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ABSTRACT
Dyes from Pterocarpus osun Craib and Lawsonia inermis Linn. were extracted using ethanol and methanol respectively. The extracted dyes were subsequently purified using chromatographic methods. Purified pigments were characterized using Ultra-Violet Visible Spectrophotometer, Fourtier Transform Infrared Spectrophotometer and Lovibond Tintometer. The UV spectra of the dyes in petrol, kerosene and diesel showed presence of chromophores. The FTIR spectra of the dyes showed presence of phenolic O-H stretching and C=C of aromatic functional groups. The dye from Lawsonia inermis Linn. was remarkably stable in colouring petrol for a period of twenty-eight days but not in kerosene and diesel while the dye from Pterocarpus osun Craib was not stable. Thus, dye from Lawsonia inermis Linn. can be used as alternative source of colourant for petrol while the dye can not be used for the same purpose for kerosene and diesel due to their instability. The dye from Pterocarpus osun Craib cannot be used because of their instability. They are not remarkably active in colouring any of the petroleum products (petrol, kerosene and diesel).
TABLE OF CONTENTS
Title Page i
Certification ii
Dedication iii
Acknowledgement iv
Abstract v
Table of Contents vi
List of Tables x
List of Figures xi
List of Appendices xii
CHAPTER ONE:
1.0 Introduction 1
- Dyestuffs 1
- Lawsonia inermis Plant 4
- Pterocarpus osun Craib plant 5
- Statement of the problems 5
- Objectives of the study 6
- Justification of the study 6
CHAPTER TWO:
2.0 Literature review 7
- Historical development 7
- Colour and constitution 9
- Nomenclature of dyes 17
- Classification of dyes 19
- Classification according to methods of application 19
- Classification according to chemical constitution 36
- Natural dyes 51
- Plant dyes 52
- Animal dyes 59
- Mineral dyes 61
- Uses of dyes 62
- Dyeing 65
- Mechanism of dyeing 65
- Natural dyeing principles 67
- Fastness properties 69
- Colour in textile industry 70
- Colour in petroleum industry 71
CHAPTER THREE:
- Materials and methods 73
- Reagents 73
- Equipment 73
- Plant materials 74
- Extraction procedure 75
- Purification of the extracts 75
- Column chromatographic purification of osun extract 76
- Vacuum liquid chromatographic purification of inermis extract76
- Solubility of the dyes in organic solvents 76
- De-colourization of petroleum products 77
- Spectroscopic analysis of the dyes 77
- Ultraviolet spectroscopy 77
- Infrared spectroscopy 77
- Colour stability analysis of the dyes 78
CHAPTER FOUR:
- Results and discussion 79
- Physical data of the dyes 79
- Solubility test of the dyes 80
- osun dye wavelengths of maximum absorption in petroleum products 81
- inermis dye wavelengths of maximum absorption in petroleum products 85
- Colour intensity of osun dye in petroleum products 89
- Colour intensity of inermis dye in petroleum products 93
- Infrared spectra analysis of osun dye 97
- Infrared spectra analysis of inermis dye 98
- Discussion 98
- Contributions to knowledge 101
- Conclusion 102
- Physical data of the dyes 79
References 103
Appendices 110
CHAPTER ONE
1.0 Introduction
1.1 Dyestuffs
Today, in the world of growing environmental consciousness, natural colourants have attracted the attention of everyone1,2. The alarming rate of high use of synthetic dyes which causes carcinogenicity, mutagenicity, green house effect and are very expensive have provided an urgent approach to the use of natural plant dyes in the petroleum industry3,4. Natural plant dyes have been discovered accidentally and their uses have become so much a part of man’s customs that it is difficult to imagine modern world without dyes. The art of dyeing spread widely as civilization advanced5.
A dye is an organic compound composed of chromophore (the coloured portion of the dye molecule) and auxochrome (which slightly alters the colour) .The auxochrome makes the dyes soluble and is a site for bonding material. Dyes are molecules that can be dissolved in water or some other carrier so that they will penetrate the material6.
For a dye to be usable in colouring materials, it must be highly coloured; must yield goods that are “colour fast”, or resistant to colour change or loss during use and care; and must be soluble or capable of being made soluble in water or other medium in which they are applied, or they must themselves be molecularly dispersible into the material7.
The archaeological evidences have shown that dyeing has been extensively carried out for over 5000 years, particularly in India and Phoenicia8,9. The dyes were obtained from animal, vegetable or mineral origin, with no or very little processing. They include cochineal obtained from dried cochineal insect, brazil-wood from caesalphia plant, madder from the roots of Rubia tinctoria, Tyrian purple from purple snail (Murex bandaris), and indigo from the leaves of Indigofera tinctoria and many more. The plant parts that were used are roots, bark, leaves and wood10,11. Colourant improve the appearance, culinary effect and promote acceptability of substrates12.
The colour index categorizes all colouring matters according to their application and characteristics. Dyes can also be classified according to their chemical structure, shade, fastness, etc13.
With advances in science and technology, dyes synthetically produced from coal tar and petroleum sources, and natural dyes have almost been replaced by synthetic dyes. The most significant discovery in synthetic dyes occurred in the 19th century when the first man-made dye was synthesized by a Chemist, William Henry Perkin14. He produced the first basic azine dye known as mauveine [1] (Mauve). The production of this dye opened door for the synthesis of many classes of dyes including the first azo dye, Congo Red [2].
Dyes are used to colour petrol, kerosene and diesel in order to improve their appearance, as well as for identification of grade, type of use or merely as a trademark of the manufacturer15. Solvent dyes used to colour refined petroleum products is to be able to differentiate between petrol, diesel, kerosene and jet fuels16. Petroleum dyes help in identification of fuel adulteration. They also help to create differentiation in various petroleum products such as leaded and unleaded, high and low octane gasoline, high and low sulphur diesel and aviation fuels attributes17. Other reasons for dyeing fuel, such as for aviation, supports the fuelling process itself, to ensure that the right type of fuel is used in the correct aircraft – as the consequences of getting this wrong can be disastrous18. However, solubility as well as hue and fastness are the major determinant factors for dyes used in these petroleum products.
Other uses of dyes include in the colouration of food items, inks, metals, leather, textiles and paper. Other areas of use include photographic paper, as indicator in chemical analysis and biological stain and as point leak detection19. With the increasing demand in petroleum industry and various sectors of the economy for dyes and pigments coupled with the high cost of synthetic dyes importation, there is need to explore plant dyes and their applications will improve the socio-economy and artistic development of the nation.
Synthetic dyes have been used over the years in the petroleum industry for colouring petroleum products. This helps in check-mating adulteration, identification of grade or quality and for aesthetic purposes in the oil industry. The cost and toxicity (carcinogenity and mutagenity) of the synthetic dyes have shifted attention for alternative dyes which are cheap and environmental friendly. Dye of Pterocarpus osun Craib have been used to colour petroleum products (petrol, kerosene and diesel) but their stabilities have not been studied or reported while dye of Lawsonia inermis Linn. have not been used to colour petroleum products.
Lawsonia inermis (Henna) plant belongs to the family lythraceae. The plant grows at temperatures higher than 11 oC and needs about 5 years to mature. It has a height of 8-10 feet 20-22. The leaves have been extensively used for centuries in the Middle East, the Far East and Northern Africa as dye for nails, skin, hands, hair and textile23. Henna is also used in treating skin problems, headache, jaundice, amebiasis and enlargement of the spleen. Leaves of Lawsonia inermis provide an important cosmetic dyes and so on 24-25. The major pigment in henna leaf is lawsone [2-hydroxyl-1,4-naphthaquinone (C10H6O3)], having a fast-dyeing property26. Lawsonia inermis has been well investigated phytochemically by various researchers. The occurrence of β-sitosterol glucoside, flavonoids, quinoids, naphthalene derivatives, gallic acid, coumarins, and xanthones in lawsonia leaf has been reported27-32.
- Pterocarpus osun Craib plant
Pterocarpus osun belongs to the family papilionaceae and it occurs throughout the tropics. The Nigerian species are trees of about 30 meters tall, with a girth size of about 2.4 meters with spreading crown and with bright yellow and usually alternate leaflets. It has distinct pinkles on twigs and young branches. The fruits are dark brown and velvety when young, with short soft and often stickly pickles mostly surrounding the centre33,34. The wood of Pterocarpus osun contains 16 % of red colour pigments, which are insoluble in water but soluble in organic acid and alkali6. Pterocarpus osun are medically useful for superficial skin diseases such as eczema and has also been used as an active ingredient in soap35,36. Other active constituents of Pterocarpus osun are tannins, phenols, saponin and flavonoids37-40.
- Statement of the problems
Synthetic dyes are no longer universally attractive in colouring petroleum products due to the numerous challenges (carcinogenic, mutagenic, toxic, cost and so on) associated with their use. The use of colourants for petroleum products cannot be avoided because it helps in quick, visual differentiation of petrol, kerosene and diesel. It also helps in identification of grade or quality of petroleum products. Presently, the dyes used by Nigerian refineries are imported, coded and used without the source of import disclosing the exact chemical names and composition either to the refinery staff or to the public. The chemical nature used of dyes in imported petroleum products are also shrouded in secrecy. These have necessitated the search for local alternative sources of colourants for petroleum products in the oil industry.
This study has the following objectives:
- To assess the stability of the heartwood of osun and young leaf of L. inermis plant extract respectively, as colourants for petroleum products (petrol, kerosene and diesel).
- To determine alternative sources of colouring petroleum products rather than using synthetic dyes, and
- To determine the stability of the dye colours when added to petroleum products.
- Justification of the study
Natural dyes have been widely reported to be non-toxic, environmentally friendly and less expensive. Therefore, the assessment of two local plant dyes (P. osun and L. inermis) as colourants for petroleum products is justified.
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