PRODUCTION, CHARACTERIZATION AND PRE-COMMERCIALIZATION OF LAUNDRY DETERGENT POWDERS INCORPORATED WITH PALM C16 METHYL ESTER SULPHONATES PARTHIBAN SIWAYANAN A dissertation submitted in partial fulfilment of the requirements for the award of the degree of Doctor of Engineering (Process Plant Management) Faculty of Chemical Engineering Universiti Teknologi Malaysia FEBRUARY 2015
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PRODUCTION, CHARACTERIZATION AND PRE-COMMERCIALIZATION OF
LAUNDRY DETERGENT POWDERS INCORPORATED WITH
PALM C16 METHYL ESTER SULPHONATES
PARTHIBAN SIWAYANAN
A dissertation submitted in partial fulfilment of the
requirements for the award of the degree of
Doctor of Engineering (Process Plant Management)
Faculty of Chemical Engineering
Universiti Teknologi Malaysia
FEBRUARY 2015
iii
DEDICATION
I dedicate this humble effort to my parents,
my beloved wife and our lovely children for their
continuous prayers, love, support and understanding
iv
ACKNOWLEDGEMENT
First and foremost, I would like to express my utmost gratitude to my
supervisors, Prof. Ramlan Aziz and Prof. Dr. Nooh Abu Bakar for their advice and
guidance throughout the course of study. My sincere appreciation also extends to
Assoc. Prof. Dr. Shreeshivadasan Cheliappan and Dr. Zainul Akmar Zakaria for their
invaluable support and assistance.
This research was supported by the Ministry of Science, Technology and
Innovation (MOSTI) and Ministry of Education (MOE) and I am very grateful for
their financial contribution. I am also thankful to the staff members of the Institute of
Bioproduct Development (IBD, UTM), my colleagues in Pentamoden Sdn. Bhd. and
Ir. Dr. Hj. Hamdan Ya and Tn. Hj. Ropien Jokiman of SIRIM Berhad for their great
help during the course of my research.
In the process of preparing this dissertation, I was in contact with many
people, including researchers, engineers, academicians, industry experts and
consultants. They have contributed extensively towards my understanding and
thoughts. My heartfelt appreciation also extends to all of them. I will forever be
thankful to Datuk Dr. Salmiah Ahmad for introducing me to the wonderful universe
of oleochemicals.
I am deeply indebted to my parents. Without them, I would not be the person
I am today. Finally, and most importantly, I would like to thank my wife, Subashini
and children, Anupreetha, Rishanthan and Rhenupriosha for their continuous love,
support and encouragement.
.
v
ABSTRACT
Palm C16 methyl ester sulphonate (C16MES) is an anionic surfactant that has
the potential as an active ingredient in the production of laundry detergent powders.
Although C16MES has been successfully applied in the production of high-density
laundry detergent powders (HDDP), it could not be employed during spray drying
process in the production of market preferred low-density laundry detergent powders
(LDDP) without compromising the detergency and other significant attributes. This
dissertation encompasses experimental research on phosphate-free laundry detergent
(PFD) powders incorporated with binary anionic surfactants of C16MES and linear
alkyl benzene sulphonic acid (LABSA) at both laboratory and pilot scales and also
include consumer studies towards laundry detergent products with special reference
to palm C16MES incorporated laundry detergent powders. Initial laboratory
experiments revealed that PFD powders resulted from C16MES/LABSA of 50:50
ratio and of pH 7 - 8 have good detergency stability upon one-week of continuous
heating in an oven at 50 oC with 85% relative humidity. Subsequent experiments were
carried out in a pilot spray dryer using PFD formulations of six different ratios of
C16MES/LABSA under the same pH condition. Three PFD formulations were
selected for further evaluation based on their suitability in the spray drying process.
The cleaning properties and particle characteristics of the resulting spray dried
detergent powders from these selected formulations were analyzed. Based on the
overall evaluation, C16MES/LABSA in 40:60 ratio was selected as the ideal PFD
formulation. Further tests confirmed that spray dried detergent powder (SDDP) from
the ideal formulation has a high level of biodegradability (60% in 13 days), low eco-
toxicity properties (LC50 of 11.3 mg/L) and moderate flowability characteristics
(Hausner ratio of 1.27 and Carr’s index of 21.3). Other than experimental studies, a pilot survey was also carried out to study consumers’ preferences (detergent format,
brand and origin) and their purchasing behaviour (awareness, knowledge and perception) towards laundry detergent products, specifically with reference to palm
C16MES incorporated detergent powders. The majority of the respondents (82%)
reported that although they neither have the knowledge about palm MES incorporated
detergent powders nor heard of its surfactants, their preferences to use this new eco-
friendly product were generally positive (94%). The results imply the commercial
potential of the MES incorporated laundry detergent powders and with effective
commercialization strategies, the product can attain success in the marketplace.
vi
ABSTRAK
C16 metil ester sulfonat berasaskan minyak sawit (C16MES) merupakan
surfaktan anionik yang mempunyai potensi sebagai bahan aktif di dalam penghasilan
serbuk detergen pakaian. Walaupun C16MES telah berjaya digunakan di dalam
penghasilan serbuk detergen berketumpatan tinggi (HDDP), tetapi ianya tidak boleh
digunakan semasa proses pengeringan semburan di dalam penghasilan serbuk
detergen berketumpatan rendah (LDDP) seperti yang dikehendaki oleh pasaran tanpa
menjejaskan ciri kebersihan detergen dan sifat-sifat lain yang penting. Disertasi ini
merangkumi penyelidikan eksperimen mengenai serbuk detergen tanpa fosfat (PFD)
gabungan surfaktan anionik binari C16MES dan asid alkil benzena sulfonik linear
(LABSA) pada skala makmal dan loji pandu serta meliputi kajian pengguna terhadap
produk detergen pakaian khasnya merujuk kepada serbuk detergen pakaian gabungan
C16MES berasaskan sawit. Eksperimen makmal peringkat awal telah mendapati
bahawa serbuk PFD detergen hasilan C16MES/LABSA pada nisbah 50:50 dan pH 7
– 8 mempunyai kestabilan ciri kebersihan yang baik apabila dipanaskan secara
berterusan selama seminggu di dalam ketuhar pada suhu 50 oC dengan kelembapan
relatif sebanyak 85%. Eksperimen berikutnya telah dijalankan di dalam loji pandu semburan kering menggunakan formulasi-formulasi PFD dari enam nisbah
C16MES/LABSA yang berlainan dan pada keadaan pH yang sama. Tiga formulasi
PFD telah dipilih untuk penilaian selanjutnya berdasarkan kesesuaian formulasi-
formulasi tersebut di dalam proses pengeringan semburan. Ciri-ciri dari segi
kebersihan dan sifat partikel serbuk detergen yang terhasil dari tiga formulasi terpilih
ini telah dianalisa. Berdasarkan kepada penilaian keseluruhan, C16MES/LABSA
pada nisbah 40:60 telah dipilih sebagai formulasi PFD yang ideal. Ujian seterusnya
telah mengesahkan bahawa serbuk detergen semburan kering (SDDP) dari formulasi
ideal mempunyai tahap biodegradasi yang tinggi (60% dalam masa 13 hari), ciri eko-
ketoksikan yang rendah (LC50 sebanyak 11.3 mg/L) dan sifat kebolehaliran partikel
yang sederhana (nisbah Hausner pada 1.27 dan indeks Carr pada 21.3). Selain dari kajian eksperimen, satu kajian rintis telah dijalankan untuk mengkaji pilihan (format,
jenama dan asal detergen) dan tabiat pembelian (kesedaran, pengetahuan dan persepsi) pengguna terhadap produk detergen pakaian, khususnya serbuk detergen
pakaian gabungan MES berasaskan sawit. Majoriti responden (82%) melaporkan
bahawa walaupun mereka tidak mempunyai pengetahuan mengenai serbuk detergen
yang digabungkan dengan MES dan juga tidak pernah mendengar mengenai surfaktan
MES, tetapi pilihan mereka untuk menggunakan produk mesra alam yang baru ini
secara amnya adalah positif (94%). Keputusan ini menunjukkan bahawa terdapat
potensi komersil untuk serbuk detergen pakaian gabungan MES berasaskan sawit dan
dengan strategi pengkomersilan yang efektif, produk ini boleh mencapai kejayaan di
dalam pasaran.
vii
TABLE OF CONTENTS
CHAPTER TITLE PAGE
TITLE i
DECLARATION ii
DEDICATION iii
ACKNOWLEDGEMENT iv
ABSTRACT v
ABSTRAK vi
TABLE OF CONTENTS vii
LIST OF TABLES xiii
LIST OF FIGURES xv
LIST OF SYMBOLS xix
LIST OF APPENDICES xxiii
1 INTRODUCTION 1
1.1 Background 1
1.2 Problem Statements 4
1.3 Research Aim and Objectives 5
1.4 Research Design 5
1.5 Research Significance and Benefits 8
1.5.1 Pentamoden Sdn. Bhd 8
1.5.2 Industry and Country 8
1.6 Scope of Research and Limitations 9
1.7 Structure of Dissertation 10
viii
2 LITERATURE REVIEW 12
2.1 Introduction 12
2.2 Modern Detergents 13
2.3 Types and Format of Laundry Detergents 13
2.4 Types and Properties of Laundry Detergent Powders 14
2.5 Unit Operations for the Production of Laundry
Detergent Powders 15
2.5.1 Agglomeration Process 15
2.5.2 Spray Drying Process 17
2.6 Components of Laundry Detergent Powders and
Their Functions 20
2.6.1 Surfactants 20
2.6.2 Builders 23
2.6.3 Auxiliary Detergent Components 25
2.7 Classifications of Surfactants 26
2.7.1 Anionic, Non-Ionic, Cationic and
Amphoteric Surfactants 27
2.7.2 Petrochemical Based Surfactants 28
2.7.2.1 Linear Alkyl Benzene Sulphonate
(LABS) 29
2.7.2.2 Alpha Olefin Sulphonates (AOS) 30
2.7.3 Oleochemical Based Surfactants 31
2.7.3.1 Oleo-Based Fatty Alcohol Sulphate
(FAS) 32
2.7.3.2 Oleo-Based Fatty Alcohol
Ether Sulphate (FAES) 33
2.7.3.3 Methyl Ester Ethoxylate (MEE) 34
2.7.3.4 Methyl Ester Sulphonate (MES) 35
2.8 History and Development of Oleochemical
Based MES 38
2.8.1 Development on MES Plants 42
2.8.2 Comparison between MES Technologies 45
2.8.3 Properties and Characteristics of MES 47
2.8.3.1 Detergency, Foaming Ability and
ix
Wetting Power of MES 48
2.8.3.2 Biological Properties of MES 49
2.8.3.3 Other Properties of MES 50
2.8.4 Economics of MES Production Compared to
LABS 51
2.8.5 Palm C16ME as Potential Feedstock for MES 52
2.8.6 Application of MES in Laundry Detergent
Powders 53
2.8.6.1 MES in the Production of HDDP 55
2.8.6.2 MES Issues in the Production of LDDP 55
2.9 Consumer Studies on Laundry Detergents 56
2.9.1 Consumer Preferences and Purchasing
Behaviour 57
2.9.2 Environmental Regulation and Green
Consumers 59
3 RESEARCH METHODOLOGY 61
3.1 Research Methodologies 61
3.1.1 Quantitative Experimentation 61
3.1.1.1 Raw Materials and Chemicals 62
3.1.1.2 Laboratory and Pilot Scale Detergent
Formulations 62
3.1.1.3 Laboratory Scale Preparation of Basic
Laundry Detergent Powders Using
C16MES and LABSA 64
3.1.1.4 Pilot Scale Production of Spray Dried
Basic Laundry Detergent Powders Using
C16MES and LABSA 65
3.1.1.5 Detergent Slurry Analysis
– pH and Concentration 74
3.1.1.6 Preparation of Detergent Powder
Samples 74
3.1.1.7 Detergent Powder Analysis 74
3.1.1.8 Detergent Powder Characterization 77
x
3.1.1.9 Biological Properties of Detergent
Powders 79
3.2 Quantitative Pilot Survey 80
3.2.1 Preparation of Palm C16MES Incorporated
Laundry Detergent Powders (OleoKleen)
for Pilot Survey 83
3.2.2 Survey Location and Questionnaire
Development 84
4 LABORATORY AND PILOT SCALE EXPERIMENTAL
ANALYSIS AND DISCUSSION 86
4.1 Introduction 86
4.2 Laboratory Scale Experimental Data Analysis 86
4.2.1 Effects on Detergency – Before and
After Accelerated Ageing Test 87
4.3 Pilot Scale Experimental Data Analysis 88
4.3.1 Effect on Concentration of Detergent Slurries 89
4.3.2 Effect on Detergency 90
4.3.3 Effect on Foaming Ability 92
4.3.4 Effect on Wetting Power 93
4.3.5 Comparison Between Properties of PFD
Formulations 94
4.3.5.1 Effect on Detergency Stability Upon
Storage 94
4.3.5.2 Effect on Bulk Density 95
4.3.5.3 Effect on Particle Size Characteristics 96
4.3.5.4 Effect on Surface Morphology 99
4.3.5.5 Selection of Ideal Detergent Formulation 101
5 PILOT SURVEY ANALYSIS AND DISCUSSION 104
5.1 Introduction 104
5.2 Pilot Survey Data Analysis 104
5.2.1 Demographic Characteristics of Respondents 107
5.2.2 Respondents Preferred Brand of Laundry
xi
Detergents 108
5.2.3 Respondents Preferred Format of Laundry
Detergents 112
5.2.4 Respondents Preferred Origin of Laundry
Detergents 116
5.2.5 Respondents Awareness/Knowledge on the
Application of Synthetic Surfactants as Laundry
Detergent Actives 120
5.2.6 Respondents Awareness/Knowledge on
Application of Natural Surfactants as Laundry
Detergent Actives 121
5.2.7 Respondents Awareness/Knowledge on the
Existence of Palm Based Surfactant (MES) 122
5.2.8 Respondents Willingness to Pay A Premium for
Palm MES Based Laundry Detergent Powder 123
6 COMMERCIALIZATION STRATEGY FOR LAUNDRY
DETERGENT POWDERS INCORPORATED WITH
C16MES (OLEOKLEEN) 124
6.1 Introduction 124
6.2 Blue Ocean Strategy (BOS) 125
6.3 Company Background 126
6.4 Competitive Analysis Using SWOT and New Strategy
Goal for the Company 127
6.5 Competitive Analysis of Leading Laundry Detergent
Powder Manufacturers in Malaysia 130
6.6 Value Innovation and Four Action Framework
(ERRC Grid) for OleoKleen 132
7 CONCLUSION AND RECOMMENDATION 137
7.1 Summary of Findings 137
7.2 Conclusions 140
7.3 Contributions to Knowledge 141
7.4 Research Contributions to Industry 142
xii
7.5 Recommendations for Further Study 142
REFERENCES 144
Appendices A - M 167 - 226
xiii
LIST OF TABLES
TABLE NO. TITLE PAGE
2.1 Compositions of phosphate and non-phosphate spray-dried
LDDP 19
2.2 Auxiliary detergent components and their functions 26
2.3 Sources of feedstock for anionic surfactants 28
2.4 Other established and newly proposed MES plants 44
2.5 Distinct differences in MES technology 45
2.6 CrMC and Krafft points for different MES homologs 48
2.7 Equations to calculate production cost of MES and LABS 51
2.8 Typical HDDP formulations used in agglomeration process 54
2.9 Typical spray-dried LDDP formulations 54
2.10 Hydrolysis of MES during spray drying process 56
3.1 Laboratory scale PFD formulations 63
3.2 Pilot scale PFD formulations 63
3.3 Components of PS-Dryer and their functions 67
3.4 PS-Dryer - Specifications, technical parameters and
optimized operating data 72
4.1 Particle diameters for different C16MES/LABSA ratios at
10%, 50% and 90% cumulative volume distribution 99
4.2 Fish mortalities after 96 h for SDDP resulted from ideal pilot
scale PFD Formulation 103
5.1 Demographic profile of respondents 107
5.2 Respondents statistical scores for awareness/knowledge on
application of synthetic surfactants 120
5.3 Respondents statistical scores for awareness/knowledge on
xiv
application of natural surfactants 121
5.4 Respondents statistical scores for awareness/knowledge on
existence of palm based MES 122
5.5 Respondents statistical scores on willingness to pay a premium
for palm MES detergent powder 123
6.1 Sun Jiang’s SWOT profile 128
6.2 SWOT analysis of leading LDDP brands in Malaysia 131
6.3 Four action framework (ERRC grid) for OleoKleen 132
6.4 Formulation cost for SDDP resulted from ideal formulation 135
(OleoKleen)
xv
LIST OF FIGURES
FIGURE NO. TITLE PAGE
1.1 Flowchart of the research activities 7
2.1 Different formats of laundry detergents 14
2.2 Dry granulation using two pressure roller compactor 16
2.3 Typical wet granulation process for base HDDP 17
2.4 Typical spray drying process for LDDP 18
2.5 Combination of spray drying and wet granulation systems
for fully formulated detergent powder production 19
2.6 Simplified structure of a surfactant 21
2.7 Spherical micelle of a surfactant 22
2.8 Critical micelle concentration (CrMC) 22
2.9 Stain removal mechanism in a washing machine 23
2.10 Classes of surfactants 27
2.11 Chemical conversion of LABSA into LABS 29
2.12 Chemical structure of AOS 30
2.13 Basic oleochemicals and oleochemical derivatives 31
2.14 Chemical structure of FAS 32
2.15 Chemical structure of FAES 33
2.16 Chemical structure of MEE 34
2.17 Formation of MES from ME 35
2.18 Process flow diagram for MES production using acid bleach
route 36
2.19 Reactions involved in the sulphonation of ME into MESA 37
2.20 Characteristics of MES compared to other commercial anionic
surfactants 38
xvi
2.21 Formation of disalt from two sources (di-adduct and MES) 39
2.22 Companies involved in the development of MES technology 41
2.23 MES paste produced from MES plant in Dalian, China 43
2.24 Conversion of ME into MES using processes developed by
Chemithon and Desmet Ballestra 47
2.25 Consumers willingness to pay extra for green products in six
selected countries 60
3.1 Laboratory setup for preparation of detergent slurry and its
powder 64
3.2 Phase 1 - Site preparation 65
3.3 Phase 2 – Unloading from container 66
3.4 Phase 3 – Installation 66
3.5 Phase 4 – Complete setup of pilot spray dryer (PS-Dryer) 67
3.6 Schematic of the PS-Dryer 69
3.7 Isometric of the PS-Dryer 70
3.8 Algorithm for optimization of spray drying process/conditions 71
3.9 Testing of PS-Dryer 71
3.10 Conceptual framework of the pilot survey 81
3.11 Refined framework of the pilot survey research 82
3.12 Preparation of palm C16MES incorporated laundry detergent
powders 83
3.13 OleoKleen box-packs filled with palm C16MES based laundry
detergent powders 83
3.14 The Waterfront, Desa Park City, Kuala Lumpur 84
3.15 Questionnaire for OleoKleen 85
4.1 Detergency of laboratory scale PFD formulations before and
after 1 week of accelerated ageing test, a. L1 (pH 10)
b. L2 (pH 7 – 8 ) 87
4.2 Detergent slurry concentration at different C16MES/LABSA
ratios 90
4.3 Detergency of pilot scale PFD formulations over different ratios
of C16MES/LABSA a. JB01 – carbon black
b. JB02 – protein c. JB03 – sebum 91
4.4 Foaming ability of pilot scale PFD formulations over different
xvii
ratios of C16MES/LABSA 93
4.5 Wetting power of pilot scale PFD formulations over different
ratios of C16MES/LABSA 93
4.6 Effect of C16MES/LABSA ratios on detergency/active upon
initial and after nine months of storage period 95
4.7 Effect of different C16MES/LABSA ratios on bulk density 96
4.8 Effect of different C16MES/LABSA ratios on particle size
distribution (PSD), a. 0:100 b. 20:80 c. 40:60 97
4.9 Effect of different C16MES/LABSA ratios on particle size
uniformity (Pu) 98
4.10 Effect of different C16MES/LABSA ratios on spread of
equivalent particle diameters (Sed) 98
4.11 Effect of different C16MES/LABSA ratios on surface
morphology of SDDP, a. 0:100 b. 20:80 c. 40:60 100
4.12 Biodegradability of ideal pilot scale PFD formulation 102
5.1 Preferred laundry detergent brand among respondents 108
5.2 Gender demographics on laundry detergent brands 109
5.3 Age demographics on laundry detergent brands 110
5.4 Race demographics on laundry detergent brands 110
5.5 Education level demographics on laundry detergent brands 111
5.6 Monthly income demographics on laundry detergent brands 111
5.7 Preferred laundry detergent format 112
5.8 Gender demographics on detergent format 113
5.9 Age group demographics on detergent format 114
5.10 Race demographics on detergent format 114
5.11 Education level demographics on detergent format 115
5.12 Monthly income demographics on detergent format 115
5.13 Preferred detergent origin 116
5.14 Gender demographics on laundry detergent origin 117
5.15 Age group demographics on laundry detergent origin 118
5.16 Race demographics on laundry detergent origin 118
5.17 Education level demographics on laundry detergent origin 119
5.18 Monthly income demographics on laundry detergent origin 119
6.1 Organizational structure of Pentamoden Sdn. Bhd. 129
xviii
6.2 Strategy canvas for OleoKleen 133
xix
LIST OF SYMBOLS
A - Reflectance after wash
AE - Alcohol ethoxylate
AES - Alcohol ether sulphate
APG - Alkylpolyglycoside
AOS - Alpha olefin sulphonate
AS - Alcohol sulphate
ASTM - American Standard Testing Method
B - Reflectance before wash
BOS - Blue Ocean Strategy
C16ME - Saturated C16 carbon chain methyl esters
C16MES - C16 carbon chain methyl ester sulphonate
cm - Centimeter
CI - Carr’s index
CMC - Carboxymethyl cellulose
Co - Reflectance of the original unsoiled test fabric
CrMC - Critical micelle concentration
D10 - Particle diameters at cumulative volume percentage of
10%
D50 - Particle diameters at cumulative volume percentage of
50%
D90 - Particle diameters at cumulative volume percentage of