Project Report

Submitted By

Bishal Dhar
Roll no- T91/PST/194148
Registration no- DO1-1111-0083-19
Intern @ Century Plyboards India Ltd
Department Of Polymer Science & Technology
University Of Calcutta

PROJECT TITLE: “REDUCTION OF PHENOLIC

COMPOUNDS IN PHENOL-FORMALDEHYDE
RESIN”

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 PREFACE

This report has been prepared as part of my project, as a part of B.Tech. This
report is prepared with the view to include all the details regarding the project
that I carried out.
The initial portion of the project describes the chemistry of resole resin and
various pollutants present in the PF resin. In the next portion I have mentioned
various processes to reduce the phenolic compounds present in the resin. We
have performed various testing on the raw resin and treated resin and we have
found that activated carbon is a good adsorbent.
I have carried out the project successfully with the help of my project guide.

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 Table of Contents
Contents Page No
 About Company………………………………………………………………….4
 Objective ……………………………………………………………………………5
 Introduction…………………………………………………………………………6-8
 Material and Method ………………………………………………………….9
 Characterisation……………………………………………………………………10
 Result and Discussion ……………………………………………………… 11-18
 Conclusion …………………………………………………………………………….19
 Acknowledgement…………………………………………………………………20
 References………………………………………………………………………………21

About company
3
Century Plyboards India limited (CPIL) is a leading manufacturer of
plyboards, veneers, decorative laminate in India. It was established by
leading visionary leader Mr. Sajjan Bhanjanka and Mr Sanjay Agarwal.
Century ply (CPIL) is the front runner of manufacturing of Borer Proof
plywood and Boiling water resistance (BWR) veneer and laminates in
India.
The products of Century ply are –
1) Plywood
2) Laminates
3) Veneer
4) Prelam
Century laminates uses a unique technology in which special resins
impact extra strengths to its laminates making them highly resistant to
scratch and abrasion. Century laminates exotic range of decorative
laminates is characterised by higher colour fastness and best bonding
properties with substrate available in the market today. Century
laminates is a product from the house of century ply. Century ply also
makes plywood which are fire retardant in nature. century ply is the
first ISO9002 company in India for veneer and plywood. In the year
1997 the company first introduced Borer proof plywood in India.

Objective

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 Pollution is a major concern for all the countries in 21 st century. Various
kinds of pollutants are being produced by the industries which major
environmental contaminants. Removal and reducing of these contaminants
are the most important for sustainable growth.
 Phenolic compounds that are present in the waste water and fumes
generate during the manufacturing process is one of the major pollutants
for the environment.
 In this study we have used activated carbon as an adsorbent of phenolics
from liquid phenol-formaldehyde resole resin.
 Quantification of phenolics in PF resin is done through spectroscopic and
chromatographic approach.
 In the final stage, % reduction of phenolics using Activated Carbon has
analysed.

Introduction
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Phenol-Formaldehyde resin is used as an adhesive to make laminates. PF resin are
two types namely resole and novolac. In the laminate industry resole type PF
resin are used. Resole phenolic resins are produced by polymerizing (heating) a
1:1 (or more) molar ratio of phenol and formalin in a reactor vessel (Figure 2.1) in
the presence of an alkaline catalyst such as ammonia, sodium carbonate, or
sodium hydroxide at 100°C for about 1 hour. It is usual to have 1.1 to 1.5 mole of
the formaldehyde for each mole of phenol.
Resole type resin content free phenolics in its
aqueous solution. Unreacted phenol is one of
them. There are various free phenolic
compounds present namely bis- (2-
hydroxyphenyl) -methane, bis- (4-
hydroxyphenyl) -methane etc. These oligomers
present in the PF resin are major environmental
contaminant. These oligomers or free phenolics
need to be reduced and removed from the
phenol-formaldehyde resin aqueous solution.
Various method can be applied to reduce the
free phenolics. Among various physical and
chemical methods Adsorption is one of the most
effective processes to reduce the free phenolics
from the solution. Adsorption process is a simple
and cost-effective method for removal of phenolic compounds from the PF resin
aqueous solution. Adsorption is the adhesion of atoms, ions or molecules from a
gas, liquid or dissolved solid to a surface. This process creates a film of the
adsorbate (solute)* on the surface of the adsorbent(solvent). This process differs
from absorption, in which a fluid (the absorbate) is dissolved by or permeates a
liquid or solid (the absorbent). Adsorption is a surface phenomenon and does not
penetrate through the surface to the bulk of the adsorbent, while absorption
involves the whole volume of the material, although adsorption does often
precede absorption. The term sorption encompasses both processes, while
desorption is the reverse of it.
Various adsorbents used for phenol removal includes iron oxide nanoparticle,
silica gel, activated alumina, polymeric resin[7], activated carbon, rice husk.

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1. Iron oxide nano-particles
Solid phase extraction of phenol by using iron oxide has been reported by Talvalli
and Shiri [1]. The optimization of the parameters like pH, agitation times, and
number of nanoparticles was carried out. The highest removal was observed in
the pH range of 5 to 7. The lowest removal was observed at the pH value of 12.
Montiel-Palacios et. al. has reported the photo catalysis of phenol derivatives with
iron oxide nanoparticles [2]. The nanoparticles were dispersed on highly ordered
hexagonal(p6mm) mesoporous silica SBA-15. Triblock copolymer, Pluronic P123
was used as direct structuring agent for synthesizing silica mesoporous support,
SBA-15.
2.Silica Gel
Laboratory Studies on possible utilization of silica gel sludge for the removal of
phenol from aqueous solutions were carried out by Idris and Saed [3]. They
studied the kinetics of phenol removal by using silica gel as an adsorbent. It was
observed that the adsorption capacity increased as the pH was decreased from
6.5 to 2. The phenol removal was found to follow both, Langmuir and Freundlich
isotherms.
3.Activated alumina
The adsorption of phenol on activated alumina was carried out by Hassan and
Hammad [4]. Five derivatives of phenol, viz. m-nitrophenol, m-aminophenol, m-
hydroxyphenol, cresol, m-hydroxybenzoicacid and phenol were used. They
determined the isotherms at 220C, 250C, 350C. The phenol uptake followed the
Langmuir isotherm rather than Freundlich. Increasing temperature led to
reduction in adsorbate without change in isotherm patterns. This means that the
mechanism is exothermic for all Investigated phenols.

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4.FUNCTIONALIZED GRAPHENE-BASEDMATERIALS AS INNOVATIVE ADSORBENTS
OF ORGANIC POLLUTANTS:
Functionalized graphene can work as an excellent adsorbent in the removal of
phenolic substances from the Phenol-Formaldehyde resin [5]. The
functionalization of graphene or graphene oxide (GO) nanosheets confers specific
properties to the composites, e.g., their chemical selectiveness, solubility, thermal
and electronic conductivity. Due to their large specific surface area and rich
porous structure, carbonaceous materials usually show high adsorption capacity
and have been successfully employed as adsorbents of organic pollutants.
5. Activated Carbon
Activated carbon have been widely used due to their high porosity and surface
area[6][8]. Activated carbon is a highly porous, amorphous solid consisting of
micro crystallites with a graphite lattice, usually prepared in small pellets or
powder. Various types of activated carbon and their different physical form is
present in the market – Granular Activated Carbon (GAC), Powder Activated
Carbon (PAC), Extruded Activated Carbon (EAC).
Various materials and nanomaterials can be used as an adsorbent in the reduction
of phenolic from Phenol-Formaldehyde resin. Among all Activated carbon is the
cost-effective adsorbent. In our project we have selected activated carbon
derived from coconut shell Coconut shell activated carbon has a very high
hardness and is more abrasion resistant than any other type. It is a totally natural,
environmentally friendly product, that has a very small carbon foot print, since it
is derived from coconut shells. As most of its pore structure consists of
micropores (more than 80%), coconut shell carbon can efficiently absorb
impurities with micropore molecular structure

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 Materials and Method
Materials
 Phenol-Formaldehyde resin stock solution has been used as base material
for the project work. The free phenolics which are present in the solution
has to be removed.
 Activated carbon has been used as the adsorbent material for adsorbing
the free phenolics present in the PF resin.

Method
 Raw Phenol-Formaldehyde resin was taken from PF resin manufacturing
plant of Laminate section.
 We have taken three types of samples for characterisation namely –
1) Raw resin(R)
2) Resin treated for 6 hours (RT 6)
3) Resin treated for 24 hours (RT24)
 All the samples were treated with Activated carbon in magnetic stirrer
(600-800rpm) for 6 hours and 24 hours respectively.
 The raw sample of PF resin and treated samples were then collected in
different containers for further experiments.

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 Characterisation
The three samples (one is Raw resin and another two treated) R, RT6, RT 24 has
been taken for different characterisation method to determine the free phenolic
present in the PF resin.
The table show the different characterization method for different sample

Raw Resin (R) RT 6 RT 24

FTIR GC-MS FTIR

GC-MS GC-MS

*FTIR- Fourier Transform Infrared Spectroscopy

*GC-MS – Gas Chromatography -Mass Spectroscopy

Sample resin containers

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 Result and Discussion

Result

1) Sample R
Sl. Test parameters Test Method unit Result
No.
1 FTIR In House SOP Wavenumbe 3389,1633,1610,
r 1478,1451,1235,
(Cm-1) 1116,756,694

2 GC-MS In House SOP % 2-methylbezofuran,

2,4-Di-tert-
butylphenol
Phenol,2,4-bis(1,1-
dimethylethyl)-,
phosphite
Phenol, free phenol
FTIR and GC-MS is used as testing method to find the different free phenolic
compound present in the PF resin (Sample R) and quantity of each compound.
Table 1 shows the result of the above two test for Sample R

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2)Sample RT6
Below table 2 shows the result of GC-MS of sample RT6

Sl. Test Parameters Test Method Unit Result

No.
1 2methylbezofuran,
2,4-Di-tert-
butylphenol
Phenol,2,4-bis(1,1-
dimethylethyl)-,
GC-MS In House SOP % phosphite
Phenol, free
phenol

3)Sample RT24
Below table shows the FTIR and GC-MS result for sample RT24

Sl. Test Parameter Test Method Unit Result

No

1 FTIR In House SOP Wavenumber 3389,1633,1610,1478,

(Cm-1) 1451,1370,1235,1116,
756,694

2 GC-MS In house SOP % 2methylbezofuran,

2,4-Di-tert-
butylphenol
Phenol,2,4-bis(1,1-
dimethylethyl)-,
phosphite
Phenol, free phenol

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The Table below shows the different wavenumbers that has been found by FTIR
method and the functional groups associated with the wavenumbers

Observed Functional groups

wavenumber
in FTIR (Cm-1)
3389 OH
1633 C=C Aromatic ring
1610 C=C Aromatic ring
1478 C-H aliphatic
1451 C=C benzene ring
1370 OH, in plane
1235 Asymmetric structure of
Sample 2- phenolic
2,4-di-tert- C-C-OH
2,4-bis(1,1- Phenol Free
1116
Methylbenzofuran C-O-C aliphatic
butylpheno ether
dimethylethyl) (%) phenol
(%) 756 l CH out of-phosphite
plane ortho (%) (%)
(%) substituted
R 3.94 694 2.26 Adjacent
16.7 5H 80.7 2.12
RT 6 3.26 1.96 14.08 86.53 1.56
RT 24 1.26 1.4 10.75 77.1 2.16

The below table shows the data of GC-MS of three sample

Table (GC-MS)

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Exhaust Air from Impregnator
Below table shows the Phenolic Percentage of the Flue Gas
Sl Test Parameters Test Method Unit Result
No.

2,4-di-tert-
butylphenol:
2.57
1 Phenolic percentage In house SOP % Phenol: 0
Phenol,2,4 bis
(1,1-
dimethylethyl)-
, phosphite

In the laminate industry during the manufacturing of Phenol- formaldehyde resin

exhaust air is produced from the dryer. This exhaust air or flue gas contains
various phenolic compounds which are hazardous for the environment. We have
applied activated carbon to adsorb the phenolics from the flue gas. From the
above table we clearly see that free phenol has reduced. The experiment is under
observation.

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FTIR Graph PF Raw resin (Sample R)

FTIR graph of Sample RT 24

Discussion

15
Two testing has been performed with the help of N.D. International to identify
and quantify free phenolics that are present in the PF resin. The two experiments
are FTIR and GC-MS. FTIR results shows different peaks with wavenumbers (Cm -1)
which is the indication of various compounds present in the resin. GC-MS results
shows that there are basically three phenolics compounds present along with free
phenol. These compounds are 2-methylbezofuran, 2,4-Di-tert-butylphenol, 2,4-
bis(1,1-dimethylethyl)-, phosphite. These phenolics compounds are free
phenolics which are hazardous for the environment so need to reduce in quantity
from the resin.
Three samples have been prepared using activated carbon which acts as an
adsorbent. One sample is raw resin (sample R) collected from the resin plant of
laminate section. The other samples are RT 6 and RT 24. They have been treated
with activated carbon for 6 and 24 hours respectively.

2-methulbenzofuran(%)
4.5

4
3.94
3.5

3 3.26

2.5

1.5

1 1.26

0.5

R RT6 RT 24

Graph 1

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 2,4-di-tert-butylphenol(%)
2.5

2.26
2
1.96

1.5
1.4

0.5

R RT 6 RT 24

Graph 2

2,4-bis(1,1-dimethylethyl) phosphite (%)

18

16 16.7

14
14.08
12

10 10.75

R RT 6 RT 24

Graph 3

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  From the Graph 1 we can observe that free phenolic i.e., 2-
methylbenzofuran is reduced. Sample RT6 and sample RT24 is treated with
activated carbon. So, we can say activated carbon has adsorbed 2-
methylbenzofuran properly.
 Graph 2 indicates that, 2,4-Di-tert-butylphenol which is a free phenolic
present in PF resin has reduced in quantity for both Sample RT 6 and RT 24.
 From the Graph 3 we can see that 2,4-bis(1,1-dimethylethyl)-, phosphite is
reduced for both Sample RT 6 and RT 24.

FTIR graph has been presented for Raw resin (Sample R) and RT 24. From the
graph we can observe that peak height has been reduced in case RT 24 which is
the indication that activated carbon has absorbed the free phenolic compounds.
That why the peak height has reduced.

Free Phenol (%)

2.5

1.5

0.5

R RT 6 RT 24

Graph 4

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 Conclusion
Three samples have been prepared i.e., Sample R, Sample RT 6, Sample RT 24
using activated carbon as an adsorbent. FTIR and GC-MS has used as a testing
method to estimate the free phenolics present in the above-mentioned samples.
We have found that there are 3 major free phenolic compounds present in the
samples. The samples have been treated with activated carbon for 6 hours and 24
hours. Activated carbon acts as an adsorbent which have adsorb the free
phenolics.
From the GC-MS and FTIR data it can be concluded that the free phenolic has
reduced for both Sample RT 6 and RT 24.

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 Acknowledgement
At first, I would like thanks to the company CENTURY PLYBOARDS INDIA LIMITED
for giving me the opportunity for industrial training in their company
I would like to express my profound gratitude to my project guide Dr. Biplab
Bhowmik (R&D Manager, Century Laminates) sir for his constant support and
enthusiasm throughout my internship period.
I also like to thanks Dr. Dipankar Chattopadhyay (Professor, Dept. of Polymer
Science and Technology, University of Calcutta) and Dr. Samit Kumar Roy (HOD,
Dept. of Polymer science and technology) for giving me the opportunity and
support whenever needed.
Special thanks to the laboratory members and staffs in research and development
of Century Laminates for their cooperation

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Fe2o3Nanoparticles Dispersed on Sba-15”, Journal of Ceramic Processing
Research. XX (4), pp.548~552, 2009.
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