CRUDE GLYCERIN AND TEXTILES WASTES: A NOVEL

RECYCLING PROCESS
J. BAUMI1, C. M. BERTOSSE1, S. B. MARTINS2, C. P. SAMPAIO2, G. M.
CARVALHO1, C. L. B. GUEDES1*
1
Universidade Estadual de Londrina, Mestrado em Bioenergia, CCE, Departamento de
Química
2
Universidade Estadual de Londrina, Departamento de Design
*[email protected]

ABSTRACT

The biodiesel industry currently produces 260.000 tons per year producing glycerin as
byproduct which finds absorption difficulties in the market that uses 30 thousand tons
per year. The textile industry produces about 3.4 million tons. of polyamides worldwide,
which are used in clothes making and about 15-51% of the fabric is discarded as
waste. This work aimed the reusing of textile polyamide 66 waste using glycerin from
biodiesel adding value to these supply chains. The procedure consists in heating crude
or pure glycerin to 190 °C and the addition of textile fabric waste and water as a non-
solvent producing recycled polyamide 66 powder. The thermal analysis showed the
thermal behavior remained like polyamide 66 showing a decay in 461 ° C and some
decays for the contaminants in crude glycerin like methanol and free fatty acids. The
recycled polyamide 66 melting point ranged from 253°C to 257°C indicating low
polymer degradation. The 13C-NMR spectroscopic analyzes and infrared spectra
exhibited profile similar to the starting material showing the maintenance of the
molecular structure. The new process was promising due to the use of two
environmental liabilities generated in great amounts, producing recycled poliamide 66
with low costs and good quality.

KEYWORDS: polyamide; waste; glycerin; biodiesel

1. INTRODUCTION

The first technology appeared thousands of years ago with the use of
utensils made from chipped stones. The evolution in quality and quantity,
especially after the industrial revolution, in the IX century until current days with
had resulted in a wide range of consumer goods such as electronics, textiles,
automobiles, food, cosmetics, furniture, among others (VERASZTO et.
al.,2008).. To support and make possible these great progresses of humanity
were required increasing amounts of energy (FARIAS;SELLITTO,2011).
The invention of the internal combustion engines in the IX century and
the marketing and popularization of automobiles in the XX century created a
large and growing demand for fuels, which for many years was only supplied
with petroleum products, a natural non-renewable resource. The impacts
caused by oil and its derivatives combustion have brought serious
environmental problems causing large increase in emissions of pollutants and
greenhouse gases, mainly CO2, SOx and NOx (CORONADO et al 2014;
DEMIRBAS, 2008).
In the last decades there is a growing demand for cleaner and renewable
energy sources such as biofuels, which can diminish the negative
environmental impacts of human action, reducing dependence of society on oil
and provide a more sustainable energy matrix.
Biodiesel is basically a mixture of fatty acids esters obtained from
transesterification of vegetable or animal triglycerides in the presence of an
alcohol producing crude glycerin as byproduct. The crude glycerin due its
contaminants such as free fat acids, methyl or ethyl alcohol, soap, water,
biodiesel, has no defined market and large-scale application; it needs to be
purified for its commercialization (OOI et. al. 2004) as USP grade (United States
Pharmacopeia) containing glycerol at least 99.6% or technical grade containing
at least 96% glycerol. To purify crude glycerin are necessary steps of filtration,
distillation, color and ion exchange processes which that are very expensive
and economically unviable for small and medium producers of biodiesel, making
this byproduct a waste (APOLINARIO et. al., 2012). Each 90 m 3 of biodiesel
produce 10 m3 of glycerin (GONÇALVES et al., 2006; AYOUB; ABDULLAH,
2012).
Brazil produced in 2014 3.419.438 m³ of biodiesel (EPE, 2015) and
generated over 280 tons of glycerin, which is well above the industrial
consumption of this byproduct that is approximately 30 thousand tons. per year.
Second generation ethanol arising from ligno-cellulosic biomass can generate
2.5 to 15% glycerin by volume (ARRUDA et al, 2007; BORZANI, 2006) a source
which tends to became more remarkable. Another important issue in this study
is synthetic textile waste, whose amount generated has increased year after
year.
The implementation and growth of biodiesel production influences the
generation and the availability of glycerin saturating the world market dropping
its prices. In 2003 the refined glycerin was quoted approximately $ 1200 / ton.
having sharp drop to US$ 600 / ton. in 2006, as well as the price of crude
glycerin in the US that was sold from $ 0 to $ 70 per ton, rising to US$ 44 / ton.
in November 2012 (QUISPE et. Al., 2013).
Textile products represent a class of consumer goods that had great and
notable technological developments, and initially constituted is only rudimentary
natural fibers and hand weaving in artisanal scale (BARBER, 1991). This was a
great leap of variety, quality and productivity since the Industrial Revolution,
allowing the emergence of an important branch of industry that moves the world
more than $ 1 trillion per year: the textile industry (SEM 2008). In Brazil, since
the late 60's are produced virtually all types of synthetic fibers (polyamide,
polyester, acrylic, elastomeric and olefin) with quality and price, similar to those
available in the international market to a considerable portion of these fibers .
This sector accounts for a production, between fibers and artificial and synthetic
multifilament, more than 380.000 tonnes per year, representing about 40% of
industrial consumption in the country. This production results in an annual
turnover of $ 1.06 billion and generates direct employment for about 9,000
people (ABRAFAS 2013). In the last decade ended in 2009, domestic
consumption of synthetic fibers showed two distinct periods (AUSTIN ASIS,
2011) Between 2000 and 2004, fiber consumption grew by an average of 4%
per year, from 592 000 tonnes in 2000, 690 thousand tons in 2004 (best result
of the entire series); The second period, in turn, was marked by the resumption
of growth in consumption between 2005 and 2008, and a drop in demand in
2009, due to the effects of the global crisis on the domestic economy. In this
industry, two types of synthetic fiber are particularly significant: The polyester
and polyamide. This article specifically addresses the textile waste compounds
of polyamide.
Current estimates indicate a global production of polyamide 6 and 66
(Nylon® 6 and 66) of 3.5 million tons. per year being applied to the clothing
industry generating fabric pieces as waste (AIZENSHTEIN, 2009). According to
SEBRAE (2006) the production of textiles waste in the garment industry range
from 15% to 51% depending on the fabric cutting, type of piece rates and
employee training (ABIT, 2013). Generation of waste can be minimize through
the concept of "cleaner production" (MARTINS; PEREZ, 2012), but there is no
avoiding the generation of millions of tons of fabric waste annually that are
mostly discarded, it is a large obstacle to be overcome in order environmentally
sustainable production. Due polyamide is a synthetic compound it is very stable,
having high resistance to degradation by microorganisms such as fungi,
bacteria and oxidation at ordinary temperatures (LAVADO, 2013), resulting in a
high lifetime in nature and may last for decades or hundreds of year old. Thus,
the polyamide can become a major environmental liability.
This study aims to develop new processes for use polyamide 66 textile waste
and glycerin derived from biodiesel production, targeting new products and
cleaner and sustainable production chains.

2. MATERIALS AND METHODS

In this study we applied the USP glycerin and crude glycerin derived from
soybean oil biodiesel. Heat glycerin previously placed in a beaker, above 190 °
C, preferably through a heater plate or microwave. the pieces of polyamide
66/Elastane fabric were slowly add to crude or USP glycerin with mechanical or
magnetic stirring until complete dissolution of the fabric maintaining the
temperature higher than 180 ° C. The ratio polyamide 66 fabric/glycerin were
1:1 (w/v). The resulting liquid at temperature greater than 180 ° C was poured in
a blender with water at 10 °C, 45 ° C or 80 ° C for 5 minutes. The resulting
heterogeneous mixture is vacuum filtered and the filtrated powder was placed in
an oven for 4 hours at 105 ° C. The samples obtained from crude glycerin were
denominated as PACGX and the samples obtained from USP glycerin were
denominated as PAUGX, where X indicates the water temperature and the
polyamide 66 fabric waste was named “PA66F”.
The residual water and the residual glycerin were distilled and reused in the
process. The resulting materials of crude glycerin and USP glycerin were
characterized by FTIR spectroscopy, thermogravimetric analysis (TGA),
Differential Scanning Calorimetry (DSC) and NMR (Nuclear Magnetic
Ressonance) and the results were compared.

2.1 Physical-Chemical Characterization

Infrared Spectroscopy (FT-IR): The infrared spectra were acquired by

the infrared spectrometer with Fourier transform from a Shimadzu model
IRPretige-21; Resolution: 4 cm -1; Module analysis ATR (Attenuated Total
Reflectance); ZnSe cell (zinc selenide); spectra range: 4000 cm -1 to 700 cm-1;
Number of scans: 100.
Differential Scanning Calorimetry (DSC): The thermal analysis were
carried out with a Shimadzu DSC-60. The samples had mass between 3 to 4
mg were placed and sealed in aluminum pans. The calorimetric curves were
obtained in the range 30 ° C to 300 ° C; Heating rate: 20 ° C min -1. Purge gas:
N2; The heat of fusion for the considered 100% crystalline polyamide 66 was
191.0 J.g -1 (VASANTHAN; SALEM, 2010). The crystallinity were calculated
from equation 1:

Eq. 1

Nuclear Magnetic Resonance (NMR): NMR spectrometer Bruker

Avance III Mod operating at 400 MHz equipped with a direct multinuclear probe
(BBO) 5 mm (Solids).
Scanning Electron Microscopy (SEM): The analyzes were performed on
a PHILIPS-FEI microscope model QUANTA 200. Samples received a gold film
(± 20 nm) in equipment sputter coater SCD model 050 (BAL-TEC).
Thermogravimetric Analysis (TGA): The analyzes were performed on a
Shimadzu device model TGA-50; Heating rate: 20 ° C min -1; Sample mass: 3
mg to 4 mg; Open platinum pan; Temperature range: 30 ° C to 600 ° C; Purge
gas: N2.

3. RESULTS AND DISCUSSION

To recycling polyamide by melting is required a heat source, which can
be provided by conventional forms such as flame or electric resistance. Using
glycerin as a solvent provides the possibility of microwave irradiation heating,
which is a considerably more efficient way than conventional means making
the process safer, faster with low costs. The 3 hydroxyl groups give a dielectric
constant considerably remarkable for glycerol (40.41 at 25 ° C) having good
thermal response to microwaves (SENGWA et. Al., 2008). There is also the
advantage of being non-toxic over the more usual options such as cresols and
formic acid for dissolution of polyamides.
The product retains the original fabric dyes and plastic properties. The
resulting powder from the recycling process is shown in Figure 1.

(a) (b) (c)

Figure 1. (a) Textile Waste (b) Crude Glycerin (c) Recycled Polyamide 66
(PACG45)

The DSC curves were obtained and compared between different contaminants
grade solvent. In Figure 2 we have a curve of the material obtained by crude and
 USP glycerin.

PACG45

PACG10

PACG80

(a) (b)

Temperature (°C)

Figure 2. Polyamide 66 powder DSC produced with (a) USP glicerin (b) Crude
glycerin

The DSC curves of the material to USP glycerin showed two endotherms
bands: 60 ° C which corresponds to the solvent residue output from the physical
structure of the material, at 254 to 257° C which corresponds to melting of the
polyamide 66. The material made with crude glycerin with water temperatures
10°C and 45°C exhibited a band with a different profile at 110 ° C, which can be
attributed to moisture of the material; at 230 ° C which indicates the presence of
free fatty acids; one shoulder in 250-260 °C range corresponding to melting of
polyamide 66; and 300 ° C which is the boiling temperature of the glycerol. The
DSC curve acquired with PACG80 samples showed a similar profile to that
seen with USP glycerin exhibiting just one band near 260 °C, indicating that the
contaminants present in crude glycerin were removed from the material due
higher solubilization in hot water.
The calculated polymer crystallinity and melting points for different
polyamide and glycerin ratios are shown in the Table 1.

Table 1. Melting points from differents procedures

Fabric/Glyceri IC Melting Point Water

n Ratio (%) (°C) Temperature
(°C)
3:1 28,19± 2,97 253,66 ± 0,66 10
2:1 22,67± 2,70 254 ± 1,52 10
1:1 26.76± 2,62 255,66 ± 0,88 10
3:1 24,96± 2,81 256,66 ± 0,33 45
2:1 24,69± 2,86 255,66 ± 1,45 45
1:1 35,07±2,33 257 ± 0,57 45
3:1 11.88±0,36 256,5 ± 1,50 80
2:1 22,16±2,06 255,66 ± 0,33 80
1:1 25,43±1,72 254,66 ± 0,33 80
 Observing the table 1 it can be concluded that the highest crystalinity
was obtained with water in 45°C and 1:1 polyamide/glycerin, ratio that was
chosen to be compared to the other water temperatures in this work. The
melting points obteined ranged from 253,66±0,66 °C to 257±0,57 °C implying in
a low degradation of the polymer structure considering that the melting point
tends to decrease due to thermal stress (CERRUTI; CARFAGNA, 2010).

(a) (b)

Figure 3. Polyamide 66 powder TGA produced with (a) USP glycerin (b) Crude
glycerin

The infrared absorption spectrum of the recycled material showed bands

and profile characteristics of polyamide 66, the main constituent of fabric and
major component of the product, consistent with is described in literature: 3300
cm-1 νN-H; 2939 cm-1 νCH2 ; 2876 cm-1 νCH3 ; 1631 cm-1 νc = o; 1538 cm-1 νN-H ;1044
cm-1 νC-N (EL-MAZRY et. al.(2012); CHEVAL et. al. (2010); PAVIA et. al.(2010)).
It is observed also the presence of characteristic peaks of hydroxyl and
carbinols of glycerin: 3600-3200 cm -1 νO-H and νC-O 1111 cm-1 indicating the
presence of glycerol and humidity since the product is hygroscopic.
Figure 4. Infrared Spectra PA66F, PACG45 and PAUG45 samples

The 13C NMR spectra obtained from powder made with both solvents
exhibited the same characteristic chemical shifts from the starting material
(PA66F) (176; 44; 38; 33; 28 ppm) and are represented in Figure 5 with peaks
assigned. There were low intensity peaks in the 60-80 ppm region
corresponding to carbinols (C-OH) of glycerin residues and dyes already
present in the fabric. Spectroscopic data indicate that the interaction of
hydrogen bonding is insignificant at room temperature since there was no shift
in the carbonyl peak in the IR and NMR spectra.

Figure 5. NMR Spectra (1) PA66F (2) PAUG45

The micrographs of the powder (Figure 6) showed an amorphous and

porous differing from fiber structure of the starting material. We observed some
small morphologically different structures which may correspond to elastane
which due to its low content (up to 5%) the material was not detectable by
spectroscopic techniques used in this work.

Figure 6. SEM Micrographs: Polyamide 66 Fabric magnification: 1600(a),

6000 (b) Recycled Polyamide 66 Powder magnification (PACG45): 1600 (c),
6000(d)

The new procedure opens up many potential applications for these two
abundant wastes, since the recycled polyamide 66 can be an important input with
wide commercial use in plastics industry, without the generation of new wastes nor
using toxic materials in the process.

4. CONCLUSION

Through the developing of a uncomplicated and clean recycling process that

uses waste widely generated in industries of biodiesel and textiles permitted the
reuse of polyamide 66 with low cost and without generation of new wastes. The
spectroscopic data showed no significant alteration in the polymer chemical
structure. DSC and TGA analyzes indicate that the thermal behavior of the material
and the degree of impurities present may be the same polyamide 66 in 80 ° C water
temperature, the higher melting point were obtained in 45°C water temperature and
fabric/glycerin ratio of 1. The new process has great potential for large-scale
application making these more environmentally sustainable supply chains.
5. ACKNOWLEDGEMENT

We would like to thank CAPES, Fundação Araucária and CNPq for financial
support.

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