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Waste Management xxx (2017) xxx–xxx

Contents lists available at ScienceDirect

Waste Management
journal homepage: www.elsevier.com/locate/wasman

Reutilization of discarded biomass for preparing functional polymer


materials
Jianfeng Wang, Wenzhen Qian, Yufeng He ⇑, Yubing Xiong, Pengfei Song, Rong-Min Wang ⇑
Key Laboratory of Eco-Environment-Related Polymer Materials of Ministry of Education, Institute of Polymer, College of Chemistry & Chemical Engineering, Northwest
Normal University, Lanzhou 730070, China

a r t i c l e i n f o a b s t r a c t

Article history: Biomass is abundant and recyclable on the earth, which has been assigned numerous roles to human
Received 2 December 2016 beings. However, over the past decades, accompanying with the rapid expansion of man-made materials,
Revised 6 April 2017 such as alloy, plastic, synthetic rubber and fiber, a great number of natural materials had been neglected
Accepted 9 April 2017
and abandoned, such as straw, which cause a waste of resource and environmental pollution. In this
Available online xxxx
review, based on introducing sources of discarded biomass, the main composition and polymer chains
in discarded biomass materials, the traditional treatment and novel approach for reutilization of dis-
Keywords:
carded biomass were summarized. The discarded biomass mainly come from plant wastes generated
Discarded biomass
Natural polymer
in the process of agriculture and forestry production and manufacturing processes, animal wastes gener-
Functional polymer materials ated in the process of animal husbandry and fishery production as well as the residual wastes produced in
Reutilization the process of food processing and rural living garbage. Compared with the traditional treatment includ-
ing burning, landfill, feeding and fertilizer, the novel approach for reutilization of discarded biomass prin-
cipally allotted to energy, ecology and polymer materials. The prepared functional materials covered in
composite materials, biopolymer based adsorbent and flocculant, carrier materials, energy materials,
smart polymer materials for medical and other intelligent polymer materials, which can effectively serve
the environmental management and human life, such as wastewater treatment, catalyst, new energy, tis-
sue engineering, drug controlled release, and coating. To sum up, the renewable and biodegradable dis-
carded biomass resources play a vital role in the sustainable development of human society, as well as
will be put more emphases in the future.
Ó 2017 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ......... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2. Sources of discarded biomass and traditional treatment. . . . . . . . ......... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3. The main composition and polymer chains of discarded biomass materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
4. The novel approach for reutilization of discarded biomass . . . . . . ......... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
5. Functional composite materials. . . . . . . . . . . . . . . . . . . . . . . . . . . . ......... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
6. Biopolymer based adsorbent and flocculant. . . . . . . . . . . . . . . . . . ......... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
7. Biopolymer based carrier materials . . . . . . . . . . . . . . . . . . . . . . . . ......... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00

Abbreviations: AA, acrylic acid; AM, acrylamide; BA, butyl acrylate; CF, chicken feather; CMC, carboxymethyl cellulose; CS, chitosan; DAAM, diacetone acrylamide;
DMDAAC, dimethyl diallyl ammonium chloride; E-PHK, pig hair keratin; E-PHKPGel, (E-PHK)-based biopolymer hydrogel; FK, feather keratin; HA, humic acid; HTC,
Hydrothermal carbonization; MAA, methacrylic acid; MMA, methyl methacrylate; MSW, Municipal solid waste; NOR, norfloxacin; ORR, oxygen reduction reaction; PAN,
polyacrylonitrile; PC, polycarbonate; PdNPs, palladium nanoparticles; PE, polyethylene; PEG, polyethylene glycol; PEO, poly(ethylene oxide); PHA, polyhydroxyalkanoates;
PLA, Polylactic acid; PLMA, polymalic acid; PNIPAAm, poly (N-isopropylacrylamide); PoSt-g-BMD, potato starch-based graft copolymer; PoSt-g-BMD-C, potato starch-based
graft copolymer coatings; PP, polypropylene; PTE, polysulfide ester; PTT, Polytrimethylene terephthalate; PVA, poly-vinyl alcohol; SDZ, sulfadiazine; SHR, soybean hulls
residue; TC, tetracycline; TTI, Time-Temperature Indicator; TYL, tylosin; WPCs, wood polymer composites; WSC, wheat straw carboxymethylcellulose; WSM, wheat straw
matrix.
⇑ Corresponding authors.
E-mail addresses: heyufeng@nwnu.edu.cn (Y. He), wangrm@nwnu.edu.cn (R.-M. Wang).

http://dx.doi.org/10.1016/j.wasman.2017.04.025
0956-053X/Ó 2017 Elsevier Ltd. All rights reserved.

Please cite this article in press as: Wang, J., et al. Reutilization of discarded biomass for preparing functional polymer materials. Waste Management
(2017), http://dx.doi.org/10.1016/j.wasman.2017.04.025
2 J. Wang et al. / Waste Management xxx (2017) xxx–xxx

8. Energy materials from waste biomass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00


9. Smart polymer for medical materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
10. Other intelligent polymer material . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
11. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00

1. Introduction and animal wastes and they are contained among them. In the glo-
bal scope, there is 140 billion metric tons of biomass generated
Biomass is abundant and recyclable on the earth, which has from agriculture annually (Oladeji and Oyetunji, 2013). These vol-
been assigned numerous roles to human beings from ancient umes of biomass are converted into a substantial amount of raw
times. However, accompanying with the rapid expansion of man- materials. Meanwhile, they produced different forms of discarded
made materials, such as alloy, plastic, synthetic rubber and fiber, biomass residue (Vaisanen et al., 2016). Extraordinarily in China,
a great number of natural materials had been neglected and aban- as a large agricultural country with a high-ranking in global crop
doned, such as straw, which cause a waste of resource and environ- production (Huang et al., 2012), it has abundant agricultural waste
mental pollution. In the beginning of 20th century, the rapid resources, such as the crops straw. The annual production of waste
expansion of relatively low-priced petrochemical production inhi- crop straw is as high as approximately 0.7 billion tons, of which
bits the development of agricultural industry. In the midst of them, 70% is composed of rice straw, wheat straw and corn stalk. So
synthetic polymer materials have lots of advantages, such as easy- China has the most discarded biomass resources in the world
machined, beautiful and practical, which met the needs of different (Liu et al., 2013). In the process of forestry production, generally,
industry areas and gradually took the place of traditional materials wastes come from the process of forest harvesting, raw wood man-
(Wong et al., 2015). Every year, millions of tons of petrochemical ufacturing and wood processing, such as wood chips, sawdust,
polymer materials, such as polyethylene (PE), polypropylene (PP) shavings (Tan et al., 2015), which are up to about 110 million tons
and polycarbonate (PC), were produced and used in daily life, each year. Urban greening and wood wastes also occupy a large
industrial and agricultural production. Most of non-renewable proportion of city solid wastes. It is also known as ‘‘another kind
and non-biodegradable synthetic materials were used in a short of forest”, which is the forest that lying on the ground. Besides,
period and promptly became wastes, which resulted in seriously there are many kinds of natural polymer in the living garbage, such
environmental ‘‘white pollution” at present. On the other side, with as walnut shell, coconut shell, fruity nucleus, chestnut shells, cot-
the depletion of fossil resources and the soaring prices of crude oil, ton seed shell and pineapple peel. Additionally, a large number
the production of petrochemicals from fossil as raw materials has of residues, such as bean curd, lees, bagasse, and food industrial
been a severe challenge (Xiong et al., 2012a,b). Therefore, biomass scraps, have been discharged from food processing industry
resources have been paid increasing attention because of their (Marcet et al., 2016; Moreno et al., 2016; Raak et al., in press;
renewability and biodegradability (Wang et al., 2016a,b; Steur et al., 2016). For instance, in the fish or shrimp processing,
Komatsu et al., 2006). In particular, the composition and energy the amount of wastes can be reached as high as 60% of the marine
utilization of biomass energy are very similar to fossil energy. Thus, animals’ weight. After obtaining the fish fillets, the remaining 50–
it has the largest potential to substitute for conventional energy 60% of the whole fish is discarded as by-products or wastes (Torres
(Zhou et al., 2016a,b). et al., 2007). It is understandable that why the problem of indus-
Biomass materials had been used as structural materials or trial by-products and wastes in food processing has attracted the
common materials from ancient times because their major compo- interest of researchers, regulatory departments, industry and con-
nents were natural polymers, such as lignin, cellulose, starch, sumers and has urged the European Union towards ‘‘a zero-waste
chitin and protein, which guaranteed enough strength and stabil- economy” by 2025 (Naziri et al., 2014).
ity. However, a lot of natural polymers were discarded as forms During development in thousands years, human have gradually
of biomass on account of the ignorant of their real value. In the past accumulated valuable experience in processing and recycling of
decades, increasing emphases were turned to natural polymers in discarded biomass resources. Except for landfill, the typical meth-
the development of environmentally-friendly products and fuels ods are burning, feeding and fertilizer. In the agrarian age, some of
(Moon et al., 2011; Wang et al., 2012). Overall, the depletion of agricultural wastes were directly used as animal feed. Part of
non-renewable resources and the environmental pollutions moti- discarded biomass materials can be disposed by microbial
vate the increasing demands of renewable resources and there is transformation, which provides microbial protein products, then
still a long way towards dealing with all of problems. In this becoming animal feed (Sun et al., 2005). Meanwhile, in some
review, from the perspective of polymer chemistry and functional undeveloped, rural and agricultural districts, as well as several
materials, the development and research progress on reutilization peri-urban areas, people cooked or heated by burning agricultural
of discarded biomass and the preparation of functional materials residues in their daily lives. Direct incineration of discarded
has been summarized. biomass is deemed to a common way of disposal in developing
countries including China (Huang et al., 2012). The direct combus-
2. Sources of discarded biomass and traditional treatment tion of discarded biomass in cropland is a kind of lower-priced way
for disposal of discarded biomass. However, the excessive combus-
Almost all discarded biomass are come from plants, animals and tion of discarded biomass releases large quantities of greenhouse
microbial wastes. The plant wastes are generated in the process of gases and dust, which not only lead to formidable air pollution
agriculture and forestry production and manufacturing processes. such as fog and haze, smog and acid rain (Ding et al., 2013; Li
The animal wastes are generated in the process of animal hus- et al., 2016a,b), but also a seriously waste of valuable natural
bandry and fishery production, and the residual wastes are pro- resources including energy, materials, nutrients and minerals
duced in the process of food processing and rural living garbage. substances. It was reported that the concentration of particulate
In addition, microbial wastes are mainly produced in the plant matter may increase dramatically in downwind suburbs and rural

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areas because of postharvest combustion of discarded biomass like polyester. Specifically, polysaccharide mainly includes cellulose,
rice straws and maize straws (Zhang et al., 2010a,b). Moreover, starch, chitosan (CS) and collagen while polyamide contains pro-
agricultural wastes could also be utilized as fertilizer, such as var- tein and amino acid, and polyphenol mainly includes lignin and
ious compost (aerobic), wet compost (facultative anaerobic) and humic acid. Moreover, polyisoprene includes natural rubber and
fertilizer from biogas (anaerobic), which may not merely raise soil gutta-percha while organic polyethylene oxide esters include poly-
porosity, but also organic minerals containing N, P and K (Zhu et al., hydroxyalkanoates (PHA), polymalic acid (PLMA) and cutin.
2015). Simultaneously, fertilizers carry out biochemical reaction Polyphosphate is the typical representative of inorganic polyester,
based on microorganisms which would transform organic wastes which exists in most of different types of cells.
into high-efficacy organic fertilizers similarly humic process. The There are three kinds of biopolymers (lignin, polysaccharide
landfill disposal is widely used in recent years, of which the rate and protein) in discarded biomass (Fig. 1). Lignin is the second
of refuse disposal, it reaches 95–100% (He et al., 2016a,b; most abundant natural polymer consisting of methoxylated phenyl
Emadian et al., 2017). This processing technology possesses lots propane structures (Singh et al., 2016) on the earth which widely
of merits, such as technical maturity, simple operability, large exists in wooden structure, approximately accounting for 25–35%
capacity and consumability. However, it could not be neglected of the organic matrix of wood (Montazeri and Eckelman, 2016).
that if wastes are biohazardous, they might cause serious Although lignin is produced 150 billion tons every year, most of
environmental pollution problems even destruction. It is also them are not used as raw materials in the industrial production
result in a waste of resources. due to its thermal and biological stability and cytotoxicity
(Numata and Morisaki, 2015). Besides, the commercial lignin basi-
cally comes from paper-making industry and ethanol industry. The
3. The main composition and polymer chains of discarded amount of by-products of lignin in papermaking industrial produc-
biomass materials tion is more than 30 million tons every year (Hatakeyama and
Hatakeyama, 2009). Therefore, lignin is an extensive biomass
On the base of polymer science, natural polymers include inor- source, with renewable, non-toxic and low-priced ability, but inad-
ganic and organic polymers. Natural organic polymer is a signifi- equate utilization may further pollute the environment.
cant biopolymer with dividing into 8 categories, such as Polysaccharide includes cellulose, starch, chitin and CS, whose
polysaccharide, polyamide, polyphenol, polyisoprene, nucleic acid, structural units are glucose. The differences are substituent or
polysulfide ester (PTE), polyethylene oxide ester and inorganic stereochemical structure. Specifically, cellulose is not merely the

Fig. 1. The typical structure of polysaccharide (Lignin, Cellulose, Starch, Alginic acid, Chitin, Chitosan and Humic acid) and Proteins (Keratin containing -S-S-).

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basic component of plant cell wall which forms about half of one-
third of plant tissues, but also the most abundant renewable and
biodegradable material available in the nature (Xu et al., 2016). It
is constantly restocked by photosynthesis, and it is estimated that
the amount of biosynthesis up to 10 11 tons yearly (Kaya et al.,
2016). Starch is the mixture of amylose and amylopectin, which
are products of photosynthesis and existing semicrystalline in
plant cell plastids (Gao et al., 2016). Hemicellulose accounts for
approximately 20–30% total amount of biomass in the nature
which is generally less than cellulose polymers. It is found that
most of hemicellulose is in xylems of hardwood with the degree
of polymerization of 100–400 (Borjesson and Westman, 2016).
Chitin mainly exists in the shells of crustaceans such as shrimps,
crabs and insects. It is a copolymer with N-acetyl-D-glucosamine
and D-glucosamine units linked through b-(1–4) - glycosidic bond,
where N-acetyl-D-glucosamine units are predominant in the poly-
meric chain. In the global, about 100 billion tons of chitins are nat-
urally generated as by-products per year, while waste chitins from
industrial production are about 10,000 tons (Kim, 2010). Chitosan,
the deacetylated form of chitin, is the sole natural alkaline polysac-
Fig. 2. The typical technical route for reutilization of discarded biomass in energy,
charide found in the nature so far, also consists of the most content
ecology and polymer materials.
of cationic polysaccharide. Moreover, CS is highly biocompatible
and biodegradable but poorly water-soluble, so CS modifications
are necessary to expand applications (He et al., 2011, 2016; products, which extensively exist in hair, feathers, wool, nails, and
Wang et al., 2005). Humic acid, generated by the death of organ- horns (Li et al., 2011a,b). Especially, the keratin content of animal
isms by biodegradation, is the main component of humus as well hair and poultry feather is more than 90% (Coward-Kelly et al.,
as the predominant organic compounds of soil, peat, and coal, 2006) and the output of abandoned feather reaches more than
many upland streams, humic nutrition lakes, and seawater 1 million tons yearly. In China, although the annual production of
(Urrea et al., 2017). It is usually showed the properties of dibasic poultry feathers is more than 700,000 tons (Xia et al., 2012), most
acid or ternary mixture acid, owing to containing carboxyl, pheno- of them are underutilized except a few of them are used as filling
lic hydroxyl and other functional groups. materials because of its thermal properties. On the other side, part
Proteins are basic materials in animal and microbial cells, which of plant proteins are outputted as a by-product, such as zein (Yang
accounts for 16–20% of body weight. The species of proteins are et al., 2014), soybean protein isolated (Wang et al., 2011).
great in the nature, and most discarded proteins are keratin, colla-
gen and plant protein. Therein, the discarded collagen mainly from
skin and tendon tissue accounts for 25–30% of total protein weight 4. The novel approach for reutilization of discarded biomass
and even over 80% in several animal bodies (Shoulders and Raines,
2009). Keratin widely exists in body parts such as skin, hair and The discarded biomass has been traditional reutilization as feed,
nails of vertebrates and it is rich in cysteine residues and disulfide fertilizer and matrix. Depending on the progress of science and
bond (Wang et al., 2010a). Nonetheless, a lot of keratin, especially technology, it has also been applied to energy, ecology and poly-
feather keratin, is abandoned, leading to a waste of resources (Guo mer materials (Xiao et al., 2016; Quispe et al., 2016; Iglesias
et al., 2014). et al., 2017). The relationship between bio-based products and
Generally, lignin and polysaccharide come from stem, leaf and their transformation are showed in Fig. 2. Since 1970, the utiliza-
root of plants, and protein comes from animal and plant seed. Agri- tion of biomass energy has been increased by many governments.
cultural straw is the most vital part of agricultural waste, contain- It is quite practical and significant that the environmentally
ing most of natural polymers such as cellulose, hemicellulose and friendly discarded biomass is converted into clean, low-priced
lignin. For example, in corn straws, the amount of cellulose, hemi- and high quality biomass energy through bio-refinery techniques.
cellulose and lignin are 45%, 35% and 15%, respectively. Rice straw As fuels, straw and other biomass wastes are approximately equiv-
contains 60% polysaccharide which are cellulose and xylan, and the alent to medium coal after transforming into solid form, and some
residuals are lignin and ash content (Swain and Krishnan, 2015). In shortcomings of conventional coal do not present in biomass
other word, straw contains most of cellulose, hemicellulose and energy. The thermal efficiency is as high as 94% after transforming
lignin, the amounts are about 33.14–45.93%, 15.58–19.32% and agricultural waste into biogas. Municipal solid waste (MSW) is cap-
21.84–27.24% (Chen et al., 2015), respectively. Plant kenaf contains able of producing clean and combustible gas according to the prin-
60–80% cellulose while the percentage of lignin is only 5–20% ciple of biomass thermal gasification by users. Wheat straw could
(Saba et al., 2015). Sugarcane bagasse contains 59.0% of fiber, be used in the production of ethanol, biological hydrogen and
20.9% of lignin and 20.6% of pentosan as well as proteins, a few methane (Poulsen and Adelard, 2016), and its waste liquid is able
minerals, waxes and other compounds (Chandel et al., 2012). Dry to be further usage of making methane (Kaparaju et al., 2009).
bean dregs contain 50% of cellulose, 16–34% of protein, fat, and Isikgor and Becer (2015) used fast pyrolysis reactor to convert dis-
ash content (Li et al., 2013a,b,c). In palm slag after being extracting carded biomass from material of agriculture and forestry into bio-
palm oil, there are roughly 90% of cellulose, hemicellulose, and lig- fuels, with 60.2% rate of production. Rocha et al. (2012) disposed
nin (Kong et al., 2014). bagasse with biological method to prepare ethanol, which could
There are abundant collagen in land and aquatic animals and be used as a biofuel as well.
their processing waste, like skin, bone, and scale. It is certainly that From a technical point of view, efficiently comprehensive uti-
collagen of marine animal has low antigenicity and hypoallergenic lization of biogas fermentation device and ecological agriculture
compared with the collagen of terrestrial animal. Keratin is the pattern are the hotspots of current research (Kennes et al., 2016).
most abandoned protein in the process of agricultural and sideline This comprehensive utilization model is also applied to biomass

Please cite this article in press as: Wang, J., et al. Reutilization of discarded biomass for preparing functional polymer materials. Waste Management
(2017), http://dx.doi.org/10.1016/j.wasman.2017.04.025
J. Wang et al. / Waste Management xxx (2017) xxx–xxx 5

materials. For example, plant straw, a typical discarded biomass, of (2013) found study demonstrates that PLA can be directly grafted
which energy utilization rate would be only 20% if it is digested by onto unmodified lignin by ring-opening polymerization with an
livestock. In contrast, using a comprehensive utilization model, organic catalyst (Fig. 3). The synthesized lignin-g-PLA copolymers
named ‘‘straw - edible fungus - pig - gas - fertile field”, the utiliza- with appropriate grafted PLA chain lengths can be utilized as dis-
tion rate of energy would be over 50%. The utilization rate of persion modifiers in PLA-based biobased composite materials,
organic matter and nutrient element could reach 95% (Zeng et al., improving UV absorbance as well as mechanical properties.
2007). The potential use of waste biomass based biochar as reinforce-
As biomass materials in organisms contains many kinds of ment in the fabrication of polymer based composites was proposed
small molecules and macromolecules with diverse functions and by Das et al. (2015a). To identify a route for organic wastes utiliza-
biological activities. Some extracts from biomass could be used tion, they collected six biochars from various feedstocks (landfill
as drugs (Tao et al., 2012; Jia et al., 2008) or functional edible food pine saw dust, sewage sludge, and poultry litter) at diverse pyrol-
except for life needs. For instance, bean dregs, one of the typical ysis conditions to manufacture the biocomposites (Das et al.,
wastes in food industry, contain a large number of dietary fiber 2016). They found that addition of biochar did not disrupt the crys-
and soy isoflavones with various efficacies such as antioxidant (Li tal structure of the PP. The poultry litter biochar (with high CaCO3
et al., 2011a,b), anti-cancer ability, cholesterol reduction, and pre- based mineral) composites were observed to have a lower heat
vention of atherosclerosis and osteoporosis. Biopolymer is derived release rate among the other composites. They also postulated that
from organisms. wood polymer composites (WPCs) being added with biochar has
Although it cannot be absorbed by human body, cellulose has good potential to mitigate wastes. Simultaneously, the obtained
the desirable function of cleaning intestine which is suitable for biocomposites might be suited for various end applications (Das
patients with IBS (irritable bowel syndrome) to eat healthy food et al., 2015b).
(Jones, 2014). Zhu et al. (2016) reported that two extracts were Ma et al. (2015a,b) prepared a macroporous nanocomposite bio-
produced by degradative solvent extraction at 250–350 °C when mass with efficient adsorption capacity to displace toxic ions via
rice straw and fir sawdust were used as the raw biomass materials. natural polymer Xanthan gum and silicate. This nanocomposite
And those extracts were good additives for coke-making. There is exhibited a special macroporous structure and properties, as well
no doubt that the soluble polysaccharide could be extracted in as a better cation exchange capacity for retaining cation ions.
bean dregs, which is capable to be converted into bioethanol and Ahmadzadeh et al.’s (2015) had incorporated cellulose nanocom-
reductive polysaccharide. posites foams with surface-modified montmorillonite through a
Our group (Wang et al., 2010a; Li et al., 2011a,b; Li et al., 2013a, high shear homogenizer method, which afforded a new kind of
b,c; Wang et al., 2015a,b,c,d) had studied reutilization of discarded material. Ardanuy et al. (2012) successfully prepared recycled
feathers with simple method. We found that feather keratin (FK), polypropylene-based composite foams reinforced with untreated
one of low-cost natural polymers, could to be effectively extracted and chemically-treated cellulose fibres obtained from agricultural
from discarded chicken feathers. The extracted pure FK had been residues were successfully prepared using a high-pressure CO2 dis-
applied to prepare novel functional polymer materials, such as solution physical foaming process. A clear increase in Tg was
packaging materials, biopolymer flocculants, biopolymer antioxi- observed with adding the cellulose fibres to PP, related to a lower
dant, biopolymer photocatalyst and keratin films based drug molecular mobility of the amorphous portion of PP induced by the
carriers. cellulose fibres. The specific storage modulus was higher for all
In summary, with the exception of usage in energy, ecology and solid composites when compared to unfilled PP, related to the
convention, the discarded biomass has been utilized to prepare higher stiffness of the cellulose fibres. These results show that
functional polymer materials, such as functional composite mate- foams prepared from recycled PP and barley straw obtained from
rials, biopolymer based adsorbent and flocculant, carrier materials, agricultural residues may find potential applications as lightweight
energy materials, medical polymer materials and other intelligent composites in different fields such as construction or automotive.
polymer materials. Fan et al. (2016) focused on preparation and structural investiga-
tion of water insoluble keratin/poly(ethylene oxide) (PEO) blend
nanofiber mat with high content of keratin for biomedical uses.
5. Functional composite materials The biocompatibility of the water insoluble keratin/PEO blend
nanofiber mat was also researched via cell cultivation, which
With new performances on macroscopic or microscopic obser- asserted that nanofiber had the potential in tissue engineering
vation through physical or chemical methods, composite materials and biomaterials field.
are becoming important construction material or functional mate-
rials. It is leading to their comprehensive performances better than
that of the original composition materials and meeting the 6. Biopolymer based adsorbent and flocculant
demands of the various and expanding its application in the future
(Yu et al., 2016; Goh et al., 2016). The miscibility properties of lig- The pollution of heavy metal has attracted widespread atten-
nin and other biological plastics could be improved with grafting tion on account of its severe effects on environment and living
modification of Polylactic acid (PLA). For instance, Chung et al. organisms. Wang et al. (2014a,b,c) had prepared wheat straw

Fig. 3. The preparation of Lignin-PLA copolymer.

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(2017), http://dx.doi.org/10.1016/j.wasman.2017.04.025
6 J. Wang et al. / Waste Management xxx (2017) xxx–xxx

matrix-g-polyacrylonitrile-based adsorbent (WSM-PAN) by means In addition to activated carbon, flocculant also has a unique
of living free radical polymerization technology (Fig. 4). Its adsorp- merit in wastewater treatment. Bentonite, a natural inorganic min-
tion capacity of Hg2+ had ascended greatly when polyacrylonitrile eral material, is a promising material in wastewater treatment
(PAN) was grafted to the surface of the WSM. We found that the because of good adsorption ability, dispersibility, stability and
wheat straw carboxymethylcellulose (WSC) could be modified by non-toxicity. Using the AlCl3, FeSO4 and carboxymethyl starch as
functional poly(acrylic acid) (PAA) with in situ polymerization, raw materials, He et al. (2014a,b) had successful prepared a kind
which afforded polymer adsorbent for removing Pb(II) ions in of flocculant with 87.8% clearance rate of COD when it was applied
wastewater, and Pb(II) removal rate get to 99.8% in one hour at to the treatment of potato starch wastewater. It was also found
room temperature (He et al., 2014a,b). that some biological macromolecular flocculants showed excellent
Activated carbon is an excellent adsorbent for removal of pollu- flocculation performance (Pan et al., 2008; Zhang et al., 2010a,b).
tants from wastewater. Regenerative waste materials were found Recently, CS and its derivatives, acting as flocculants in wastew-
to serve as inexpensive alternative precursors for activated carbon ater treatment, have gained wide attention. Yang et al. (2016)
preparation (Suhas et al., 2016). Sun et al. (2016) had successfully reviewed CS-based flocculants and their applications in wastewa-
prepared activated carbons by grinding, sieving, drying and clean- ter treatment and discussed the mechanism of flocculation. It sug-
ing the arundo donax and pomelo peel, and it could be used for gested that the CS-based flocculants with proper structures have
adsorbing ciprofloxacin. Saucier et al. (2015) prepared activated great application potentials in wastewater treatment. Sun et al.
carbon from cocoa shell as adsorbents for removing sodium (2017) prepared CS-based graft polymer flocculant through
diclofenac and nimesulide from aqueous effluents. plasma-initiated polymerization using acrylamide (AM), dimethyl
As we know, CS has strong adsorption performance. It could be diallyl ammonium chloride (DMDAAC) as monomer. The obtained
modified by polyethylene imine for improving the amino func- CS-based graft polymer flocculant exhibited high flocculation per-
tional groups of CS. The prepared CS adsorbent with high specific formance with 99 % of turbidity removal rate and 96 % of COD
surface area porous can adsorb CO2, mainly applying in the treat- removal rate. Similarly, Wang et al., 2016a,b synthesized a cationic
ment of industrial waste gas (Fujiki and Yogo, 2014). The algal bio- CS-based polymer flocculant via grafting polymerization of cationic
mass, being derived from sea, is typical biological adsorbents for monomer onto CS. It also showed a highly effective flocculation
removing heavy metals (He and Chen, 2014). Soybean hulls resi- capability for activated sludge. Jia et al. (2016a) synthesized an
dues (SHR), a kind of food industrial waste, contains a plenty of aromatic rings-functionalized CS-based flocculant, which exhibits
hydroxyl groups. We successfully extracted SHR adsorbent from enhanced removal efficiency in the flocculation of binary contam-
residues in soybean milk through non-toxic and edible eluent inants of Cu (II) and tetracycline (TC). They also reported (Jia et al.,
(Wei et al., 2014). It is capable of quickly removing Pb2+ (Fig. 5), 2016b) amino-acid-modified-CS, a novel environmental-friendly
and could be used as edible antidotes. Shui et al. (2012) studied flocculant for removal of trace antibiotics in water by flocculation
on decolorization of dye wastewater through adsorption- in the coexistence of inorganic suspended particles and natural
microwave degradation of activated carbon that comes from bean organic matter.
dregs.

O
Br
OH
OH HO O n
HO OH 1) 2-BiBBr/Py N
10% NH3 H2O
WSM OH
WSM H2N
1 M HNO3 HO 2) CH2=CH2CN HO OH
OH O
OH 3) NH2OH HCl
70 0C, 20 hr O Br
n
N
OH
H2N

Fig. 4. The preparation of WSM-g-PAN-based adsorbent.

Fig. 5. The adsorption Pb2+ mechanism of SHR.

Please cite this article in press as: Wang, J., et al. Reutilization of discarded biomass for preparing functional polymer materials. Waste Management
(2017), http://dx.doi.org/10.1016/j.wasman.2017.04.025
J. Wang et al. / Waste Management xxx (2017) xxx–xxx 7

7. Biopolymer based carrier materials electrode materials of capacitor because of its good electronic con-
ductivity, large specific surface area, high chemical stability and
Protein, cellulose, chitin and CS with secondary and tertiary highly developed pore structure. Ma et al. (2015a,b) prepared a
structure all have a variety of active groups with easy to be modi- kind of nitrogen-doped porous carbon by utilizing potato waste
fied, which afforded to carry active compounds. They could also be residues. The nitrogen-doped porous carbon exhibited high capac-
produced into different shapes, such as flake, gel ball, film, fiber, itive performance, and the specific capacitance is up to 255 Fg 1 in
hollow fiber membrane and spongy, as well as loading on inert 2 M KOH electrolyte when using carbon as electrode materials. Jin
materials. The sugarcane agriculture residues from agro-industry et al. (2007) utilized a coconut shell to prepare activated carbon
are biomass feedstock (Alonso et al., 2007). Marcelo et al. (2016) with the function of oxygen storage. At present, it is usage of acti-
prepared a lignin inspired polyethylene glycol (PEG) hydrogel by vated carbon as electrode materials that have already been a
using catechol as the cross-linking species. The obtained hydrogel mature technology.
with high water-swelling capability (swelling degree near 2400%) Although the porous carbon has lots of benefits, it is still a high-
could be used as an advanced drug delivery system. The largest priced product. So, N doped porous carbon is increasingly becom-
cumulative release rate could reach 60% while the longest time ing an interesting research since it possesses higher activity and
of release up to near 2 months. Duan et al. (2011) found that CS- easier storage. Using pig bones (Wang et al., 2015a,b,c,d), bean
graft-PNIPAAm could be used as effective drug carriers for intra- dregs (Zhang et al., 2015) and chicken bones (Song et al., 2014)
cameral pilocarpine administration. Lai and Luo (2017) found that as materials, some novel energy materials of N doped porous car-
CS-graft-PNIPAAm systems exhibited good cytocompatibility with bon had been prepared, which have multilevel pores, high specific
lens epithelial cell cultures. That mean the injectable and surface areas and active sites. Additionally, they have good cat-
biodegradable CS-based thermogels with can be potentially uti- alytic activity, stability and anti-poisoning ability of methanol for
lized as ophthalmic biomaterial carriers. oxygen reduction reaction (ORR) in alkaline electrolyte. The oxy-
Due to strong affinity of metal ions, CS is as well as commonly gen reduction activity of N doped porous carbon is much higher
used to load catalyst (Chang et al., 2004). We found that CS has the than commercial Pt/C catalyst. Therefore, this kind of materials
porous surface structure which is available to light degradation of would exhibit good application potentials for catalyst material of
dye wastewater through loading active center cobalt phthalocya- fuel cell.
nine (Wang et al., 2014a). It is found that the -SH from FK modified Clarke et al. (2008) analyzed and assessed the methane yield
CdS effectively (Fig. 6), which means it is simple to synthesize a from the banana waste. They demonstrated that the banana waste
novel photocatalyst of FK-decorated CdS with co-precipitation produced over 398 ± 20 l CH4 kg VS 1 of dry banana. With this
method. The production FK-Cd (II) has the ability of degradation yield, 1 t d 1 can generate 7.5 kW of electricity, which was enough
of dye wastewater (Wang et al., 2015a,b,c,d). Latha et al. (2015) to supply six to eight houses. The potential of material recovery
synthesized the catalyst with excellent activity of Suzuki cross- and energy production by organic solid wastes generated from
coupling reaction between aryl halides and phenylboronic acid. slaughterhouse though anaerobic digestion has been carried out
In detail, firstly they synthesized magnetic nanoparticles (Fe3O4) to assess by Yoon et al. (2014). The methane productions were
coated with chicken feather (CF) and subsequently grafted with achieved above 80% within 10 days in poultry manure & feather,
palladium nanoparticles (PdNPs) using in-situ preparation blood and sludge cake. Thermal treatment technology is an indis-
approach. This kind of catalyst is stable and easy to be separated. pensable part of every integrated waste management system,
In addition, lignosulfonate, as a cost-effective and renewable including combustion, incineration, gasification and pyrolysis
supporting material, is capable of loading cationic catalyst through (Lombardi et al., 2015). Hydrothermal carbonization (HTC) is also
Michael addition and catalytic oxidation coupling reaction (Sun a thermal conversion technique that converts food wastes and
et al., 2014). Hence, it as well as is applied as catalyst carrier. associated packaging materials to a valuable, energy-rich resource
(Li et al., 2013a,b,c).

8. Energy materials from waste biomass


9. Smart polymer for medical materials
When it refers to a kind of new energy material, such as hydro-
gen storage materials, battery materials, luminescence materials Through hydrolysis, fermentation and biological refining, waste
and phase change materials, they have abilities of storing, convert- biomass as raw material could be obtained lactic acid, ethanol,
ing, and supporting. In addition to the common synthetic materials glucose acid, citric acid, amino acid, acrylic acid, succinic acid,
and biomass materials, the source of carbon materials has been 1,3-propanediol, etc. These products are typical chemical raw
gradually extended to the waste biomass materials. Carbon mate- materials which can be used as food additives. What is more, some
rials have many advantages, such as large amount of hydrogen monomers are applied for preparing degradable polymer materials
absorption, low mass, strong resistance of poison and easy to strip. via polymerization, such as PLA, Polytrimethylene terephthalate
Therefore, it has attracted a lot of attention as a new type of hydro- (PTT). Medicinal materials enable to be obtained by making use
gen storage matrix (Sun et al., 2016a,b). Likewise, porous carbon of its biocompatibility and biodegradability, including surgical
(activated carbon) that prepared by biomass is very suitable for sutures, antiblocking films, temporary stent catheters, stents,

Fig. 6. The structure of FK-Cd (II) complex.

Please cite this article in press as: Wang, J., et al. Reutilization of discarded biomass for preparing functional polymer materials. Waste Management
(2017), http://dx.doi.org/10.1016/j.wasman.2017.04.025
8 J. Wang et al. / Waste Management xxx (2017) xxx–xxx

tissue engineering repair scaffolds and drug controlled-release car- outside. The studies of intelligent polymer materials have made
riers. Chitin and CS material have either the function of antibacte- great progress, especially some temperature and acid-sensitive
rial and anti-inflammatory analgesic or good compatibility and polymer materials (Hoffman, 2013). Stimulus responsive of
degradability, so it is possible for them to be applied as biomedical intelligent polymer materials attribute to either polymer chain or
polymer materials (Wan and Tai, 2013; He et al., 2012). pendant group. As a result, when the natural polymer was
Protein, as a kind of biological macromolecule, has unique used as raw materials, the preparation of intelligent polymer
advantages like good biocompatibility, biodegradability, stability, materials would be achieved through self-assembly, composite
low cytotoxicity and high potency. In a variety of existing drug car- (Xiong et al., 2012a,b), hybrid technology and polymerization
riers, one of the most potential and notable drug delivery system is (Zhou et al., 2016a,b). Specifically, the hybrid of proteins and
the drug carrier based on the animal protein (Wang et al., 2010b; polysaccharides shows certain regularity, which laid the foundation
Mao et al., 2011). After effectively extracted FK from discarded for preparation of intelligent biological macromolecule material.
feathers (Yin et al., 2013), we had prepared keratin-based films The humidity control composite material was prepared by car-
materials (Li et al., 2011a,b) and polymer gel with controlled boxymethyl cellulose (CMC), sepiolite and AA-AM copolymer
release behaviors (Pan et al., 2015; Guo et al., 2015). In addition, (Yang et al. 2011). This material maintained a relative humidity
it had good antioxidant activity after being conjugated with metal in the 57–60.5% range at 25 °C, and reached the equilibrium levels
complexes (Li et al., 2013a,b,c). Choosing pig hair keratin (PHK) within 3.5 h. And the adsorption capacities for NO2 and SO2 are
with short polymer chains as raw materials and using methacrylic 227 mg/g and 288 mg/g respectively. Therefore, it is considered
acid (MAA) as a functional monomer, we prepared a novel keratin- to be suitable for the applications for maintaining a proper
based biopolymer pH-sensitive hydrogel via grafting copolymer- micro-environment for museum or gallery display cases or arti-
ization (Fig. 7) (Li et al. 2016). It can carry small molecular and facts transportation in particular. Jr et al. (2015) report a PVA/CS
macromolecular drugs. And in 12 h, the cumulative release rate polymeric doped with anthocyanins, a Time-Temperature Indica-
was 89 % at pH 7.2 for the small molecular model drug, while the tor (TTI) for applications in intelligent food packaging, which indi-
cumulative release rate reached 70.7 % at pH 7.2 for the macro- rectly indicates food quality changes through the detection of
molecular drug (Bovine Serum Albumin). changes in the pH of packaged food products when subjected to
Besides, it is also found that the hybrid nanoparticles could be improper storage temperatures. Using agar, potato starch, and nat-
fabricated when the cheap zein (Liu et al., 2015a) and soybean pro- ural dyes extracted from purple sweet potato, Choi et al. (2017)
tein isolated (Wang et al., 2014b; Liu et al., 2015b) were used as prepared a new colorimetric pH indicator film which showed color
raw materials. variations to different pH values and spoilage point of pork sam-
ples that changing from red to green. Liu et al. (2017) prepared
an intelligent starch/poly-vinyl alcohol (PVA) film that is capable
10. Other intelligent polymer material
of monitoring pH changes and inhibiting microbial growth in
foods, such as Bacillus subtilis, Aspergillus niger and Staphylococ-
The intelligent polymer is a kind of polymer material that
cus aureus.
responds to physical, chemical or biological stimulations from the

Fig. 7. The preparation of hydrogel for drug release.

Fig. 8. The graft copolymerization of BA, MMA and DAAM on potato starch (PoSt).

Please cite this article in press as: Wang, J., et al. Reutilization of discarded biomass for preparing functional polymer materials. Waste Management
(2017), http://dx.doi.org/10.1016/j.wasman.2017.04.025
J. Wang et al. / Waste Management xxx (2017) xxx–xxx 9

In recent years, we had developed intelligent coatings on the Clarke, W.P., Radnidge, P., Lai, T.E., Jensen, P.D., Hardin, M.T., 2008. Digestion of
waste bananas to generate energy in Australia. Waste Manage. 28 (3), 527–533.
basis of new special functional coatings (Lv et al., 2008; Lv et al.,
Coward-Kelly, G., Agbogbo, F.K., Holtzapple, M.T., 2006. Lime treatment of
2009). A kind of waterborne polyurethane-polyacrylate miniemul- keratinous materials for the generation of highly digestible animal feed: 2.
sion, whose maximum water absorption rate reaches 206%, was Animal hair. Bioresour. Technol. 97 (11), 1344–1352.
prepared, and was acted as the interior humidity controlling coat- Das, O., Sarmah, A.K., Bhattacharyya, D., 2015a. A sustainable and resilient approach
through biochar addition in wood polymer composites. Sci. Total Environ. 512–
ings (Wu et al. 2014). The discard natural polymers were also 513, 326–336.
applied to prepare intelligent coatings. A new kind of crosslinkable Das, O., Sarmah, A.K., Bhattacharyya, D., 2015b. A novel approach in organic waste
potato starch-based graft copolymer emulsion (PoSt-g-BMD) utilization through biochar addition in wood/polypropylene composites. Waste
Manage. 38 (1), 132–140.
(Wang et al. 2013) was prepared using diacetone acrylamide Das, O., Sarmah, A.K., Bhattacharyya, D., 2016. Biocomposites from waste derived
(DAAM) as a functional monomer, as well as butyl acrylate (BA) biochars: Mechanical, thermal, chemical, and morphological properties. Waste
and methyl methacrylate (MMA) used as basic monomers Manage. 49, 560–570.
Ding, A.J., Fu, C.B., Yang, X.Q., Sun, J.N., Petäjä, T., Kerminen, V.M., Nie, W., 2013.
(Fig. 8). The rate of water absorption of PoSt-g-BMD-C was 105% Intense atmospheric pollution modifies weather: a case of mixed biomass
which has the ability to be widely applied to indoors controlling burning with fossil fuel combustion pollution in eastern China. Atmos. Chem.
humidity coatings. The CMC grafted acrylate copolymer emulsion Phys. 13 (20), 10545–10554.
Duan, C., Zhang, D., Wang, F., Zheng, D., Jia, L., Feng, F., Liu, Y., Wang, Y., Tian, K.,
was also reported, which is a kind of biosafety humidity controlling Wang, F., Zhang, Q., 2011. Chitosan-g-poly (N-isopropylacrylamide) based
coatings with 173% water absorption rate (Wang et al. 2015). nanogels for tumor extracellular targeting. Int. J. Pharm. 409, 252–259.
Emadian, S.M., Onay, T.T., Demirel, B., 2017. Biodegradation of bioplastics in natural
environments. Waste Manage. 59, 526–536.
11. Summary Fan, J., Lei, T.-D., Li, J., Zhai, P.-Y., Wang, Y.-H., Cao, F.-Y., Liu, Y., 2016. High protein
content keratin/poly (ethylene oxide) nanofibers crosslinked in oxygen
In nowadays, there is a tendency that an increasing number of atmosphere and its cell culture. Mater. Des. 104, 60–67.
Fujiki, J., Yogo, K., 2014. Carbon dioxide adsorption onto polyethylenimine –
studies focus towards environmental-friendly and renewable functionalized porous chitosan beads. Energy Fuel. 28 (10), 6467–6474.
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of resources and environmental pollution which is brought from degradation in postharvest ripening of two banana cultivars: Focus on starch
structure and amylases. Postharvest Biol. Technol. 119, 1–8.
discarded biomass materials. The traditional disposal methods of Goh, C.K., Valavan, S.E., Low, T.K., Tang, L.H., 2016. Effects of different surface
reutilization of discarded biomass were simple and direct; but, modification and contents on municipal solid waste incineration fly ash/epoxy
inadequate. However, based on bio-refinery technology and poly- composites. Waste Manage. 58, 309–315.
Guo, J.H., Li, T., Zhao, T.T., Wang, Y., He, Y.F., Wang, R.M., 2014. Advanced in Keratin
mer science, the discarded biomass could be converted into energy, modified materials and its applications. Polym. Bull (in Chin.) 4, 16–23.
as well as producing monomer for manufacturing synthetic poly- Guo, J.H., Pan, S.J., Yin, X.C., He, Y.F., Li, T., Wang, R.M., 2015. PH-sensitive keratin-
mers. Furthermore, the discarded biomass was mainly composited based polymer hydrogel and its controllable drug-release behavior. J. Appl.
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towards dealing with all of problems. charges of albumin-chitosan hybrids. Sci. China Chem. 55 (9), 1788–1795.
He, N.P., Wang, R.M., He, Y.F., Zhou, Y., Wang, X.J., Pei, F., 2011. PH-induced self-
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Acknowledgements He, W.J., He, Y.F., Yan, D.Z., Wang, Y., Wang, R.M., 2014a. Adsorption of lead ion
using polymer-modified wheat straw carboxymethylcellulose. J. Disper. Sci.
The project was supported by the NSFC (21364012, 21263024) Technol. 35 (10), 1378–1385.
He, Y., He, W., Liu, S., Wang, Y., Wang, R., Huang, Y., Wang, Y., 2014b. Preparation of
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