20–1

60 °C

Opt

imiz

atio

n of

the

subc

ritic

al

wat

er e

xtra

ctio

n of

phe

nolic

an

tioxi

dant

s fro

m C

rocu

s sat

ivus

pe

tals

of s

affro

n in

dustr

y re

sidu

es:

Box

–Beh

nken

des

ign

and

prin

cipa

l co

mpo

nent

ana

lysi

s [10

1]20

16B

anan

asPe

els

Ant

ioxi

dant

sM

alay

sia

and

Turk

eySo

lven

t ext

ract

ion

Solv

ents

: ace

tone

, eth

anol

, hex

ane,

m

etha

nol,

H2O

Extra

ctio

n tim

e: 1

–5 h

Opt

imiz

atio

n of

ext

ract

ion

para

m-

eter

s on

the

antio

xida

nt p

rope

rties

of

ban

ana

was

te [4

7]

1 3

Top Curr Chem (Z) (2018) 376:3 Page 19 of 54 3

Tabl

e 1

(con

tinue

d)

Year

Cro

pW

aste

stre

amTa

rget

com

poun

dsG

eogr

aphi

cal l

ocat

ion

Gre

en o

r sus

tain

able

sepa

ratio

n ap

proa

chRe

fere

nces

2016

Pea

vine

Pea

vine

was

tePo

tent

ial p

latfo

rm m

olec

ules

(5

-hyd

roxy

furf

ural

; et

hano

ic a

cid)

; sug

ars

(levo

gluc

osen

one,

rham

-no

se, x

ylos

e, fr

ucto

se);

biop

olym

er w

ith p

ecti-

nace

ous a

nd st

arch

-like

ch

arac

teris

tics

Uni

ted

Kin

gdom

Pseu

do-s

ubcr

itica

l wat

er e

xtra

ctio

nTe

mpe

ratu

re: 1

25–1

75 °C

Pres

sure

: 20–

60 b

arFl

ow ra

te: 1

–5 m

l/min

Pote

ntia

l util

izat

ion

of u

navo

idab

le

food

supp

ly c

hain

was

tes-

valo

riza-

tion

of p

ea v

ine

was

tes [

6]

2016

Ker

atin

-con

tain

ing

prod

ucts

stor

ed

in la

rge

was

te

depo

sits

Proc

essi

ng w

aste

Ker

atin

Rom

ania

Revi

ewK

erat

ins s

olub

iliza

tion

(pro

tect

ed

and

unpr

otec

ted

met

hods

) fo

llow

ed b

y de

hydr

o-th

erm

al,

phys

ical

-type

bon

ding

or c

hem

i-ca

l tre

atm

ents

Prac

tical

way

s of e

xtra

ctin

g ke

ratin

fro

m k

erat

inou

s was

tes a

nd b

y-pr

oduc

ts: a

revi

ew [1

69]

2016

Taxu

s bac

cata

L.

Cas

e stu

dy b

ased

on

Euro

pean

yew

10-d

eace

tylb

acca

tin II

I (1

0-D

AB

)G

erm

any

Revi

ewTh

eore

tical

app

roac

h in

ther

mod

y-na

mic

s and

pro

cess

mod

ellin

g as

an

alte

rnat

ive

proc

ess d

esig

n

Proc

ess d

esig

n fo

r int

egra

tion

of

extra

ctio

n, p

urifi

catio

n an

d fo

r-m

ulat

ion

with

alte

rnat

ive

solv

ent

conc

epts

[170

]20

16O

lives

Oliv

e m

ill w

aste

wat

erB

ioph

enol

s (hy

drox

ytyr

osol

an

d ty

roso

l)Ita

lyLi

quid

–liq

uid

extra

ctio

nSo

lven

ts: n

-hex

ane,

EtO

Ac

Qui

ck a

sses

smen

t of t

he e

cono

mic

va

lue

of o

live

mill

was

te w

ater

[1

71]

2016

Oliv

esO

live

mill

was

te w

ater

Tyro

sol

Spai

n, U

nite

d K

ing-

dom

and

Spa

inH

ydro

phob

ic io

nic

liqui

dsSo

lven

ts: I

LsEx

tract

ion

time:

2 h

Tem

pera

ture

: 303

–323

 K

Reco

very

of t

yros

ol fr

om a

que-

ous s

tream

s usi

ng h

ydro

phob

ic

ioni

c liq

uids

: a fi

rst s

tep

tow

ards

de

velo

ping

sust

aina

ble

proc

esse

s fo

r oliv

e m

ill w

aste

wat

er (O

MW

) m

anag

emen

t [13

3]20

16C

upua

ssu

Seed

sC

upua

ssu

butte

r (ph

enol

ic

cont

ent/t

ocop

hero

ls/fa

tty

acid

s)

Bra

zil

Supe

rcrit

ical

CO

2 ext

ract

ion

Tem

pera

ture

: 50

and

70 °C

Pres

sure

s: 2

0–40

 MPa

Supe

rcrit

ical

CO

2 ext

ract

ion

of

cupu

assu

but

ter f

rom

def

atte

d se

ed re

sidu

e: e

xper

imen

tal d

ata,

m

athe

mat

ical

mod

elin

g an

d co

st of

m

anuf

actu

ring

[86]

Top Curr Chem (Z) (2018) 376:3

1 3

3 Page 20 of 54

Tabl

e 1

(con

tinue

d)

Year

Cro

pW

aste

stre

amTa

rget

com

poun

dsG

eogr

aphi

cal l

ocat

ion

Gre

en o

r sus

tain

able

sepa

ratio

n ap

proa

chRe

fere

nces

2016

Coff

eeSp

ent c

offee

gro

unds

Oil

frac

tion

Portu

gal,

Bra

zil,

Portu

gal

Supe

rcrit

ical

CO

2Ex

tract

ion

time:

1 h

Tem

pera

ture

: 55 

°CPr

essu

re: 2

50 b

arFl

ow ra

te: 1

5 kg

/h

The

gree

n ge

nera

tion

of su

nscr

eens

: us

ing

coffe

e in

dustr

ial s

ub-p

rod-

ucts

[87]

2016

Gin

ger

Not

defi

ned

Esse

ntia

l oil,

phe

nolic

s, fib

-er

s and

phe

nolic

aci

dsFr

ance

Mic

row

ave

hydr

odiff

usio

n an

d gr

avity

pro

cess

ing

(MH

G) a

nd

UA

ESo

lven

ts: w

ater

Extra

ctio

n tim

e: 8

3 an

d 90

 min

Tem

pera

ture

: up

to 1

00 a

nd 5

0 °C

Tow

ards

a “

dry”

bio

-refi

nery

with

out

solv

ents

or a

dded

wat

er u

sing

m

icro

wav

es a

nd u

ltras

ound

for t

otal

va

loriz

atio

n of

frui

t and

veg

etab

le

by-p

rodu

cts [

56]

2016

Pass

ion

frui

tPa

ssio

n fr

uit s

eeds

and

pa

ssio

n fr

uit s

eed

cake

(the

resi

due

from

th

e se

ed o

il pr

oduc

-tio

n by

col

d pr

essi

ng)

Oil

and

extra

ct w

ith

prom

isin

g an

tioxi

dant

and

an

timic

robi

al a

ctiv

ities

Bra

zil a

nd U

SASF

E, L

PE, M

AC

, UE

Solv

ents

: sCO

2, he

xane

, eth

yl

acet

ate,

eth

anol

, H2O

Extra

ctio

n tim

e: 4

5 m

in–7

 day

ste

mpe

ratu

re: r

oom

tem

p.−

 50 

°C

Valo

rizat

ion

of p

assi

on fr

uit (

Pas-

siflo

ra e

dulis

sp.)

by-p

rodu

cts:

su

stai

nabl

e re

cove

ry a

nd b

iolo

gica

l ac

tiviti

es [8

8]

2016

Woo

dB

roke

n pa

llets

, cra

tes,

and

was

te ti

mbe

r fro

m

build

ing

and

dem

oli-

tion

wor

ks

Rene

wab

le e

nerg

y so

urce

Rom

ania

Revi

ewO

verv

iew

of t

he te

chni

cal a

nd

econ

omic

opp

ortu

nity

of u

sing

w

ood

was

te a

s a re

new

able

en

ergy

sour

ce

Woo

d w

aste

as a

rene

wab

le so

urce

of

ener

gy [1

72]

2015

Plan

ts o

f spo

ntan

e-ou

s flor

a, c

ulti-

vate

d pl

ant,

and

was

tes r

esul

ted

in

agric

ultu

ral a

nd

food

indu

stry

Gen

eral

bio

-der

ived

m

ater

ials

Poly

phen

ols

Rom

ania

Revi

ewM

icro

wav

e-as

siste

d ex

tract

ion

(MA

E), s

uper

criti

cal fl

uid

extra

c-tio

n (S

FE),

and

ultra

soun

d-as

siste

d ex

tract

ion

(UA

E)

A c

ompa

rativ

e an

alys

is o

f the

‘gre

en’

tech

niqu

es a

pplie

d fo

r pol

yphe

nols

ex

tract

ion

from

bio

reso

urce

s [17

3]

1 3

Top Curr Chem (Z) (2018) 376:3 Page 21 of 54 3

Tabl

e 1

(con

tinue

d)

Year

Cro

pW

aste

stre

amTa

rget

com

poun

dsG

eogr

aphi

cal l

ocat

ion

Gre

en o

r sus

tain

able

sepa

ratio

n ap

proa

chRe

fere

nces

2015

Oni

onO

nion

solid

was

tes

Poly

phen

ol- a

nd p

igm

ent-

enric

hed

extra

cts w

ith

antio

xida

nt a

ctiv

ity

Gre

ece

Ultr

asou

nd e

xtra

ctio

n (1

40 W

, 37

 kH

z)Ex

tract

ion

time:

60 

min

Tem

pera

ture

: 45 

°C

A g

reen

ultr

asou

nd-a

ssist

ed e

xtra

c-tio

n pr

oces

s for

the

reco

very

of

ant

ioxi

dant

pol

yphe

nols

and

pi

gmen

ts fr

om o

nion

solid

was

tes

usin

g B

ox–B

ehnk

en e

xper

imen

tal

desi

gn a

nd k

inet

ics [

174]

2015

Six

type

s of p

lant

fib

ers (

bast,

leaf

, se

ed, s

traw

, gra

ss,

and

woo

d) a

nd

anim

al fi

bers

and

re

gene

rate

d ce

l-lu

lose

fibe

rs

Seed

(coi

r) a

nd a

nim

als

(chi

cken

feat

her)

as

they

are

seco

ndar

y or

mad

e fro

m w

aste

pr

oduc

ts

Fibe

rsSw

eden

Revi

ewD

ew, s

tand

, col

d an

d w

arm

wat

er,

steam

, enz

yme,

mec

hani

cal,

ultra

soun

d ch

emic

al a

nd S

ur-

fact

ant r

ettin

g

A re

view

of n

atur

al fi

bers

use

d in

bi

ocom

posi

tes:

pla

nt, a

nim

al a

nd

rege

nera

ted

cellu

lose

fibe

rs [1

75]

2015

Non

edi

ble

vege

ta-

bles

Seed

sB

iodi

esel

Egyp

tRe

view

A re

view

on

gree

n tre

nd fo

r oil

extra

ctio

n us

ing

subc

ritic

al w

ater

te

chno

logy

and

bio

dies

el p

rodu

c-tio

n [1

02]

2015

Nee

mN

eem

seed

cak

e (N

SC)

Nee

m P

rote

in (N

P)U

SAA

lkal

ine

extra

ctio

nSo

lven

ts: H

2O a

nd N

aOH

Extra

ctio

n tim

e: 6

0 m

inTe

mpe

ratu

re: 7

5 °C

Bio

-bas

ed p

olym

eric

resi

n fro

m a

gri-

cultu

ral w

aste

, nee

m (A

zadi

rach

ta

indi

ca) s

eed

cake

, for

gre

en

com

posi

tes [

118]

2015

Ora

nges

Peel

Esse

ntia

l oil,

pol

yphe

nols

an

d pe

ctin

Alg

eria

and

Fra

nce

MH

G, U

AE,

MA

ESo

lven

ts: “

in si

tu”

wat

erEx

tract

ion

time:

25

and

3 m

inTe

mpe

ratu

re: 5

9 °C

Bio

-refi

nery

of o

rang

e pe

els w

aste

: a

new

con

cept

bas

ed o

n in

tegr

ated

gr

een

and

solv

ent f

ree

extra

ctio

n pr

oces

ses u

sing

ultr

asou

nd a

nd

mic

row

ave

tech

niqu

es to

obt

ain

esse

ntia

l oil,

pol

yphe

nols

and

pe

ctin

[57]

Top Curr Chem (Z) (2018) 376:3

1 3

3 Page 22 of 54

Tabl

e 1

(con

tinue

d)

Year

Cro

pW

aste

stre

amTa

rget

com

poun

dsG

eogr

aphi

cal l

ocat

ion

Gre

en o

r sus

tain

able

sepa

ratio

n ap

proa

chRe

fere

nces

2015

Cor

n, su

garc

ane,

so

rghu

m, s

oybe

an,

rice,

bar

ley,

pot

ato,

ot

her l

igno

cel-

lulo

se, v

eget

able

oi

ls, o

ilsee

d

By-

prod

ucts

(bag

asse

, str

aw, c

obs,

stal

ks,

stove

r, gr

ass e

tc.)

Bio

fuel

, 1,3

-pro

pane

diol

, su

ccin

ic a

cid,

adh

esiv

es,

solv

ents

, sur

fact

ants

, eth

yl

lact

ate,

eru

cic

acid

, am

yl-

ose

ethe

rs, a

mon

g ot

hers

Den

mar

kRe

view

Focu

s on

inte

grat

ing

sust

aina

bilit

y as

sess

men

t pro

cedu

res a

nd to

ols

(LCA

and

eva

luat

ion

appr

oach

es)

Bio

refin

ing

in th

e pr

evai

ling

ener

gy

and

mat

eria

ls c

risis

: a re

view

of

sust

aina

ble

path

way

s for

bio

refin

-er

y va

lue

chai

ns a

nd su

stai

nabi

lity

asse

ssm

ent m

etho

dolo

gies

[144

]

2015

Agr

o-in

dustr

ial

prod

ucts

Agr

o-in

dustr

ial c

o-pr

oduc

tsPh

enol

ic c

ompo

unds

Bra

zil

Solid

-sta

te fe

rmen

tatio

n, e

ven

as fr

iend

ly e

nzym

e-as

siste

d ex

tract

ions

Bio

trans

form

atio

n an

d bi

ocon

vers

ion

of p

heno

lic c

ompo

unds

obt

ain-

men

t: an

ove

rvie

w [1

76]

2015

Cas

hew

-nut

Hus

kN

atur

al d

yes

Indi

aEn

zym

e-as

siste

d ex

tract

ion

cel-

lula

se a

nd p

ectin

ase

Solv

ent:

wat

erEx

tract

ion

time:

60–

180 

min

pH 9

.5

Cas

hew

-nut

hus

k na

tura

l dye

ext

rac-

tion

usin

g Ta

guch

i opt

imiz

atio

n:

gree

n ch

emist

ry a

ppro

ach

[109

]

2015

Bee

tSu

gar b

eet p

ulp

Mon

osac

char

ides

pre

sent

in

hydr

olyz

ed S

BP

pect

in:

l-rh

amno

se, l

-ara

bino

se,

d-g

alac

tose

and

d-g

alac

tu-

roni

c ac

id

Uni

ted

Kin

gdom

Cen

trifu

gal p

artit

ion

chro

mat

ogra

-ph

y as

cend

ing

mod

e, 1

000 

rpm

Mob

ile p

hase

flow

rate

: 8 m

l/min

Cen

trifu

gal p

artit

ion

chro

mat

ogra

phy

in a

bio

refin

ery

cont

ext:

sepa

ratio

n of

mon

osac

char

ides

from

hyd

ro-

lyze

d su

gar b

eet p

ulp

[141

]

2015

Man

goes

(Man

gife

ra

indi

ca L

.) an

d ry

e gr

ains

(Sec

ale

cere

als L

.)

Peel

s and

gra

ins

Alk

(en)

ylre

sorc

inol

s (A

Rs)

Ger

man

yU

ltras

ound

-ass

isted

ext

ract

ion

Solv

ent:

dich

loro

met

hane

Extra

ctio

n tim

e: 1

5 s c

oole

d in

ic

e ba

th

Dev

elop

men

t and

val

idat

ion

of a

n H

PLC

met

hod

for t

he d

eter

min

a-tio

n of

alk

(en)

ylre

sorc

inol

s usi

ng

rapi

d ul

traso

und-

assi

sted

extra

ctio

n of

man

go p

eels

and

rye

grai

ns [7

8]

1 3

Top Curr Chem (Z) (2018) 376:3 Page 23 of 54 3

Tabl

e 1

(con

tinue

d)

Year

Cro

pW

aste

stre

amTa

rget

com

poun

dsG

eogr

aphi

cal l

ocat

ion

Gre

en o

r sus

tain

able

sepa

ratio

n ap

proa

chRe

fere

nces

2015

Oliv

esW

aste

from

oliv

e oi

l pr

oduc

tion

Hig

h-ad

ded

valu

e co

m-

poun

ds (p

olyp

heno

ls,

fatty

aci

ds, c

olor

ing

pig-

men

ts (c

hlor

ophy

lls a

nd

caro

teno

ids)

, toc

ophe

rols

, ph

ytos

tero

ls, s

qual

ene,

vo

latil

e an

d ar

omat

ic c

om-

poun

ds)

Spai

n, F

ranc

e,

Mor

occo

and

Po

rtuga

l

Revi

ewC

onve

ntio

nal (

solv

ent,

heat

, gr

indi

ng) a

nd n

on-c

onve

ntio

nal

met

hodo

logi

es (u

ltras

ound

s, m

icro

wav

es, s

ub- a

nd su

perc

riti-

cal fl

uid

extra

ctio

ns, p

ress

uriz

ed

liqui

d ex

tract

ion,

pul

sed

elec

tric

field

s and

hig

h vo

ltage

ele

ctric

al

disc

harg

es)

Emer

ging

opp

ortu

nitie

s for

the

effec

tive

valo

rizat

ion

of w

aste

s an

d by

-pro

duct

s gen

erat

ed d

urin

g ol

ive

oil p

rodu

ctio

n pr

oces

s:

non-

conv

entio

nal m

etho

ds fo

r th

e re

cove

ry o

f hig

h-ad

ded

valu

e co

mpo

unds

[142

]

2015

Asp

arag

usD

ried

segm

ents

(res

i-du

es)

Ant

ioxi

dant

com

poun

dsC

hina

Solid

–liq

uid

extra

ctio

nSo

lven

ts: a

ceto

ne, m

etha

nol o

r et

hano

lEx

tract

ion

time:

2 h

Tem

pera

ture

: 70 

°C

Extra

ctio

n an

d an

alys

is o

f ant

ioxi

dant

co

mpo

unds

from

the

resi

dues

of

Aspa

ragu

s offi

cina

lis L

. [17

7]

2015

Gra

pes

Skin

Ant

hocy

anin

sK

orea

Dee

p eu

tect

ic so

lven

ts (D

ESs)

Extra

ctio

n tim

e: 4

5 m

in ro

om

tem

pera

ture

Hig

hly

effici

ent e

xtra

ctio

n of

an

thoc

yani

ns fr

om g

rape

skin

usi

ng

deep

eut

ectic

solv

ents

as g

reen

and

tu

nabl

e m

edia

[138

]20

15G

reen

tea

Gre

en te

a le

af re

sidu

eH

G p

ectin

, RG

II p

ectin

, or

gani

c ac

ids,

cellu

lose

an

d he

mi-c

ellu

lose

The

Net

herla

nds

Alk

alin

e ex

tract

ion

Solv

ents

: 0.1

 M N

aOH

Extra

ctio

n tim

e: 2

 h (p

rote

in),

5 m

in–2

4 h

(car

bohy

drat

es o

r lig

nin)

Tem

pera

ture

: 95 

°C

How

doe

s alk

ali a

id p

rote

in e

xtra

c-tio

n in

gre

en te

a le

af re

sidu

e: a

ba

sis f

or in

tegr

ated

bio

refin

ery

of

leav

es [1

19]

2015

Papa

ya (C

aric

a pa

paya

L.)

Proc

essi

ng w

aste

Lyco

pene

Chi

naU

ltras

ound

ext

ract

ion

(600

 W,

40 k

Hz)

Solv

ents

: eth

anol

/eth

yl a

ceta

teEx

tract

ion

time:

15–

40 m

inTe

mpe

ratu

re: 2

0–70

 °C

Opt

imiz

atio

n of

ultr

asou

nd-a

ssist

ed

extra

ctio

n of

lyco

pene

from

pap

aya

proc

essi

ng w

aste

by

resp

onse

su

rface

met

hodo

logy

[77]

Top Curr Chem (Z) (2018) 376:3

1 3

3 Page 24 of 54

Tabl

e 1

(con

tinue

d)

Year

Cro

pW

aste

stre

amTa

rget

com

poun

dsG

eogr

aphi

cal l

ocat

ion

Gre

en o

r sus

tain

able

sepa

ratio

n ap

proa

chRe

fere

nces

2015

Car

rots

, gre

en b

eans

, le

eks a

nd c

eler

iac

Vege

tabl

e w

aste

stre

ams

(rej

ecte

d ca

rrot

s, ca

r-ro

t ste

am p

eels

, gre

en

bean

s cut

ting

was

te,

leek

cut

ting

was

te a

nd

cele

riac

steam

pee

ls)

Pect

inB

elgi

umA

lcoh

ol in

solu

ble

resi

due

Solv

ents

: eth

anol

and

ace

tone

Pect

in c

hara

cter

izat

ion

in v

eget

able

w

aste

stre

ams:

a st

artin

g po

int

for w

aste

val

oriz

atio

n in

the

food

in

dustr

y [1

78]

2015

Ber

ries o

f A. m

el-

anoc

arpa

Bla

ck c

hoke

berr

y w

aste

sA

ntio

xida

nts

Fran

ceEx

tract

ion-

adso

rptio

n pr

oces

sEx

tract

ion

time:

2–8

 hTe

mpe

ratu

re: 2

2 °C

Pilo

t sca

le d

emon

strat

ion

of

inte

grat

ed e

xtra

ctio

n-ad

sorp

tion

eco-

proc

ess f

or se

lect

ive

reco

very

of

ant

ioxi

dant

s fro

m b

errie

s was

tes

[179

]20

15C

ashe

w n

uts (

CN

S)Sh

ells

Ana

card

ic a

cid

Tanz

ania

Revi

ewFo

cus o

n na

tura

l ana

card

ic a

cids

fro

m C

NS

and

othe

r pla

nts a

nd

thei

r sem

i-syn

thet

ic d

eriv

ativ

es

as p

ossi

ble

lead

com

poun

ds in

m

edic

ine

Pote

ntia

l bio

logi

cal a

pplic

atio

ns o

f bi

o-ba

sed

anac

ardi

c ac

ids a

nd th

eir

deriv

ativ

es [1

80]

2015

Soy,

suga

rcan

e, te

aSo

y sa

uce

resi

dues

, su

garc

ane

baga

sse

and

tea

dreg

s

Hem

icel

lulo

ses

Chi

naIo

nic

liqui

dSo

lven

ts: i

onic

liqu

ids

Extra

ctio

n tim

e: 1

–5 h

Tem

pera

ture

: 70–

100 

°C

Qua

ntita

tive

indu

stria

l ana

lysi

s of

ligno

cellu

losi

c co

mpo

sitio

n in

ty

pica

l agr

o-re

sidu

es a

nd e

xtra

ctio

n of

inne

r hem

icel

lulo

ses w

ith io

nic

liqui

d [1

34]

2015

Tom

atoe

sPr

oces

sing

tom

ato

Nut

ritio

nal b

ioac

tive

com

-po

unds

, lyc

open

eIta

lyB

ioco

mpa

tible

tech

nolo

gy e

xtra

c-tio

nRe

cove

ry o

f tom

ato

bioa

ctiv

e co

m-

poun

ds th

roug

h a

bioc

ompa

tible

an

d ec

o-su

stai

nabl

e ne

w te

chno

l-og

y fo

r the

pro

duct

ion

of e

nric

hed

“nut

race

utic

al to

mat

o pr

oduc

ts”

[181

]

1 3

Top Curr Chem (Z) (2018) 376:3 Page 25 of 54 3

Tabl

e 1

(con

tinue

d)

Year

Cro

pW

aste

stre

amTa

rget

com

poun

dsG

eogr

aphi

cal l

ocat

ion

Gre

en o

r sus

tain

able

sepa

ratio

n ap

proa

chRe

fere

nces

2015

Citr

us si

nens

is

(Ham

lin, V

alen

cia,

Pe

ra ri

u an

d Pe

ra

Nat

al)

Alb

edo

and

flave

doFl

avan

one

Bra

zil

Enzy

mat

ic p

roce

ss ta

nnas

e, p

ecti-

nase

and

cel

lula

seEx

tract

ion

time:

30 

hTe

mpe

ratu

re: 4

0 °C

pH 5

Sim

ulta

neou

s ext

ract

ion

and

biot

rans

form

atio

n pr

oces

s to

obta

in h

igh

bioa

ctiv

ity p

heno

lic

com

poun

ds fr

om B

razi

lian

citru

s re

sidu

es [1

10]

2015

Sunfl

ower

Seed

sO

il- (f

atty

aci

ds a

nd th

eir

antio

xida

nt c

apac

ities

) an

d w

ater

-sol

uble

pha

se

(pro

tein

s, ca

rboh

ydra

tes

and

phen

olic

s)

Slov

enia

Subc

ritic

al w

ater

ext

ract

ion

Extra

ctio

n tim

e: 5

–120

 min

Tem

pera

ture

: 60–

160 

°CPr

essu

re: 3

0 ba

r

Sim

ulta

neou

s ext

ract

ion

of o

il- a

nd

wat

er-s

olub

le p

hase

from

sunfl

ower

se

eds w

ith su

bcrit

ical

wat

er [1

03]

2015

Cer

eals

, roo

t cro

ps,

frui

ts, v

eget

able

s,oi

lsee

ds, m

eat,

dairy

pr

oduc

ts

Food

was

teN

utrit

iona

lly in

tere

sting

co

mpo

unds

, che

mic

als

and

biof

uels

Bra

zil

Revi

ewSu

b- a

nd su

perc

ritic

al te

chno

logi

esSu

b- a

nd su

perc

ritic

al fl

uid

tech

nol-

ogy

appl

ied

to fo

od w

aste

pro

cess

-in

g [8

9]

2015

Agr

icul

tura

l bio

mas

sB

y-pr

oduc

ts su

ch a

s du

rian

peel

, man

go

peel

, cor

n str

aw, r

ice

bran

, cor

n sh

ell a

nd

pota

to p

eel

Bio

-fue

l, w

ater

solu

ble

suga

rs a

nd p

heno

lic

com

poun

ds

Mal

aysi

a an

d N

iger

iaRe

view

Sub-

criti

cal w

ater

Sub-

criti

cal w

ater

as a

gre

en

solv

ent f

or p

rodu

ctio

n of

val

uabl

e m

ater

ials

from

agr

icul

tura

l was

te

biom

ass:

a re

view

of r

ecen

t wor

k [1

82]

2015

Suga

rcan

eSu

garc

ane

was

te (r

ind,

le

af a

nd b

agas

se)

Wax

/long

-cha

in a

ldeh

ydes

an

d n-

polic

osan

ols

(nut

race

utic

al c

ompo

unds

) tri

terp

enoi

ds

UK

and

Bra

zil

Supe

rcrit

ical

CO

2 (sc

CO2)

Extra

ctio

n tim

e: 4

 hTe

mpe

ratu

re: 5

0 °C

Pres

sure

: 350

 bar

Flow

rate

: 40 

g/m

in

Suga

rcan

e w

aste

as a

val

uabl

e so

urce

of

lipo

phili

c m

olec

ules

[183

]

2015

Man

goes

Peel

Pect

inG

erm

any

and

Saud

i A

rabi

aH

ot-a

cid

extra

ctio

nEx

tract

ion

time:

90 

min

pH 1

.5

The

arab

inog

alac

tan

of d

ried

man

go

exud

ate

and

its c

o-ex

tract

ion

dur-

ing

pect

in re

cove

ry fr

om m

ango

pe

el [1

84]

2015

Coff

eeSp

ent c

offee

gro

unds

Tann

in c

ompo

unds

Mal

aysi

aA

lkal

ine

extra

ctio

nSo

lven

t: N

aOH

Extra

ctio

n tim

e: 3

0–90

 min

Tem

pera

ture

: 60–

100 

°C

The

influ

ence

of e

xtra

ctio

n pa

ram

-et

ers o

n sp

ent c

offee

gro

unds

as a

re

new

able

tann

in re

sour

ce [1

85]

Top Curr Chem (Z) (2018) 376:3

1 3

3 Page 26 of 54

Tabl

e 1

(con

tinue

d)

Year

Cro

pW

aste

stre

amTa

rget

com

poun

dsG

eogr

aphi

cal l

ocat

ion

Gre

en o

r sus

tain

able

sepa

ratio

n ap

proa

chRe

fere

nces

2014

Euca

lypt

us g

lobu

lus

woo

dTr

imm

ings

of E

uca-

lypt

us g

lobu

lus w

ood

vene

ers

Phen

olic

com

poun

dsSp

ain

Aqu

eous

two-

phas

e ex

tract

ion

PEG

200

0 an

d am

mon

ium

sulp

hate

Extra

ctio

n tim

e: 3

0–39

0 m

inTe

mpe

ratu

re: 2

5–65

 °C

Aqu

eous

two-

phas

e sy

stem

s for

the

extra

ctio

n of

phe

nolic

com

poun

ds

from

euc

alyp

tus (

Euca

lypt

us g

lobu

-lu

s) w

ood

indu

stria

l was

tes [

124]

2014

Pom

egra

nate

sB

y-pr

oduc

ts a

fter

win

emak

ing

of p

ome-

gran

ate

(pol

y)ph

enol

ic c

ompo

unds

Spai

n, M

exic

o an

d Ita

lyEx

tract

ion

with

MeO

H 7

0% (v

/v)

and

soni

catio

nA

sses

smen

t of p

omeg

rana

te w

ine

lees

as a

val

uabl

e so

urce

for t

he

reco

very

of (

poly

)phe

nolic

com

-po

unds

[186

]20

14C

itrus

Peel

, pul

p an

d se

eds

Seve

ral v

alue

-add

ed p

rod-

ucts

, suc

h as

ess

entia

l oils

, pe

ctin

, enz

ymes

, sin

gle

cell

prot

ein,

nat

ural

ant

i-ox

idan

ts, e

than

ol, o

rgan

ic

acid

s, an

d pr

ebio

tics

Gre

ece

and

Swed

enRe

view

Bio

trans

form

atio

n of

citr

us b

y-pr

oduc

ts in

to v

alue

add

ed p

rodu

cts

[187

]

2014

Oliv

esO

live

solid

was

teN

atur

al d

yeTu

nisi

aA

queo

us e

xtra

ctio

n in

clo

sed

flask

sSo

lven

t: N

aOH

Extra

ctio

n tim

e: 1

5–12

0 m

inTe

mpe

ratu

re: 3

0–90

 °C

Dev

elop

men

t and

opt

imis

atio

n of

a

non-

conv

entio

nal e

xtra

ctio

n pr

oces

s of n

atur

al d

ye fr

om o

live

solid

was

te u

sing

resp

onse

surfa

ce

met

hodo

logy

(RSM

) [12

5]20

14C

offee

Was

te c

offee

gro

unds

Bio

dies

el p

rodu

ctio

nU

nite

d K

ingd

omSu

spen

ded

in fr

esh

hept

ane

room

te

mpe

ratu

reEff

ect o

f the

type

of b

ean,

pro

cess

-in

g, a

nd g

eogr

aphi

cal l

ocat

ion

on

the

biod

iese

l pro

duce

d fro

m w

aste

co

ffee

grou

nds [

188]

2014

Gra

pevi

ne a

nd

haze

lnut

Gra

pevi

ne w

aste

and

ha

zeln

ut sk

ins

Poly

phen

ols c

onte

ntIta

ly a

nd F

ranc

eU

AE

and

MA

ESo

lven

ts: e

than

ol, m

etha

nol,

ace-

tone

, but

anon

e, β

-cyc

lode

xtrin

Extra

ctio

n tim

e: 5

–40 

min

Tem

pera

ture

: 20–

60 °C

Effici

ent g

reen

ext

ract

ion

of

poly

phen

ols f

rom

pos

t-har

veste

d ag

ro-in

dustr

y ve

geta

l sou

rces

in

Pied

mon

t [58

]

2014

Bam

boo

Raw

bam

boo

culm

Lign

inM

alay

sia

Revi

ewC

hem

ical

and

stea

m e

xplo

sion

m

etho

ds

Extra

ctio

n an

d pr

epar

atio

n of

bam

-bo

o fib

re-r

einf

orce

d co

mpo

site

s [1

89]

1 3

Top Curr Chem (Z) (2018) 376:3 Page 27 of 54 3

Tabl

e 1

(con

tinue

d)

Year

Cro

pW

aste

stre

amTa

rget

com

poun

dsG

eogr

aphi

cal l

ocat

ion

Gre

en o

r sus

tain

able

sepa

ratio

n ap

proa

chRe

fere

nces

2014

Spru

ceSp

ruce

saw

dust

Car

boxy

lic a

cids

Finl

and

Alk

alin

e ex

tract

ion

Solv

ents

: Na 2

CO3 o

r Na 2

S.9H

2OEx

tract

ion

time:

30 

min

 + 3

0 m

in;

Tem

pera

ture

: 80 

°C u

p to

160

 °C

and

210 

°C

Prod

uctio

n of

car

boxy

lic a

cids

from

al

kalin

e pr

etre

atm

ent b

ypro

duct

of

softw

ood

[120

]

2014

Varie

ty o

f bio

mas

s so

urce

s (ra

pese

ed,

soyb

ean,

pal

m

oil a

nd n

oned

ible

fe

edsto

cks)

Pref

erab

ly 2

nd–4

th

gene

ratio

n fe

edsto

ck

(non

-edi

ble

mat

eria

ls

as b

agas

se, o

il w

aste

, m

icro

alga

e, c

yano

bac-

teria

and

mic

robe

s)

Bio

dies

elM

alay

sia

Revi

ewSu

perc

ritic

al fl

uid

proc

ess a

nd

cata

lytic

in si

tu o

r rea

ctiv

e ex

tract

ion

proc

ess

Inte

grat

ion

of re

activ

e ex

tract

ion

with

supe

rcrit

ical

flui

ds fo

r pro

cess

in

tens

ifica

tion

of b

iodi

esel

pro

duc-

tion:

pro

spec

ts a

nd re

cent

adv

ance

s [9

0]

2014

Che

rrie

sC

herr

y se

eds

Tota

l phe

nolic

con

tent

Bra

zil a

nd F

ranc

ePr

essu

rized

flui

d ex

tract

ion

(PFE

)So

lven

t: an

hydr

ous e

than

olEx

tract

ion

time:

2–1

0 m

inTe

mpe

ratu

re: 4

0–80

 °C

Isol

atio

n by

pre

ssur

ized

flui

d ex

tract

ion

(PFE

) and

iden

tifica

tion

usin

g C

PC a

nd H

PLC

/ESI

/MS

of

phen

olic

com

poun

ds fr

om B

razi

l-ia

n ch

erry

seed

s (Eu

geni

a un

iflor

a L.

) [19

0]20

14C

orn

Cor

n sto

ver

Lign

inU

SAPr

otic

ioni

c liq

uid

(PIL

)Ex

tract

ion

time:

24 

hTe

mpe

ratu

re: 9

0 °C

Lign

in e

xtra

ctio

n fro

m b

iom

ass w

ith

prot

ic io

nic

liqui

ds [1

35]

2014

Ora

nges

Peel

d-li

mon

ene

Uni

ted

Kin

gdom

Mic

row

ave-

assi

sted

extra

ctio

n20

0 W

, clo

sed

vess

elSo

lven

t: he

xane

Tem

pera

ture

: 70–

110 

°C

Mic

row

ave-

assi

sted

extra

ctio

n as

an

impo

rtant

tech

nolo

gy fo

r val

oris

ing

oran

ge w

aste

[59]

2014

Swee

t Lim

esPe

elA

ntio

xida

nt p

heno

lics

Paki

stan

Enzy

mat

ic tr

eatm

ent

Incu

batio

n tim

e: 3

0–12

0 m

inTe

mpe

ratu

re: 3

0–75

 °CpH

5 to

8

Opt

imiz

atio

n of

enz

yme-

assi

sted

reva

loriz

atio

n of

swee

t lim

e (C

itrus

lim

etta

Ris

so) p

eel i

nto

phen

olic

an

tioxi

dant

s [11

1]

Top Curr Chem (Z) (2018) 376:3

1 3

3 Page 28 of 54

Tabl

e 1

(con

tinue

d)

Year

Cro

pW

aste

stre

amTa

rget

com

poun

dsG

eogr

aphi

cal l

ocat

ion

Gre

en o

r sus

tain

able

sepa

ratio

n ap

proa

chRe

fere

nces

2014

Arti

chok

eA

rtich

oke

scra

psPh

enol

ic c

ompo

unds

Italy

Ultr

asou

nd-a

ssist

ed e

xtra

ctio

n (U

AE)

Tim

e: 6

0 m

inSo

lven

t: w

ater

Phen

ols a

nd a

ntio

xida

nt a

ctiv

ity

in v

itro

and

in v

ivo

of a

queo

us

extra

cts o

btai

ned

by u

ltras

ound

-as

siste

d ex

tract

ion

from

arti

chok

e by

-pro

duct

s [79

]20

14C

achr

ys p

unge

ns Ja

n (U

mbe

llife

rae)

Aer

ial p

arts

of C

achr

ys

pung

ens J

an (U

mbe

l-lif

erae

)

Bio

activ

e co

mpo

unds

Italy

Solv

ent e

xtra

ctio

nSo

lven

ts: m

etha

nol

Extra

ctio

n tim

e: 7

2 h

room

tem

-pe

ratu

re d

ark

cond

ition

s

Phyt

otox

ic a

ctiv

ity o

f Cac

hrys

pu

ngen

s Jan

, a M

edite

rran

ean

spec

ies:

sepa

ratio

n, id

entifi

catio

n an

d qu

antifi

catio

n of

pot

entia

l al

lelo

chem

ical

s [19

1]20

14W

heat

Whe

at st

raw

Maj

or o

rgan

ic c

ompo

nent

s (e

.g.,

N-h

eter

ocyc

les,

fatty

ac

ids,

phen

ols a

nd li

gnin

s)

Can

ada

Fast

pyro

lysi

s ste

el sh

ots 4

75 °C

Whe

at st

raw

bio

mas

s: a

reso

urce

for

high

-val

ue c

hem

ical

s [19

2]

2013

Cra

nber

ries

Cra

nber

ry ju

ice

and

pom

ace

Poly

phen

olic

sC

anad

a an

d M

exic

oPi

lot s

cale

met

hods

Solv

ents

: eth

anol

Extra

ctio

n tim

e: 2

4 h

Bio

activ

ities

of p

ilot-s

cale

ext

ract

ed

cran

berr

y ju

ice

and

pom

ace

[48]

2013

Frui

ts, v

eget

able

s, eg

gs, s

hrim

pPl

ant r

esid

ues,

indu

stria

l an

d po

st-ha

rves

t m

ater

ials

Car

oten

oids

Mex

ico

Revi

ewN

ovel

env

ironm

enta

lly fr

iend

ly

solv

ents

(e.g

., et

hyl l

acta

te,

bioe

than

ol, v

eget

al o

il, c

omm

er-

cial

enz

ymes

)

Car

oten

oids

ext

ract

ion

and

quan

tifi-

catio

n: a

revi

ew [1

93]

2013

Tom

atoe

sPe

els

Lyco

pene

Italy

Enzy

mat

ic-a

ssist

ed e

xtra

ctio

nTe

mpe

ratu

re: 4

5 an

d 60

 °CpH

4–5

and

9–1

0.5

Envi

ronm

enta

lly fr

iend

ly ly

cope

ne

purifi

catio

n fro

m to

mat

o pe

el

was

te: e

nzym

atic

-ass

isted

aqu

eous

ex

tract

ion

[112

]20

13C

offee

Coff

ee re

sidu

e le

ft af

ter

the

prep

arat

ion

of th

e br

ew (s

pent

coff

ee

grou

nds—

SCG

)

Poly

sacc

harid

esPo

rtuga

lA

lkal

i ext

ract

ion

Solv

ent:

H2O

and

4 M

NaO

HEx

tract

ion

time:

3 h

Tem

pera

ture

: 20–

120 

°C

Extra

ctab

ility

and

stru

ctur

e of

spen

t co

ffee

grou

nd p

olys

acch

arid

es b

y ro

astin

g pr

e-tre

atm

ents

[194

]

1 3

Top Curr Chem (Z) (2018) 376:3 Page 29 of 54 3

Tabl

e 1

(con

tinue

d)

Year

Cro

pW

aste

stre

amTa

rget

com

poun

dsG

eogr

aphi

cal l

ocat

ion

Gre

en o

r sus

tain

able

sepa

ratio

n ap

proa

chRe

fere

nces

2013

Coff

eeSp

ent c

offee

gro

unds

Lipi

ds, o

ilIr

anSo

xhle

t, U

AE,

MA

E, S

FESo

lven

ts: p

etro

leum

ben

zene

and

n-

hexa

neSo

xhle

t: 6 

h, b

oilin

g te

mpe

ratu

reU

AE:

45 

min

, am

bien

t con

ditio

nsM

AE:

30 

s, 20

0 an

d 80

0 W

SFE:

200

–250

 bar

, 40–

60 °C

, m

odifi

er (w

ater

, eth

anol

, hex

ane)

Extra

ctio

n of

lipi

ds fr

om sp

ent c

offee

gr

ound

s usi

ng o

rgan

ic so

lven

ts a

nd

supe

rcrit

ical

car

bon

diox

ide

[60]

2013

Fore

st In

dustr

yFo

rest

resi

dues

, inc

lud-

ing

bark

Bio

activ

e m

olec

ules

Can

ada

Revi

ewG

reen

alte

rnat

ives

for t

he d

esig

n,

form

ulat

ion,

and

man

ufac

ture

of

new

pro

duct

s with

app

licat

ions

in

var

ious

mar

kets

(cos

met

ics,

natu

ral h

ealth

pro

duct

s, bi

ocid

es,

adhe

sive

s, co

atin

gs)

Fore

st ex

tract

ives

, the

4th

pat

hway

of

the

fore

st bi

orefi

nery

con

cept

[195

]

2013

Coff

eeSp

ent c

offee

gro

unds

(S

CG

)Li

pid

frac

tion

Portu

gal a

nd B

razi

lSu

perc

ritic

al c

arbo

n di

oxid

eEx

tract

ion

time:

1 h

Tem

pera

ture

: 55 

°CPr

essu

re: 2

50 b

arCO

2 flow

rate

: 15 

kg/h

From

coff

ee in

dustr

y w

aste

mat

eria

ls

to sk

in-f

riend

ly p

rodu

cts w

ith

impr

oved

skin

fat l

evel

s [91

]

2013

Wal

nuts

Gre

en h

usk

Nat

ural

com

poun

ds w

ith

antio

xida

nt a

nd a

ntim

icro

-bi

al p

rope

rties

Spai

n an

d Po

rtuga

lSo

lven

t ext

ract

ion

Solv

ents

: wat

er, m

etha

nol,

etha

nol

Extra

ctio

n tim

e: 4

5 m

in ro

om

tem

pera

ture

Influ

ence

of s

olve

nt o

n th

e an

tioxi

-da

nt a

nd a

ntim

icro

bial

pro

perti

es

of w

alnu

t (Ju

glan

s reg

ia L

.) gr

een

husk

ext

ract

s [49

]20

13C

offee

Spen

t coff

eeA

ntio

xida

nts

Spai

nSo

xhle

t, SP

E, fi

lter c

offee

mak

erSo

lven

ts: w

ater

, eth

anol

, met

hano

lEx

tract

ion

time:

6–1

65 m

inTe

mpe

ratu

re: 8

0–10

0 °C

Influ

ence

of e

xtra

ctio

n pr

oces

s on

antio

xida

nt c

apac

ity o

f spe

nt c

offee

[5

0]

Top Curr Chem (Z) (2018) 376:3

1 3

3 Page 30 of 54

Tabl

e 1

(con

tinue

d)

Year

Cro

pW

aste

stre

amTa

rget

com

poun

dsG

eogr

aphi

cal l

ocat

ion

Gre

en o

r sus

tain

able

sepa

ratio

n ap

proa

chRe

fere

nces

2013

Tom

atoe

sPe

elFa

tty a

cids

Fran

ceD

epol

ymer

izat

ion

1.5 

M K

OM

e ov

erni

ght t

reat

men

t at r

oom

te

mpe

ratu

re

Inte

rfaci

al p

rope

rties

of f

unct

iona

l-iz

ed a

ssem

blie

s of h

ydro

xy-fa

tty

acid

salts

isol

ated

from

frui

t tom

ato

peel

s [19

6]20

13C

offee

Spen

t coff

ee g

roun

ds

(SC

G)

Poly

sacc

harid

esPo

rtuga

lM

icro

wav

e su

perh

eate

d w

ater

ex

tract

ion

Extra

ctio

n tim

e: 5

 min

Tem

pera

ture

: 200

 °C

Mic

row

ave

supe

rhea

ted

wat

er e

xtra

c-tio

n of

pol

ysac

char

ides

from

spen

t co

ffee

grou

nds [

61]

2013

Turk

ish

red

pine

tim

ber

Was

te b

arks

Nat

ural

dye

Turk

eyN

atur

al d

yestu

ff ex

tract

ion

mac

hine

Solv

ents

: wat

er a

nd e

than

olEx

tract

ion

time:

24 

h (o

smos

is)

Nat

ural

dye

ext

ract

ion

from

was

te

bark

s of T

urki

sh re

d pi

ne (P

inus

br

utia

Ten

.) Ti

mbe

r and

eco

-fr

iend

ly n

atur

al d

yein

g of

var

ious

te

xtile

fibe

rs [1

26]

2013

Cot

ton,

jute

, flax

, he

mp,

ram

ie a

nd

natu

ral c

olor

ants

Was

tes a

nd m

anuf

actu

r-in

g by

-pro

duct

sFi

bres

, pol

ysac

char

ides

, dy

es a

nd p

igm

ents

, po

lyph

enol

s, oi

ls a

nd

othe

r bio

logi

cally

act

ive

com

poun

ds

Indi

aRe

view

Con

vent

iona

l mac

erat

ion,

soxh

let,

MA

E, S

FE, u

ltras

onic

ext

ract

ion

Pers

pect

ives

for n

atur

al p

rodu

ct

base

d ag

ents

der

ived

from

indu

s-tri

al p

lant

s in

text

ile a

pplic

atio

ns: a

re

view

[197

]

2013

Coff

eeSp

ent c

offee

gro

unds

Nat

ural

ant

ioxi

dant

sIta

lySo

lven

t ext

ract

ion

Solv

ents

: H2O

, eth

anol

,Ex

tract

ion

time:

30 

min

Tem

pera

ture

: 60 

°C

Reco

very

of n

atur

al a

ntio

xida

nts

from

spen

t coff

ee g

roun

ds [1

98]

2013

Feijo

a fr

uits

Prim

arily

skin

and

som

e fle

shTo

tal s

olub

le so

lids (

TSS)

, pe

ctin

fibr

e co

nten

t, to

tal

extra

ctab

le P

P co

nten

t (T

EPC

) and

tota

l ant

ioxi

-da

nt a

ctiv

ity

New

Zea

land

Acc

eler

ated

solv

ent e

xtra

ctio

nSo

lven

ts: (

acid

ified

) wat

er, e

than

olTe

mpe

ratu

re: 2

0 or

50 

°C

Util

isat

ion

pote

ntia

l of f

eijo

a fr

uit

was

tes a

s ing

redi

ents

for f

unct

iona

l fo

ods [

127]

2012

Gre

en te

aG

reen

tea

was

teN

onca

ffein

e te

a po

lyph

enol

sC

hina

Wat

er b

ath

20 m

in90

 °C

A n

ovel

way

of s

epar

atio

n an

d pr

epa-

ratio

n no

n-ca

ffein

e te

a po

lyph

enol

s fro

m g

reen

tea

was

te [1

99]

1 3

Top Curr Chem (Z) (2018) 376:3 Page 31 of 54 3

Tabl

e 1

(con

tinue

d)

Year

Cro

pW

aste

stre

amTa

rget

com

poun

dsG

eogr

aphi

cal l

ocat

ion

Gre

en o

r sus

tain

able

sepa

ratio

n ap

proa

chRe

fere

nces

2012

Larc

hLa

rch

woo

d-de

rived

lig

noce

llulo

sic

resi

due

Ara

bino

gala

ctan

, pec

tin, a

nd

crys

talli

ne g

luco

seRu

ssia

Wat

er e

xtra

ctio

nEx

tract

ion

time:

2–3

 hTe

mpe

ratu

re: 6

0–80

 °C

An 

eco-

frie

ndly

 tech

nolo

gy fo

r po

lysa

ccha

ride

prod

uctio

n fro

m

logg

ing

and

saw

ing

was

te [1

28]

2012

Oliv

esO

live

leav

esO

leur

opei

nG

reec

eSF

E an

d PL

ESF

E: 3

0 M

Pa, 5

0 °C

, 9.6

 kg/

hPL

E: 1

0.34

 MPa

, 10 

min

, 40

–150

 °CSo

lven

ts: H

2O a

nd E

tOH

Dev

elop

men

t of a

gre

en e

xtra

ctio

n pr

oced

ure

with

supe

r/sub

criti

cal

fluid

s to

prod

uce

extra

cts e

nric

hed

in o

leur

opei

n fro

m o

live

leav

es

[92]

2012

Woo

dW

ood

bark

s, ob

tain

ed

from

pul

p m

ills a

s in

dustr

ial w

aste

s

Nat

ural

phe

nolic

pol

ymer

s of

tann

ins a

nd li

gnin

Fran

ceA

queo

us e

xtra

ctio

nur

ea a

nd su

lfite

use

d as

wat

er-

addi

tives

Extra

ctio

n tim

e: 1

 h u

nder

reflu

xTe

mpe

ratu

re: 7

5 °C

Dev

elop

men

t of g

reen

adh

esiv

es fo

r fib

rebo

ard

man

ufac

turin

g, u

sing

ta

nnin

s and

lign

in fr

om p

ulp

mill

re

sidu

es [1

29]

2012

Whe

atW

heat

mill

ing

by-

prod

ucts

Hig

h qu

ality

oil

and

vita

min

E

Italy

Revi

ewSo

lven

t ext

ract

ion,

mec

hani

cal

pres

sing

or t

he e

co-f

riend

ly

supe

rcrit

ical

car

bon

diox

ide

(SC

-CO

2) e

xtra

ctio

n te

chno

logy

Dur

um w

heat

by-

prod

ucts

as n

atur

al

sour

ces o

f val

uabl

e nu

trien

ts [2

00]

2012

Tree

bar

kW

aste

pro

duct

from

pa

per p

ulp

indu

strie

sA

ntio

xida

nts

Swed

enSF

E, P

FE, S

LESo

lven

ts: s

cCO

2, et

hano

l, H

2OEx

tract

ion

time:

30 

min

–24 

hTe

mpe

ratu

re: 7

0–18

0 °C

Extra

ctio

n of

ant

ioxi

dant

s fro

m

spru

ce (P

icea

abi

es) b

ark

usin

g ec

o-fr

iend

ly so

lven

ts [9

3]

2012

Tim

ber

Empt

y fr

uit b

unch

esFi

ber

Mal

aysi

aPe

rspe

ctiv

e pa

per

Fibe

r res

in m

atrix

com

posi

tes:

na

ture

’s g

ift [2

01]

2012

Ora

nges

Peel

Esse

ntia

l oil

Uni

ted

Kin

gdom

Stea

m d

istill

atio

n an

d m

icro

wav

e irr

adia

tion

SD: w

ater

, 1 h

MW

: 12.

5 m

in, 2

00 °C

, pow

er

grad

ient

from

400

to 1

200 

W

p-cy

men

esul

phon

ic a

cid:

an

orga

nic

acid

synt

hesi

zed

from

citr

us w

aste

[2

02]

Top Curr Chem (Z) (2018) 376:3

1 3

3 Page 32 of 54

Tabl

e 1

(con

tinue

d)

Year

Cro

pW

aste

stre

amTa

rget

com

poun

dsG

eogr

aphi

cal l

ocat

ion

Gre

en o

r sus

tain

able

sepa

ratio

n ap

proa

chRe

fere

nces

2012

Bla

ck te

aB

lack

tea

was

tes

Panc

reat

ic li

pase

-inhi

bitin

g po

lyph

enol

sJa

pan

Hot

-com

pres

sed

wat

er (H

CW

) io

n-ex

chan

ge w

ater

ext

ract

ion

tem

pera

ture

: 100

–200

 °C

Poly

phen

ols e

xtra

cted

from

bla

ck

tea

(Cam

ellia

sine

nsis

) res

idue

by

hot-c

ompr

esse

d w

ater

and

thei

r in

hibi

tory

effe

ct o

n pa

ncre

atic

lip

ase

in v

itro

[203

]20

12G

reen

tea

Gre

en te

a w

aste

Poly

phen

ols

Chi

naLi

quid

–liq

uid

extra

ctio

nSo

lven

ts: H

2O, g

lyce

ryl,

triac

etat

e,

n-bu

tano

l, et

hyl a

ceta

teEx

tract

ion

time:

12 

h +

 2 h

Reco

very

of t

ea p

olyp

heno

ls fr

om

gree

n te

a w

aste

by

liqui

d–liq

uid

extra

ctio

n [2

04]

2012

Citr

usPe

els

Poly

met

hoxy

flav

onoi

dsC

hina

Solv

ent e

xtra

ctio

nSo

lven

ts: m

etha

nol a

nd e

than

olEx

tract

ion

time:

1–3

 hTe

mpe

ratu

re: 6

5–85

 °C

Stud

y on

the

extra

ctio

n te

chni

que

of

poly

-met

hoxy

flavo

noid

s fro

m c

it-ru

s pee

ls b

y us

ing

resp

onse

surfa

ce

met

hodo

logy

[205

]20

11C

offee

Hus

ksC

affei

neSp

ain

Supe

rcrit

ical

CO

2Ex

tract

ion

time:

20 

min

Tem

pera

ture

: 323

 KPr

essu

re: 6

0 ba

rCO

2 flow

rate

: 2–3

 g/m

in

Extra

ctio

n of

caff

eine

from

Rob

usta

co

ffee

(Coff

ea c

anep

hora

var

. Ro

bust

a) h

usks

usi

ng su

perc

ritic

al

carb

on d

ioxi

de [9

4]

2011

Ora

nges

Peel

Esse

ntia

l oils

Fran

ce a

nd T

unis

iaM

icro

wav

e ste

am d

iffus

ion

(MSD

f)Ex

tract

ion

time:

12 

min

Tem

pera

ture

:100

 °C

Mic

row

ave

steam

diff

usio

n fo

r ex

tract

ion

of e

ssen

tial o

il fro

m

oran

ge p

eel:

kine

tic d

ata,

ext

ract

’s

glob

al y

ield

and

mec

hani

sm [6

2]20

11G

rape

Skin

sA

ntho

cyan

ins

Spai

nM

icro

wav

e-as

siste

d ex

tract

ion

Solv

ents

: H2O

, met

hano

lEx

tract

ion

time:

5–2

0 m

inTe

mpe

ratu

re: 5

0–10

0 °C

Mic

row

ave-

assi

sted

extra

ctio

n of

an

thoc

yani

ns fr

om g

rape

skin

s [63

]

2011

Tea

(gre

en, o

olon

g an

d bl

ack)

Tea

resi

dues

(gre

en,

oolo

ng a

nd b

lack

tea

resi

dues

)

Phen

olic

com

poun

dsJa

pan

Mic

row

ave-

assi

sted

extra

ctio

n w

ater

und

er a

utoh

ydro

lytic

co

nditi

ons

Extra

ctio

n tim

e: 2

 min

Tem

pera

ture

: 110

–230

 °C

Mic

row

ave-

assi

sted

extra

ctio

n of

ph

enol

ic c

ompo

unds

from

tea

resi

dues

und

er a

utoh

ydro

lytic

co

nditi

ons [

64]

1 3

Top Curr Chem (Z) (2018) 376:3 Page 33 of 54 3

Tabl

e 1

(con

tinue

d)

Year

Cro

pW

aste

stre

amTa

rget

com

poun

dsG

eogr

aphi

cal l

ocat

ion

Gre

en o

r sus

tain

able

sepa

ratio

n ap

proa

chRe

fere

nces

2011

Sea

Buc

ktho

rn

(Hip

poph

ae rh

am-

noid

es

By-

Prod

ucts

of j

uice

pr

oduc

tion

Flav

onoi

dsFr

ance

Solv

ent-f

ree

mic

row

ave

hydr

odiff

u-si

on a

nd g

ravi

ty (M

HG

) with

out

addi

tion

of so

lven

t or w

ater

at

mos

pher

ic p

ress

ure

Solv

ent f

ree

mic

row

ave-

assi

sted

extra

ctio

n of

ant

ioxi

dant

s fro

m se

a bu

ckth

orn

(Hip

poph

ae rh

am-

noid

es) f

ood

by-p

rodu

cts [

206]

2011

Whe

atW

heat

stra

wEn

ergy

and

CO

2 sec

onda

ry

met

abol

ites i

nclu

ding

fatty

ac

ids,

wax

este

rs a

nd fa

tty

alco

hols

Engl

and

Supe

rcrit

ical

CO

2 ext

ract

ion

Tem

-pe

ratu

re: 4

0–10

0 °C

Pres

sure

: 100

–300

 bar

CO2 fl

ow ra

te: 4

0 g/

min

Use

of g

reen

che

mic

al te

chno

logi

es

in a

n in

tegr

ated

bio

refin

ery

[95]

2011

Oliv

esB

y-pr

oduc

ts g

ener

ated

du

ring

stora

ge o

f ex

tra v

irgin

oliv

e oi

l

Phen

olic

com

poun

ds,

hydr

oxyt

yros

ol, t

yros

ol,

deca

rbox

ymet

hyl

oleu

rope

in a

glyc

one,

and

lu

teol

in

Italy

and

Spa

inSo

lid–l

iqui

d an

d liq

uid–

liqui

d ex

tract

ion

Solv

ents

: n-h

exan

e, m

etha

nol,

H2O

Extra

ctio

n tim

e: 1

 h

Was

tes g

ener

ated

dur

ing

the

stora

ge

of e

xtra

virg

in o

live

oil a

s a n

atur

al

sour

ce o

f phe

nolic

com

poun

ds

[207

]

2010

Tom

atoe

sG

roun

d to

mat

oes w

ith-

out s

eeds

Lyco

pene

Fran

ce a

nd A

lger

iaSo

lven

t ext

ract

ion

Solv

ent:

d-li

mon

ene

Car

oten

oid

extra

ctio

n fro

m to

mat

o us

ing

a gr

een

solv

ent r

esul

ting

from

ora

nge

proc

essi

ng w

aste

[2

08]

2010

Tea

plan

tTe

a st

alk

and

fiber

w

aste

sC

affei

neTu

rkey

Supe

rcrit

ical

CO

2 eth

anol

as c

o-so

lven

tEx

tract

ion

time:

1–5

 hTe

mpe

ratu

re: 5

0–70

 °CPr

essu

re: 2

50 b

arse

mi-c

ontin

uous

flow

Effec

t of e

than

ol c

onte

nt o

n su

per-

criti

cal c

arbo

n di

oxid

e ex

tract

ion

of c

affei

ne fr

om te

a st

alk

and

fiber

w

aste

s [96

]

2010

Portu

gues

e el

der-

berr

yPo

mac

eA

ntho

cyan

ins

Portu

gal

Supe

rcrit

ical

CO

2 ext

ract

ion

Solv

ents

: CO

2, w

ater

, eth

anol

Extra

ctio

n tim

e: 4

0 m

inTe

mpe

ratu

re: 3

13 K

Effec

t of s

olve

nt (C

O2/e

than

ol/

H2O

) on

the

frac

tiona

ted

enha

nced

so

lven

t ext

ract

ion

of a

ntho

cyan

ins

from

eld

erbe

rry

pom

ace

[97]

2010

Gre

en te

aG

reen

tea

was

tePo

lyph

enol

s, to

tal c

atec

hins

, an

d re

duci

ng su

gars

Sout

h K

orea

and

USA

Solv

ents

: col

d w

ater

(25 

°C),

hot

wat

er (9

0 °C

), su

lfuric

aci

d,

hydr

ochl

oric

aci

d an

d m

etha

nol

Extra

ctio

n tim

e: 2

0 m

in25

0 rp

m

Effec

ts o

f cel

lula

se fr

om A

sper

gillu

s ni

ger a

nd so

lven

t pre

treat

men

ts o

n th

e ex

tract

abili

ty o

f org

anic

gre

en

tea

was

te [1

30]

Top Curr Chem (Z) (2018) 376:3

1 3

3 Page 34 of 54

Tabl

e 1

(con

tinue

d)

Year

Cro

pW

aste

stre

amTa

rget

com

poun

dsG

eogr

aphi

cal l

ocat

ion

Gre

en o

r sus

tain

able

sepa

ratio

n ap

proa

chRe

fere

nces

2010

Tea

Tea

was

teC

affei

neIr

anSu

bcrit

ical

wat

er e

xtra

ctio

nTe

mpe

ratu

re: 1

00–2

00 °C

Pres

sure

: 20–

40 b

arw

ater

flow

rate

: 1–4

 g/m

in

Isol

atio

n of

caff

eine

from

tea

was

te

usin

g su

bcrit

ical

wat

er e

xtra

ctio

n [1

04]

2010

Citr

us su

dach

iPe

els

Flav

ones

Japa

nM

icro

wav

e-as

siste

d ex

tract

ion

Solv

ents

: met

hano

lex

tract

ion

time:

10

to 1

2 m

in

Mic

row

ave-

assi

sted

extra

ctio

n an

d m

ethy

latio

n of

use

ful fl

avon

es fr

om

was

te p

eels

of C

itrus

suda

chi [

209]

2010

Mat

e (I

lex

para

guar

-ie

nsis

)M

ate

resi

due

Com

poun

ds w

ith a

nti-

oxid

ant p

rope

rties

, suc

h as

phe

nolic

aci

ds a

nd

met

hylx

anth

ines

, suc

h as

ca

ffein

e

Bra

zil

Solv

ent e

xtra

ctio

nSo

lven

t: m

etha

nol,

H2O

, eth

anol

soni

catio

n fo

r 15 

min

room

te

mpe

ratu

re

Phen

olic

aci

ds a

nd m

ethy

lxan

thin

es

com

posi

tion

and

antio

xida

nt p

rop-

ertie

s of m

ate

(Ile

x pa

ragu

arie

nsis

) re

sidu

e [2

10]

2010

Ric

eR

ice

bran

Phen

olic

com

poun

ds a

s wel

l as

oth

er v

alua

ble

mat

eria

lsJa

pan

Subc

ritic

al w

ater

Preh

eate

d oi

l: 10

0–18

0 °C

, 10 

min

Preh

eate

d w

ater

bat

h: 1

80–3

60 °C

, 10

 min

and

220

 °C fo

r 2–3

0 m

in

Prod

uctio

n of

phe

nolic

com

poun

ds

from

rice

bra

n bi

omas

s und

er su

b-cr

itica

l wat

er c

ondi

tions

[105

]

2009

Citr

usPe

els

Esse

ntia

l oil

Fran

ce a

nd A

lger

iaM

icro

wav

e hy

drod

iffus

ion

grav

ityEx

tract

ion

time:

15 

min

atm

osph

eric

pre

ssur

e 50

0 W

A n

ew p

roce

ss fo

r ext

ract

ion 

of

esse

ntia

l oil

from

citr

us p

eels

: m

icro

wav

e hy

drod

iffus

ion

and

grav

ity [6

5]20

09K

iwifr

uit

By-

prod

ucts

der

ived

fro

m k

iwifr

uit p

ro-

cess

ing

Phen

olic

s and

pec

tin p

oly-

sacc

harid

esN

ew Z

eala

ndSo

lven

t ext

ract

ion

Solv

ents

: wat

er, e

than

olEx

tract

ion

time:

1 h

room

tem

-pe

ratu

re

Eval

uatio

n of

the

extra

ctio

n effi

cien

cy fo

r pol

yphe

nol e

xtra

cts

from

by-

prod

ucts

of g

reen

kiw

ifrui

t ju

icin

g [2

11]

2009

Palm

Bla

ck li

quor

of o

il pa

lm

was

teLi

gnin

Mal

aysi

aSo

lven

t ext

ract

ion

Che

mic

al e

xtra

ctio

ns: d

i-eth

yl

ethe

r, al

coho

l-ben

zene

mix

ture

tre

atm

ent w

ith H

2SO

4 for

30

–45 

min

Expl

orin

g th

e an

tioxi

dant

pot

entia

l of

ligni

n is

olat

ed fr

om b

lack

liqu

or o

f oi

l pal

m w

aste

[212

]

1 3

Top Curr Chem (Z) (2018) 376:3 Page 35 of 54 3

Tabl

e 1

(con

tinue

d)

Year

Cro

pW

aste

stre

amTa

rget

com

poun

dsG

eogr

aphi

cal l

ocat

ion

Gre

en o

r sus

tain

able

sepa

ratio

n ap

proa

chRe

fere

nces

2009

Turk

ish

tea

plan

tsTe

a st

alk

and

fiber

w

aste

sC

affei

neTu

rkey

Supe

rcrit

ical

car

bon

diox

ide

Extra

ctio

n tim

e: 1

–10 

hTe

mpe

ratu

re: 5

5–75

 °C in

crea

sing

pr

essu

re u

p to

250

 bar

sem

i-co

ntin

uous

flow

Extra

ctio

n of

caff

eine

from

tea

stal

k an

d fib

er w

aste

s usi

ng su

perc

ritic

al

carb

on d

ioxi

de [9

9]

2009

Ric

eR

ice

bran

Oil

(val

ue-a

dded

mat

eria

ls

such

as a

min

o ac

ids,

orga

nic

acid

s, an

d w

ater

-so

lubl

e sa

ccha

rides

)

Japa

nSu

bcrit

ical

wat

er p

rehe

ated

oil

bath

: 100

–180

 °CPr

ehea

ted

salt

bath

: 200

–360

 °CRe

actio

n tim

e: 5

 min

Sub-

criti

cal w

ater

trea

tmen

t of r

ice

bran

to p

rodu

ce v

alua

ble

mat

eria

ls

[106

]

2009

Seve

ral b

iom

ass

Resi

dues

rich

in li

gno-

cellu

losi

csB

io-b

ased

che

mic

als (

e.g.

, su

ccin

ic, l

actic

, fum

aric

l-

mal

ic, l

-asp

artic

aci

ds)

Engl

and

Revi

ewFo

cus o

n gr

een

chem

ical

con

ver-

sion

of l

igni

n in

to h

ighe

r val

ue

chem

ical

s

The

inte

grat

ion

of g

reen

che

mist

ry

into

futu

re b

iore

finer

ies [

21]

2009

App

leIn

dustr

ially

gen

erat

ed

appl

e po

mac

eA

ntio

xida

nts a

nd p

oly-

phen

ols

Irel

and

Pres

suriz

ed li

quid

ext

ract

ion

acce

l-er

ated

solv

ent e

xtra

ctor

stat

ic

extra

ctio

n of

5 m

inTe

mpe

ratu

re: 7

5–19

3 °C

The

optim

izat

ion

of e

xtra

ctio

n of

an

tioxi

dant

s fro

m a

pple

pom

ace

by

pres

suriz

ed li

quid

s [21

3]

2008

Chi

cory

, citr

us, c

au-

liflow

er, e

ndiv

e,

and

suga

r bee

t

Plan

t by-

prod

ucts

(c

hico

ry ro

ots,

citru

s pe

el, c

aulifl

ower

flo

rets

and

leav

es,

endi

ve, a

nd su

gar b

eet

pulp

s)

Pect

ins

Fran

ce a

nd F

inla

ndEn

zym

atic

ext

ract

ion

Extra

ctio

n tim

e: 4

 hTe

mpe

ratu

re: 5

0 °C

Extra

ctio

n of

gre

en la

bele

d pe

ctin

s an

d pe

ctic

olig

osac

char

ides

from

pl

ant b

y-pr

oduc

ts [1

13]

2008

Tea

(gre

en, o

olon

g,

and

blac

k)G

reen

, ool

ong,

and

bl

ack

tea

resi

dues

Poly

sacc

harid

es, p

olyp

he-

nols

, ara

bino

se, g

alac

tose

, xy

lose

, cat

echi

ns

Japa

nM

icro

wav

e he

atin

gSo

lven

t: w

ater

Tem

pera

ture

: 110

–230

 °C

Mic

row

ave

heat

ing

of te

a re

sidu

e yi

elds

pol

ysac

char

ides

, pol

yphe

-no

ls, a

nd p

lant

bio

poly

este

r [66

]20

08Pl

ant l

ipid

sPl

ant o

ils a

nd o

ther

na

tura

l lip

idic

pha

ses

Phyt

oste

rols

, vita

min

sC

zech

Rep

ublic

Revi

ewEn

zym

es a

s effi

cien

t nat

ural

ca

taly

sts

Plan

t pro

duct

s for

pha

rmac

olog

y:

appl

icat

ion

of e

nzym

es in

thei

r tra

nsfo

rmat

ions

[114

]

Top Curr Chem (Z) (2018) 376:3

1 3

3 Page 36 of 54

Tabl

e 1

(con

tinue

d)

Year

Cro

pW

aste

stre

amTa

rget

com

poun

dsG

eogr

aphi

cal l

ocat

ion

Gre

en o

r sus

tain

able

sepa

ratio

n ap

proa

chRe

fere

nces

2007

Bro

ccol

iB

rocc

oli s

eeds

Nat

ural

sulfo

raph

ane

Chi

na a

nd A

ustra

liaLi

quid

–liq

uid

and

solid

-pha

se

extra

ctio

nSo

lven

ts: e

than

ol, h

exan

e, e

thyl

ac

etat

e

Sepa

ratio

n an

d pu

rifica

tion

of

sulfo

raph

ane

from

bro

ccol

i see

ds

by so

lid p

hase

ext

ract

ion

and

pre-

para

tive

high

-per

form

ance

liqu

id

chro

mat

ogra

phy

[214

]20

06Te

aTe

a w

aste

Caff

eine

Turk

eySo

lid–l

iqui

d ex

tract

ion

solv

ents

: hot

wat

er a

nd c

hlor

ofor

mTe

mpe

ratu

re: 3

70 K

and

293

 K

Solid

–liq

uid

extra

ctio

n of

caff

eine

fro

m te

a w

aste

usi

ng b

atte

ry ty

pe

extra

ctor

: pro

cess

opt

imiz

atio

n [2

15]

1 3

Top Curr Chem (Z) (2018) 376:3 Page 37 of 54 3

components in these matrices, such as water or high molecular weight compounds [39].

The decision concerning the best method to separate the compounds of inter-est from the raw material is dependent on several aspects, such as the charac-teristics of the target extracts and raw material (physical–chemical properties), available technology, required purity, selectivity, stability and, more importantly here, the greenness of the whole process. As can be seen in Fig.  5, the most cited techniques in these research papers were based on solvent/maceration (25% of the total), microwave (19%), ultrasonication (14.7%) and supercritical fluid processing (13%), followed by methods using ionic liquids (7%), enzymatic and subcritical fluid treatment (6%), as well as the association of two or more techniques.

According to the literature, the most widespread approaches for separat-ing natural products from a number of matrices are based on liquid–liquid or solid–liquid extraction (LLE and SLE). Several greener alternatives have been proposed by replacing toxic or non-renewable organic solvents, as well as the extraction times. In some cases, solid-phase extractions (SPE) were also car-ried out and decreased both the amount of solvent and the number of extrac-tion cycles, offering high enrichment factors [39, 40]. Actually, the mass transfer enhancement for SLE has been largely studied and applied, contributing to tech-nology innovation, process intensification and integration, and energy saving, especially important for microwave, ultrasound, and high-pressure processing, for instance [41]. An overview of these techniques and related examples will be discussed in this section.

Fig. 5 Main green and sustainable techniques used to separate natural products from waste described in research papers (ISIS Web of Knowledge, January 2006 to December 2017)

Top Curr Chem (Z) (2018) 376:3

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3 Page 38 of 54

3.1 From Conventional Solvent Separation to Enhancement Processing Approaches Over the Last 10 Years

Solvent processing is one of the most traditional methods to remove natural products from bio-derived materials. In this extraction approach, the raw material in adequate size is exposed to different solvents, mostly organic, which remove soluble compo-nents of interest. The samples are then usually centrifuged and filtered to separate the solid residue, and the extract is used in this way (as a food supplement or for pre-paring functional foods, for example) or treated after this step. Solvent extraction is attractive compared to other methods due to low cost and simplicity. However, this method does not always use benign solvents; it frequently requires an evaporation/concentration step for recovery, it usually demands large amounts of solvent and needs a long time to be carried out. Additionally, the possibility of thermal degrada-tion of natural bioactive components is also possible due to the high temperatures used during the extraction process [42]. Despite this, it is largely used in industries, where solvent reuse is of great economic importance. In general, the raw material (in its liquid or solid form) is mixed with a solvent, and the separation kinetic of the target compounds is influenced by parameters such as the solvent ratio, pH, and tem-perature and, for SLE, the particle size. The solvent should be atoxic, non-flammable and stable at working conditions, ideally renewable and cheap, with low viscosity and an adequate boiling point, allowing for easier solvent removal from the extract/fraction [43]. Recently, several models have been proposed to predict the best sol-vents to be used in a specific case, which do not only take into account physical descriptors, such as enthalpy of vaporization, dielectric constant, refractive index, boiling point, etc., but also empirical descriptors to evaluate, for instance, intermo-lecular forces (specific and non-specific solute–solvent interactions, e.g., hydrogen bond donor and/or hydrogen bond acceptor, Van der Waals and ion/dipole forces). Purely theoretical descriptors have been also introduced, offering the most impor-tant advantage of not requiring any experiments, as is the case of the model known as quantitative structure property relationship (QSPR), able to predict 127 polarity scales for more than 700 solvents [44].

The solvent selection also depends on the physical–chemical proprieties of the compounds of interest, considering principally the selectivity and greenness degree of the process, aiming at obtaining high recoveries and the integrity of the target compounds. In general, the raw material stays in contact with the solvent for a cer-tain period (from minutes to days), when the soluble compounds are transferred from the matrix to the extractor phase, usually by shaking the system. For SLE, the dispersion of the particles in the solvent is facilitated agitating them, optimizing their contact and accelerating the separation process. Traditionally, solvent treatment is performed at room temperature, although heating can promote higher recoveries to these compounds that are not thermosensitive. In some cases, LLE and SLE can be time-consuming, demanding further purification and concentration steps, which are their main drawbacks [41, 45].

Maceration using green and non-toxic solvents for the separation of natural prod-ucts from plant-derived waste has been described over the last years (e.g., to remove dyes from quince leaves or catechins, theaflavins, gallic acid, and antioxidants in

1 3

Top Curr Chem (Z) (2018) 376:3 Page 39 of 54 3

general from walnut green husk, cranberry pomace, black tea and banana process-ing waste). According to these studies, using water, methanol, ethanol or a mixture of them at 70–100 °C can be a low-cost, benign alternative for the recovery of high added-value compounds derived from residual biomass [46–49]. Scaling-up was also studied, whose results showed to be useful in determining industrial process feasibility and the economic value of polyphenols for commercial use, increasing the overall profitability of the cranberry industry [48].

Whenever possible, higher temperatures allow for higher mass transfer in a shorter time with lower energy consumption in general, resulting in better recovery efficiency than conventional systems [50]. As observed in Fig. 5, the second most cited green and sustainable separation process is based on microwave heating and can be considered a non-conventional technique nowadays. Heating is based on non-ionizing electromagnetic waves. Those between 0.915 and 2.45 GHz are used for industrial, scientific and medical applications. The overall principle of heat-ing is rooted in its direct impact with polar materials/solvents and is dependent on ionic conduction and dipole rotation, occurring simultaneously in most cases. The increased temperature can overcome the natural product-matrix interaction caused by Van der Waals forces, dipole attraction, hydrogen bonding of the compounds of interest and active sites in the matrix. Therefore, thermal energy can disrupt both solute–solute and solute–matrix interactions, providing the activation energy required for the desorption process. The mass transfer of the compounds from the raw material to the solvent is also accomplished by convection and diffusion mecha-nisms, causing the explosion of plant cells and releasing their content into the liquid phase [51].

The eco-friendly removal of essential oils, pectin and polyphenols from a number of plant raw materials mediated by microwave irradiation has been described over the last years, paying special attention to citrus waste [52–66]. In fact, the orange juice processing industry can be considered more than a good case study. This sec-tor is highly wasteful, generating 50% of waste from the total fruit/starting material (e.g., peel, bagasse, seeds and yellow water). Around 20 million tonnes of orange peel per year are produced worldwide, which consist of water (80%) and sugars, cel-lulose, hemicellulose, pectin and d-limonene (20%). Recently, it was shown using a mathematical model that d-limonene extraction consisted of a two stage diffusion process for a microwave (MW) heating approach: initial extraction from the exte-rior of cells followed by trans-membrane diffusion. Compared to other conventional extraction methods, it was found that the microwave treatment was more efficient, resulting in a higher overall yield due to the access to a higher amount of d-limonene [59].

The successful microwave-assisted solvent-free modification of pectin derived from citrus waste has also been reported [53]. These approaches not only allow for the separation of the major components of citrus peel, but they also add further value through the production of other high value-added products, such as pectin, d-limonene and a rare form of mesoporous cellulose which are produced in a sin-gle step, without added acid [67]. Along these lines, the concept of dry-biorefinery is gaining momentum, since valuable products can be recovered from plant by-products without adding solvents or water, using green processes such as MW [56].

Top Curr Chem (Z) (2018) 376:3

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3 Page 40 of 54

Innovation relies on the separation of the target compounds from raw materials, which are rich in water, achieved without adding solvents or water, illustrating a cir-cular systemic process; i.e., all materials and resources could be reintegrated into the integrated and zero-waste biorefinery [19]. Although very attractive, as expected, the design and use of real MW industrial scale equipment requires additional studies related to safety, corrosion and maintenance intervals [68].

The combination of two or more extraction/concentration methods is quite com-mon in the literature (Table 1). As described by Boukroufa et al. [56], the removal of essential oil, polyphenols and pectin from orange waste was conducted using micro-wave and ultrasound technology, without adding any solvents. Essential oil separa-tion was performed by Microwave Hydrodiffusion and Gravity (MHG), and there-after the remaining water of this process was used as a solvent for the subsequent extraction of flavonoids and pectin. For polyphenol separation, ultrasound-assisted extraction (UAE) was used, and response surface methodology (RSM) using the central composite design (CCD) approach was used to investigate the influence of some variables. The CCD revealed that the optimized conditions of ultrasound power and temperature were 0.956 W/cm2 and 59.83 °C giving a polyphenol yield of 50.02 mg GA/100 g dm, which, compared to conventional extraction, promoted an increase of 30% in the yield. Pectin was extracted by microwave-assisted extrac-tion, resulting in a maximal yield of 24.2% for microwave power of 500 W (3 min), whereas traditional extraction provides18.32% (120 min). As can be seen, the com-bination of microwave, ultrasound and recycled water resulted in higher recoveries of the compounds of interest in a shorter time, so that a systemic loop/cycle could be closed using only the resources generated in the plant. This makes the whole pro-cess optimized in terms of time, energy savings, cleanliness and reduced amount of waste.

As can be noted, ultrasound has been widely utilized for helping to extract target components from waste plant-derived sources, reducing separation time, solvents, energy consumption and improving the product quality. The effectiveness of ultra-sound is attributed to the cavitation phenomenon, assisting the solubilization of the compounds of interest into the solvent, enhancing their removal from the bulk raw material [69]. According to Chemat [70], the ultrasound waves (from 20 kHz to 10 MHz) pass through an elastic medium, inducing a longitudinal displacement of particles resulting in a succession of compression and rarefaction phases in this medium. Every medium has a critical molecular distance and, below this critical point, the liquid remains intact. However, above this distance, the liquid would break down, creating voids (cavitation bubbles) in the liquid. When the size of these bub-bles reaches a critical point they collapse, releasing a large amount of energy. The estimated temperature and pressure at this time are estimated at 5000 and 2000 K atmospheres. This creates hotspots that accelerate the chemical reactivity into the medium, generating microjets directed towards the solid surface, also responsible for the general higher effectiveness of this technique, as the high pressure and tem-perature involved in the process destroy the cell walls of the plant matrices and their content can be released into the medium more easily.

Some new process aiming at agro-industrial waste application in food indus-tries based on ultrasound-assisted extraction of natural products have been reported

1 3

Top Curr Chem (Z) (2018) 376:3 Page 41 of 54 3

[71–79], as is the case of carotenoid separation from pomegranate peels using differ-ent vegetable oils as solvents [72]. Sunflower and soybean oils were used as solvents and parameters such as time, temperature, solid/oil ratio used were analyzed con-sidering the yield. It was found that the optimum mild operating conditions were: extraction temperature, 51.5  °C; peel/solvent ratio, 0.10; amplitude level, 58.8%; solvent, sunflower oil. Additionally, a subsequent separation of oil and carotenoids was not necessary, since the pigmented oil can be used as a carotenoid source in dif-ferent commercial products in this format.

The green recovery of cellulose from oil palm bunches by autoclave-based and ultrasonication pre-treatments were successfully developed to replace the non-green chlorite method [73]. An ultrasonic process with hydrogen peroxide yielded 49% cellulose with 9.13% alpha-cellulose content and 68.7% crystallinity, as compared to 64% cellulose with an autoclave treatment. The cellulose/polypropylene composites generated with high tensile strength, high thermal stability, and low water and diesel sorption showed great potentials for conversion into eco-composite products such as polymeric material insulated cables for high voltage engineering, automotive parts, sports tools and other household or office items.

Another highly cited green and sustainable technique to isolate organic com-pounds from bio-based waste is based on supercritical fluid processing (Fig. 5). It is widely known that substances at temperatures and pressures near or above their critical points have exceptional solvent characteristics for analytical purposes. These supercritical fluids possess liquid-like solvating and gas-like diffusivity power, and other tuneable properties that can be adjusted varying temperature, pressure and the addition of other components acting as a modifier. Due to its gas-like low viscosity and high diffusivity, the supercritical fluid can easily penetrate into plant materials with a fast mass transfer rate. Possibly, the most important property of supercritical fluids for separation processes is diffusion, obtaining solubility and diffusion good enough to provide quantitative extraction yield [80, 81]. Carbon dioxide (scCO2) is the fluid most widely used for extractions, with critical parameters of 31.1 °C and 73 atm (7.39 MPa), at relatively low operating conditions. It behaves as a nonpolar or polarizable solvent and low molar mass alcohols (co-solvents) are often added in small quantities to modify the solvent polarity. Because carbon dioxide can be depressurized to the gaseous state, the solvent is easily removed and supercritical fluid-based separation methods are easily coupled with subsequent analysis. There-fore, scCO2 provides miscibility to the majority of natural products, availability and low cost, reliably high purity, negligible toxicity, facility for removal and reuse, resulting in many advantages for downstream processing in terms of product purifi-cation and/or catalyst recycling [80].

The approach using scCO2 has been widely used for isolation and purification of chlorophylls, carotenoids, lipids, alkaloids, antioxidants from matrices such as filter tea, spruce bark, tomato and elderberry pomace, grape, passiflora, coffee and cupuassu seed waste [82–99]. In addition to the optimization of the separation pro-cess, some studies also aim to evaluate the techno-economic viability of large-scale commercial production, for example, to obtain cupuassu butter from cold-pressed seed residues, also evaluating the influence of thermodynamic and kinetic variables of yield, chemical composition and production costs of the extracts [86]. Optimal

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conditions related to extraction kinetics, chemical composition and production costs were 30–35 MPa and 50 °C. It was shown that the phenolic content (0.47–2.82 mg/g) was lower than those commonly found using other methods (20–23 mg/g). The high contents of tocopherols, as well as the unsaturated fatty acids (48%) compared to the saturated fatty acids (52%) present in the butter obtained by scCO2 demonstrated its great potential as an ingredient in food, pharmaceutical and cosmetic industries. In addition, process intensification for biodiesel production involving supercritical fluids has been reported [84, 90]. Such approaches can allow biodiesel production without any addition of catalyst, or via catalytic in situ or reactive extraction pro-cess, combining the extraction and reaction phase together in a single operation unit. These studies also discuss both processes towards the future bio-refinery setup and more efficient use of all waste produced.

The use of fluids different to CO2 has been described in the literature, but as they are usually organic solvents, they do not show any distinct advantages and often have high critical temperatures. Despite having a very high critical temperature, water shows unique properties in the subcritical region (200–300 °C), as a reduc-tion in dielectric constant (20–30) and density (0.7–0.8 g/cm3) compared to water at room temperature, improving its ability to dissolve nonpolar organic and inorganic compounds. Under these conditions, the water dissociation constant into hydroxide and hydrogen ions are more than three orders of magnitude higher, so that near-critical water acts as a self-neutralizing acid or base catalyst, avoiding salt waste generation. Moreover, using subcritical and supercritical water conditions greatly simplifies the product purification step in some cases, since nonpolar products are insoluble in water in lower temperatures [80, 100–106].

Other potential scalable approaches have been described, such as enzymatic [107–114], alkaline [115–120] and based on different types of aqueous media (e.g., cyclodextrins, montmorillonite K-10/LiOH, green liquor) [121–130]; ionic liquids [131–135], deep eutectic solvents [136–138], constituting alternative methods for the recovery of high added-value compounds from agro-industrial waste aiming at obtaining the best analytical, economical and socio-environmental compromise [139–142].

Based on the investigated literature [143], Table  2 summarizes the advantages and disadvantages of the four most cited green and sustainable techniques.

4 Conclusions

The establishment of vanguard biorefineries for bioeconomy and circular economy urgently demands innovation in green and sustainable separation for the recovery of natural products from agro-industrial by-products all over the world. Sustaina-ble separation includes the idea of integrated valorization not only in an economic sense, but also strengthens other social and environmental dimensions, from small to large producing scales. According to the literature over the last decade, the num-ber of studies in this field has grown significantly in recent years. New approaches incorporating holistic extraction and/or purification techniques, also integrating sys-temic chemical transformation through the design and use of renewable materials

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Top Curr Chem (Z) (2018) 376:3 Page 43 of 54 3

Tabl

e 2

Adv

anta

ges a

nd d

isad

vant

ages

of d

iffer

ent t

echn

olog

ies t

hat w

ere

mos

t cite

d as

gre

en a

nd su

stai

nabl

e te

chni

ques

ove

r the

last

10 y

ears

Adv

anta

ges

Dis

adva

ntag

es

Solv

ent p

roce

ssin

gIn

expe

nsiv

e an

d si

mpl

icity

; allo

ws f

or so

lven

t reu

seD

oes n

ot a

lway

s use

s ben

ign

solv

ents

; fre

quen

tly re

quire

s an

evap

ora-

tion/

conc

entra

tion

step

for r

ecov

ery;

usu

ally

dem

ands

larg

e am

ount

s of

solv

ent a

nd lo

ng e

xtra

ctio

n tim

e; p

ossi

bilit

y of

ther

mal

deg

rada

tion

Mic

row

ave

proc

essi

ngRe

duce

d ex

tract

ion

time;

redu

ced

solv

ent u

sage

; im

prov

ed e

xtra

ctio

n yi

eld;

sim

ple

and

inex

pens

ive

Not

goo

d w

hen

eith

er ta

rget

com

poun

ds o

r sol

vent

s are

non

-pol

ar o

r vo

latil

esU

ltras

onic

atio

nIn

expe

nsiv

e, si

mpl

e an

d effi

cien

t; ca

n re

duce

the

oper

atin

g te

mpe

ratu

re

(goo

d fo

r the

rmol

abile

com

poun

ds);

can

be u

sed

with

any

solv

ent

Its e

ffici

ency

may

be

linke

d to

the

natu

re o

f pla

nt m

atrix

; the

act

ive

part

of u

ltras

ound

insi

de th

e ex

tract

or is

restr

icte

d to

a z

one

loca

ted

in th

e vi

cini

ty o

f the

ultr

ason

ic e

mitt

erSu

perc

ritic

al fl

uid

Mod

erat

e ex

tract

ion

tem

pera

ture

(goo

d fo

r the

rmol

abile

com

poun

ds);

rapi

d m

ass t

rans

fer (

larg

er e

xtra

ctio

n ra

te);

solu

bilit

y of

a c

hem

ical

in

a su

perc

ritic

al fl

uid

can

be m

anip

ulat

ed; c

an e

limin

ate

conc

entra

tion

proc

ess;

the

solu

tes c

an b

e se

para

ted

from

supe

rcrit

ical

flui

ds w

ithou

t lo

sing

vol

atile

s due

to it

s ext

rem

e vo

latil

ity; a

dditi

onal

filtr

atio

n or

ce

ntrif

ugat

ion

to re

mov

e so

lid re

sidu

e is

not

nec

essa

ry

One

rous

ope

ratin

g co

nditi

ons

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and optimized processes should combine the best green analytical figures of merit with online evaluation of the whole production chain. These approaches should gen-erate healthier and more efficient products, methods and processes at an affordable and fair cost.

Overall, solvent processing and its modification towards the enhancement of mass transfer to remove the compounds of interest from selected waste have been widely used (25%), also on industrial scales. Alternative extraction or purification methods have shown increasingly more applications, such as for microwave, ultrasonication and supercritical fluid processing. It was shown that a wide range of natural products and their derivatives are used mainly in food (as dyes, aromas, flavors) in medicines or green formulations in agriculture. According to the data available, one paradig-matic case largely studied is the valorization of citrus waste, representing more than 10% of all residues considered in the research papers.

Moreover, an emergent challenging topic is to evaluate biorefinery processing alternatives, i.e., sustainability assessment tools, for example LCA, which include parameters such as feedstock supply (to verify the suitability and adequacy of a potential biomass feedstock for the separation or transformation treatment), process performance (to assess the input–output balance of material and energy flows) and bio-based chemical production [144]. Therefore, the decision about the best separa-tion approach takes into account various fundamental aspects and is based on green and sustainable assessment tools, considering the type of agro-industrial waste (e.g., quantity, periodicity, chemical variability, water amount, distance to the processing unit), the natural target products (chemical quality, purity, humidity, costs etc.) and available technologies.

Using sustainability indicators and tools will be increasingly demanded in this field, contributing to the greenness or sustainability of the whole processing system. The development of a sustainable separation method which provides better recovery efficiency will not only add value to the agro-industrial waste, reducing the over-all manufacturing costs and the use of synthetic chemicals, but will also aggregate value to the whole production chain, including its final products. The emergence of bio-based industries is changing the current status of the producing systems, con-tributing to the current biomass residual losses. Based on the literature, the scenario for future research and innovation in green and sustainable separation for the recov-ery of agro-industrial waste is truly beginning, bringing together various areas and sectors towards more efficient and circular systems.

Acknowledgements The authors wish to thank FAPESP (13/12052-5, 14/50827-1), Capes (2032/2014-07), EPSRC-UK (EP/M028763/1) and Mateus Segatto.

Open Access This article is distributed under the terms of the Creative Commons Attribution 4.0 Inter-national License (http ://crea tive comm ons.org/lice nses /by/4.0/), which permits unrestricted use, distribu-tion, and reproduction in any medium, provided you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made.

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