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Cyclic Intermediates and Dyes
Cyclic Intermediates and Dyes
Submitted to:
Engr. Edwin Richard R. Ortiz
ChE 511 Instructor
Submitted by:
Ilea A. Verano
BS ChE 5
I. Dye Intermediates
a. Inorganic Materials
b. Primary Intermediates
c. Dye Intermediates
V. Nomenclature of Dyes
b. Colour Index
a. Reaction
b. Product Isolation
d. Waste Characteristics
I. DYE INTERMEDIATES
The precursors of dyes are called dye intermediates. They are obtained from
reactions. Usually, the raw materials are cyclic aromatic compounds, but acyclic
are derived from two principal sources, coal tar and petroleum.
Coal tar results from the pyrolysis of coal and is obtained chiefly as a by-product in
the manufacture of coke for the steel industry. Products recovered from the
fractional distillation of coal tar have been the traditional organic raw material for
the dye industry. Among the most important are benzene, toluene, xylene
cresol.
The petroleum industry is now the principal supplier of benzene, toluene, the
xylenes, and naphthalene. Petroleum displaced coal tar as the primary source for
these aromatic compounds after World War II because it was relatively cheap and
abundantly available. However, the re-emergence of king coal is predicted for the
twenty-first century, when oil supplies are expected to dwindle and the cost of
producing chemicals from coal (including new processes based on synthesis gas)
and dye intermediates. Large amounts of inorganic materials are consumed in both
a. Inorganic Materials
These include acids (sulfuric, nitric, hydrochloric, and phosphoric), bases (caustic
soda, caustic potash, soda ash, sodium carbonate, ammonia, and lime), salts
(sodium chloride, sodium nitrite, and sodium sulfide) and other substances such as
chlorine, bromine, phosphorus chlorides, and sulfur chlorides. The important point
processes, and the overall tonnage used by, and therefore the cost to, the dye
industry is high.
b. Primary Intermediates
descriptions, which associate them with raw materials rather than with
intermediates.
2. At least 1000 t/yr capacity from a single plant and may be up to 100,000 t/yr, e.g.,
aniline.
3. Manufacturing process and/or operation is continuous or semicontinuous, i.e., at
c. Dye Intermediates
manufactured within the dyes industry, and they are nearly always colorless.
Colored precursors are conveniently termed color bases. As distinct from primaries
operational stages in their manufacture, and therefore cost. Prices may be classed
Frequently the color of a product is the reason for its sale. For this reason, it is
dyes are important for manufacturers to control and manipulate the color or hue of
their final product. Dyes add value to products far beyond their cost.
Dyes are colored, ionizing and aromatic organic compounds which show an affinity
The preparation and application of dyestuffs is one of the oldest forms of human
where ancient fabrics were unearthed. There is also mention of it in the Bible and
other works of classical antiquity. It was in 2600 BC when earliest written records
Perhaps one of the real breakthroughs in the history of dyes came in 1856 when a
certain discovery that acted as a sort of launching pad for the modern chemicals
industry.
natural products. William Perkin chanced upon his now famous 'Aniline Mauve' dye
while he was attempting to synthesize quinine, the only cure for malaria. Perkin
named his color Mauveine, after the French name of non-fast color which was
made of natural dyes. So "Mauve" (a basic dye) was the first synthetic dye stuff.
Mauve was a derivative of coal tar. It was the first mass-produced dye, that was
commercially available and the idea was born that a color could be made in the
factory.
For dyes to be effective, they must be colored and must impart its color to
a part to regulate the solubility and dyeing properties, the auxochrome (electron
appearance of, absorbent bands in the visible spectrum. The chromophore groups
Some molecules lose their colors when the chromophore groups are saturated.
The auxochromes, the part of the dye which causes it to adhere to the material
which it colors usually are: -NH2, -OH, -NR2, -COOH and SO3H. These
auxochromes are salt-forming which aids the solubility of the dye in acidic and
Dryers and Colourists and the American Association of Textile Chemists and
Colorists. Published as the Colour Index, dyes may be classified according to (1)
its chemical class, expressed an assigned number and (2) its usage or application,
According to Hunger (2003), the most appropriate system for the classification of
properties. Ex. Azo dyes are known for being strong, good all-round
properties, and cost-effective; while anthraquinone dyes are known for being
3. It is the classification used most widely by both synthetic dye chemists and dye
technologists.
The twenty-six recognized types of dyes by chemical classification are as follows:
follows:
1. Acid dyes
Dyes termed as acid dyes are derived their name from being insoluble in acid
nylon. Acid dyes are also used in dyeing leather and paper.
From Knutson’s Synthetic Dyes for Natural Fibers, acid dyes can further
classified into:
2. Azoic dyes
These “ice colors” are made right on the fiber by coupling diazotized materials
while in contact with the fibers. Low temperature keeps the diazonium
compound from decomposing until ready to couple. These are brilliant and
long-lasting and are used primarily for printing on cotton. Rayon, cellulose
3. Basic dyes
Basic dyes are mostly amino and substituted amino compounds soluble in acid
and made insoluble by the solution being made basic. Most are triarylmethane
or xanthenes. These can be used to dye wool or cotton with a mordant, but are
usually used for duplicator inks, carbon paper, and typewriter ribbons. In
solvents other than water, they form writing and printing inks. Basic dyes can
Direct dyes are water-soluble anionic dyes. These dyes are used to dye cotton
directly, that is, without the addition of a mordant. They are also used to dye
union goods (mixed cotton, and wool, or silk). Other direct dyes are used on
leather, paper, rayon and nylon.These are generally azo dyes, and their
solubility in the dye bath is often reduced by adding salt. Some are developed
on the fiber by forming the diazonium salt on the cloth then coupling to
increase insolubility. Most of the dyes in this class are polyazo compounds,
5. Disperse dyes
Modern synthetics are difficult to dye. Disperse dyes are applied as very finely
divided materials which are adsorbed onto the fibers with which the then form
a solid solution. Simple, soluble azo dyes can be used, but anolamine group is
commonly found in this group and aids both in dispersion and adsorption.
Disperse dyes are substantially water soluble and are used to dye polyester
but they can also be used to dye nylon, cellulose triacetate, and acrylic fibers.
dyebath is used. The very fine particle size gives a large surface area that aids
dissolution to allow uptake by the fiber. The dyeing rate can be significantly
These dyes react to form a covalent link between the dye and the cellulose
fiber which they are customarily used to dye. This produces goods of
ink-jet printing of textiles. Reactive dyes can also be used on rayon and some
nylon. The principal chemical classes of reactive dyes are azo (including
anthraquinone.
Everyone knows what is meant by white, but its accurate definition and
description prove to be quite elusive. “Bluing” has been used for a very long
obtained with soap, textiles, plastics, paper, and detergents by the addition of
these “optical brighteners”. They absorb ultraviolet light and emit bright blues,
which give greatly improved whiteness. Brighteners are stilbenes with some
recycled paper.
8. Food, drug, and cosmetic dyes
Food, drug and cosmetic dyes include those coming from anthraquinone, azo
and indigoid classes. Some of these dyes are from the class of carotenoid and
triaryl methane.
9. Mordant dyes
Some dyes combine with metallic salts to form highly insoluble colored
materials called lakes. These materials are usually used as pigments. If a cloth
chromium, or iron salt and then contacted with a lake-forming dye, the metallic
precipitate forms in the fiber, and the colors become far more resistant t light
and washing. Substituent groups such as –OH and –COOH attached to azo or
dyes.
dyes that are devoid of polar solubilizing groups such as sulfonic acid,
and anthraquinone, but phthalocyanine and triarylmethane dyes are also used.
Solvent dyes are used for coloring plastics, gasoline, oils, shoe polishes,
Sulfur dyes are a large, low-cost group of dyes which produce dull shades on
cotton. They have good fastness to light, washing, and acids but are very
Vat dyes have chemical structures that are highly complex and most are
soluble and colorless, and are called leuco vats. Vat dyes are applied mainly
Vat dyes are expensive and are used to color fabrics (cotton, rayon or wool)
that are washed often like men and women’s shirts. Some vats are supplied as
The best known vat dye is the indigo which makes dark (navy) shades. As a
dye for cotton denim, its lack of fastness seems to be prized as a fad.
Table 1: Usage classification of dyes
PRINCIPAL
CLASS METHOD OF APPLICATION CHEMICAL TYPES
SUBSTRATES
Acid nylon, wool, silk, paper, usually from neutral to acidic dyebaths azo (including
inks and leather premetallized),
anthraquinone,
triphenylmethane, azine,
xanthenes, nitro and nitroso
Direct cotton, rayon, paper, applied from neutral or slightly alkaline azo, phthalocyanine,
leather, and nylon baths containing additional electrolyte stilbene, and oxazine
Disperse polyester, polyamide, fine aqueous dispersions often applied azo, anthraquinone, styryl,
acetate, acrylic and by high temperature/pressure or lower nitro and benzodifuranone
plastics temperature carrier methods; dye may
be padded on cloth and baked on or
thermofixed
Fluorescent soaps and detergents, all from solution, dispersion or stilbene, pyrazoles,
brighteners fibers, oils, paints, and suspension in a mass coumarin, and
plastics naphthalimides
Mordant wool, leather, and applied in conjunction with Cr salts azo and anthraquinone
anodized aluminum
Reactive cotton, wool, silk, and reactive site on dye reacts with azo, anthraquinone,
nylon functional group on fiber to bind dye phthalocyanine,
covalently under influence of heat and triphendioxazine, formazan,
ph oxazine and basic
Sulfur cotton and rayon aromatic substrate vatted with sodium indeterminate structures
sulfide and reoxidized to insoluble
sulfur-containing products on fiber
Vat cotton, rayon, and wool water insoluble dyes solubilized by anthraquinone (including
reducing with sodium hydrogen sulfite, polycyclic quinones) and
then exhausted on fiber and reoxidized indigoids
VI. NOMENCLATURE OF DYES
Two ways are available for naming dyes. Dyes are either named by
a. Commercial Name
4. Color
more precisely the hue and also to indicate important properties of the dye
The common letters used by manufacturers to describe dyes are tabulated below:
LETTER MEANING
Hue
R Reddish
G Greenish
B Bluish
Dyeing and fastness properties
W Washfast dye
E Exhaust dye
For solvent and disperse dyes
A Lowest level of heatfastness
B Mid level of heatfastness
C Mid level of heatfastness
D Highest level of heatfastness
For reactive dyes
M Warm-dyeing dye
H Hot-dyeing dye
There are instances when some manufacturers designate a bluish red dye as Red
4B while other manufacturers use Violet 2R for the same dye. TO resolve such
company.
It is not uncommon for a single dye to have multiple names if one follows the
nomenclature of dyes using the method in the previous section. The term fuchsin
was once called magenta and light green can also be called methyl green. To
avoid further confusion, it is better to use the Colour Index method in naming dyes.
of Dyers and Colourists and the American Association of Textile Chemists and
dyes.
The general way of identifying dyes using the Colour Index is given below.
The CI generic name (CI Name) identifies dyes using the pattern given above. Its
Name enables the easy identification of the hue and dye type at a glance. The CI
Name, however, may vary from one manufacturer to another. A dye dubbed as CI
Direct Blue 99 from one company may not be identical to the CI Direct Blue 99 of
another company.
structure has already been identified by the manufacturer. Dyes with similar
confusion.
below.
Chemical structure:
perylene-5,10-dione]
The basic steps of dye (and intermediate) manufacture are shown below.
Product drying,
Materials
Reaction Product Isolation grinding, and/or
Charging
finishing
a. Reaction
a. sulfonation,
b. halogenations,
c. amination,
d. diazotization, and
e. coupling
The reactor itself is usually the focal point of the plant, but this does not mean that
it is the most important part of the total manufacture, or that it absorbs most of the
capital or operational costs. The processes after the reaction are often termed as
workup stages. Workup stages differ from one product to another. For example,
The specifications for the reaction vessel for the production of intermediates and
b. The reaction vessel may be made from cast iron, stainless steel, or steel lined
c. The volume of the reaction vessel is between 2-40 m3 (500-10 000 gallons).
Jackets or coils may be used for the heating and cooling of the reactor. High-
boiling fluids (e.g. hot oil or Dowtherm), steam, or hot water may be used to raise
the temperature; while air, cold water, or chilled brine may be used to lower it.
Unjacketed vessels are often used for reactions in aqueous solutions. Heating may
be done through direct introduction of steam, and cooling may be done by addition
of ice. Heat exchangers can also be used. The reaction vessels normally span two
b. Product Isolation
Products are transferred from one piece of equipment to another by gravity flow,
pumping, or blowing with air or inert gas. Solid products are separated from liquids
a. centrifuge
b. filter boxes
In some cases products, usually in the form of pastes discharged from a filter, must
be dried. Even with optimization of physical form, the water content of pastes
b. rotary dryers
c. spray dryers
d. drum dryers
The final stage in dye manufacture is grinding or milling. Dry grinding is usually
carried out in impact mills; considerable amounts of dust are generated and well-
especially continuous drying, allow the production of materials that do not require a
final comminution stage. The ball mill has been superseded by sand or bead mills.
Wet milling has become increasingly important for pigments and disperse dyes.
arrangements.
Figure 1 below shows the layout of a typical azo dye manufacturing plant.
Figure 1: Layout of azo dye manufacturing plant. 1, storage tanks for liquid starting
filter presses; 9, filtrate to waste liquor treatment plant; 10, dryers; 11, emptying of
dyestuffs for feeding to the mill; 12, outgoing air purification plant.
d. Waste Characteristics
Liquid effluents from the cleaning of the equipments after batch operation can
Wastewater generation rate is usually 1-700 liters/kg of product except for vat
dyes. Vat dye production can generate wastewater of up to 8,000 L/kg of product.
a. filtration sludge
c. container residues
b. spent acids
c. process residues from the manufacture of chrome yellow and orange pigments,
molybdate orange pigments, zinc yellow pigments, chrome and chrome oxide
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