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To,
I hereby certify that the work which is presented in the Minor project entitled “Super-Critical
Carbon Dyeing” in fulfillment of the requirements for the award of the Degree of Bachelor of
Technology and submitted to the Department of Civil and Environmental Engineering, Delhi
Technological University (Formerly Delhi College of Engineering), New Delhi is an authentic
record of my own, carried out during a period from August 2016 to December 2016, under the
supervision of Dr. Munendra Kumar, Assistant Professor, Department of Civil
Engineering, Delhi Technological University.
The matter presented in the report has not been submitted by me for the award of any other
degree of this or any other Institute/University.
Signature
It is further certified that the work done in this dissertation is a result of candidate’s own efforts.
Assistant Professor
ACKNOWLEDGMENT
“The successful completion of my work would be incomplete without accomplishing the people
who made it all possible and whose constant guidance and encouragement secured us the
success”.
First of all, we are grateful to the Almighty for establishing us to complete this minor project.
We are grateful to Prof. A.K. Gupta, HoD, Department of Environmental Engineering,
Delhi Technological University (Formerly Delhi College of Engineering), New Delhi and all
other faculty members of our department, for their astute guidance, constant encouragement and
sincere support for this project work.
I also place on record, my sense of gratitude to one and all, who directly or indirectly have lent
their helping hand in this venture. We feel proud and privileged in expressing my deep sense of
gratitude to all those who have helped me in presenting the project.
Last but never the least, we thank our parents for always being with us, in every sense.
TABLE OF CONTENTS
1) ABSTRACT
2) CONVENTIONAL DYEING
i) Introduction
i) Introduction
4) CONCLUSION
1) ABSTRACT
A German patent was granted in 1994 for a process in which a dye, free of additives is
dissolved in a supercritical fluid and the substrate to be dyed is suffused with this.
Research of supercritical fluids as reaction medium and as a solvent medium has seen
recent resurgence, driven by needs to satisfy environmental regulations using efficient
processing and separation techniques. From solid-fluid to liquid-fluid extractions,
polymerization to particle formation, alkylation to hydrogenation to nitration,
chromatographic separation to chiral separation, polymer cleaning to parts cleaning,
potentially, all aspects of chemical processing will be touched by supercritical fluids in
future. Carbon dioxide is the most investigated and used supercritical fluid. It is a
naturally occurring fluid that is chemically inert, physiologically compatible, and
relatively inexpensive and is readily available for industrial consumption.
2) CONVENTIONAL DYEING
i) INTRODUCTION
The procedure for conventional dyeing is an environmentally unfriendly process. The procedure
of conventional dyeing is toxic and wasteful. The process can discharge polluted water and
chemicals, killing aquatic life , ruining soil and poisoning drinking water. It also uses too much
energy, which contributes to global warming.
The procedure for conventional dyeing mainly includes the following steps;
Raw cotton is grown, harvested and ginned to remove impurities. The raw fibers are then spun
into yarn. A mill knits or weaves the yarn into fabric, and that fabric enters the dyeing process.
STEP 2:DYE
Dye colors are created by mixing different amounts of red, blue, and yellow into a solution that
is then poured into the dye bath. The dye is then fixed onto the cotton fabric.
3 ) CHEMICALS
The dyeing process requires extensive use of chemicals. In order for the dye to bond and adhere
to the fabric, salt and alkali must be used to force a reaction.
4)WATER
Dye houses typically use two sources of water: local municipal water and/or ground water,
otherwise known as well water. There are many different steps needed steps needed to fix dye
onto cotton including extensive washing. This means the dye bath is filled and drained six or
more times for a conventional dye cycle. The wastewater ultimately ends up in streams, rivers
and lakes.
Air Pollution :
Water Pollution :
In the textile industry, up to 200,000 tons of these dyes are lost to effluents
every year during the dyeing and finishing operations due to the inefficiency
of the dyeing process.
In addition, the increased demand for textile products and the proportional
increase in their production, and the use of synthetic dyes have together
contributed to dye wastewater becoming one of the substantial sources of
severe pollution problems in current times.
Unfortunately, most of the dyes escape conventional wastewater treatment
processes and persist in the environment as a result of their high stability to
light, temperature , water , detergents, chemicals , soap and other parameters
such as bleach and perspiration. Dyes can remain in the environment for an
extended period of time, because of high thermal and photo stability to resist
bio degradation.
4) Textile dyes can cause allergies such as contact dermatitis and respiratory
diseases, allergic reaction in eyes, skin irritation and irritation to mucous
membrane and the upper respiratory tract.
5) Reactive dyes form covalent bonds with cellulose, woolen and PA fibres.
Certain reactive dyes have caused respiratory sensitization of workers
occupationally exposed to them .
6) The presence of very small amounts of dyes in the water, which are
nevertheless highly visible, seriously affects the quality and transparency
of water bodies such as lakes, rivers and others, leading to damage of
aquatic environment.
7) The highly toxic and mutagenic dyes decrease light penetration and
photosynthetic activity, causing oxygen deficiency and limiting
downstream beneficial uses such as recreation , drinking water and
irrigation.
Supercritical Fluid
Any gas above its critical temperature retains the free mobility of the gaseous state but
with increasing pressure its density will increase towards that of a liquid. Supercritical
fluids are such high compressed gases and as such they combine valuable properties of
both liquid and gas.
1) A supercritical fluid is a substance under pressure above its critical temperature. Under
these described conditions the distinction between gases and liquids does not apply and
substance can only be described as fluid.
3) Supercritical fluids have properties intermediate between those of gases and liquids,
controlled by the pressure.
4) Supercritical fluids have solvent power similar to a light hydrocarbon for most
solutes. However, fluorinated compounds are often more soluble in carbon dioxide
than in hydrocarbons; this increased solubility is important for polymerization
5) Solubility increases with increasing density (i.e. with increasing pressure). Rapid
expansion of supercritical solutions leads to precipitation of a finely divided solid.
The fluids are completely miscible with permanent gases (e.g. N2 or H2) and this
leads too much higher concentrations of dissolved gases than can be achieved
in conventional solvents. This effect has been exploited in both organ metallic
reactions and hydrogenation
The critical values of T and p for some selected compounds and typical properties of
supercritical fluids are compared to those of gases and liquids in Table 1.
Carbon dioxide is the best choice .It is non-toxic, it is used in the food and beverage industry, it
is nonflammable, it is supplied in large amounts either from combustion processes or volcanic
sources without the need of producing new gas and it can be recycled in a closed system.
The low viscosity of supercritical fluids and the rather high diffusion properties of the dissolved
molecules are especially promising aspects for dyeing processes. A supercritical dyeing fluid
should easily dissolve solid dyestuffs and should penetrate even the smallest pores without the
need of vigorous convection procedures.
2) Since carbon dioxide is a constituent of natural metabolic processes occurring in the biosphere
it is consumed by assimilation and is returned to the natural circuit by dissimilation .It is not only
biodegradable as nutrient promoting the growth of plants, but is an essential element of natural
processes.
3) Carbon dioxide does not affect the edibility of foodstuffs and will only have toxic effects at
extremely high concentrations.
4) It is produced on the commercial scale and is readily available together with the necessary
logistics.
5) No disposal problems. It is recovered from the process in the form of an uncontaminated gas
and can be reused.
6) Being easy to handle and combustible, carbon dioxide does not cause problems at working
places.
7) The critical point of the carbon dioxide is within the range which is readily manageable by
technical means( 31C and 73 bar )
10) Processing with supercritical carbon dioxide often generates no waste effluent stream.
11) Maintenance and running cost for wastewater treatment and drying process is not necessary.
The solubilizing power of carbon dioxide in the supercritical state corresponds to that of the
weekly polar solvents. In contact to the conditions governing dyeing in an aqueous liquor, the
disperse dyestuff is transferred to the fiber out of a molecularly disperse solution and not by
micelles which will then allow it to molecularly disperse liberation. In this respect, there exists a
certain similarity to solvent dyeing techniques which, some times ago, were frequently discussed
as an option to dye polyester fibers, which, however, did not gain acceptance for environmental
and toxicological reasons Other reasons for discarding this option included high prices and
unfavorable energy balances in the case of recovery of the solvents. All these shortcomings are
avoided in this case of carbon dioxide. On the other hand, potential merits of solvent dyeing
techniques are surpassed in many respects.
As will be noted from table 1, the density and thus the dissolvability of the supercritical fluid is
more or less similar to relative properties of liquids, whereas the viscosity is similar to that of a
gas. This has an impact on the dyestuff transfer.
Due to its low viscosity, the fluids will ore readily enter pores and capillaries of fibers and/or
fiber bundles. The penetration, for instance of yarn packages, by the supercritical fluid will cause
a substantially lower pressure drop. In a practical case, this means high degrees of solved
molecules such as for dyestuff are higher by more than three powers of ten compared to those of
liquids. This will allow a faster mass transport and, therefore, significantly higher dyeing rates.
Due to the favorable diffusion properties of the supercritical fluid, even the times needed for the
dissolution of the solid dyestuff will be cut to a negligible minimum.
The state of the dyestuff in a super critical solution can virtually be described as gaseous. This
means that it will be absorbed by the fiber at a rate comparable to the high diffusion rates
corresponding to that of a gas. In addition, the dissolved dyestuff will be quickly available for
diffusion into the boundary layers. This results in high degrees of levelness and low convection
in spite of high absorption rates. In addition, the absorption equilibrium will be achieved very
quickly, which in turn will favorably influence the degree of levelness. In this connection, we
would like to mention that in the case of using dyestuff free carbon dioxide and changing of
processing parameters it is possible to extract dyestuff from the fiber.
A crucial difference to dyeing process using a liquid phase is to be seen in the fact that the
solubility of the dyestuff in a supercritical fluid can be continuously changed across a wide
range. The distribution balance dyestuff-fluid/dyestuff-polymer can in fact be continuously
shifted in favor of the polymer until after expansion of the gas to standard pressure the solubility
in the fluid will be equal to zero, where a theoretical exhaustion level of 100 percent is reached.
In the case of using liquid media this would only be possible by evaporation of the solvent.
Spectrophotometric measurements in a supercritical medium during stepwise reduction of the
density have shown that short-time over saturated solutions will be formed which accelerate the
absorption of the dyestuff molecules lack other condensation nuclei during the gaseous phase.
Supercritical carbon dioxide will be partly dissolved in the polymer. It has a softener-like effect
which accelerates the diffusion processes by increasing the chain mobility of the polymeric
molecules. This indicates possibilities of cutting dyeing times and/or an option to use lower
dyeing temperatures.
As soon as the fluid expanded to the atmospheric pressure again it will completely lose its
capacity to dissolve the dyestuff. Any unfixed dyestuff will drop out during the expansion phase
in the form of a dry powder and can be disposed of. The textile goods leave the dyeing
equipment in a dry state and do not contain any solvent because the carbon dioxide is completely
eliminated.
The necessary convection of the liquor can be achieved by an agitator within the dyeing
autoclave or by moving the substrate. Another option is to penetrate the goods, either by the
circulation of the liquor or by utilizing the current produced by continuous replenishment of
carbon dioxide. In the latter case, the flow of replenished carbon dioxide will have to be
continuously loaded with dyestuff. Residues of dyestuff or fiber admixtures to be extracted prior
to dyeing will be collected in a conventional separator. The separation of phase will in this case
be initiated by expansion or by raising the temperature.
Dyeing Apparatus:
An apparatus for dyeing in supercritical carbon dioxide is consists of a temperature controller, a
vessel heater which surrounds the vessel, a stainless steel dyeing vessel of 50ml capacity (with a
quick release
cap), a manometer, a Varex HPLC carbon dioxide pump and a cooler for cooling the head of the
carbon dioxide pump. The apparatus was pressure-tested for use up to 350 bars and 100 degree
Celsius. A side arm connects the top and the bottom of the cell outside the heater to allow the
supercritical carbon dioxide to circulate by thermal convection.
The sample to be dyed (usually 10-25 cm) is wrapped around a perforated stainless steel tube and
mounted inside the autoclave (1) around the stirrer (as shown in figure). The autoclave is then
closed, evacuated and cooled with ice water. Liquid carbon dioxide (8) is filled into the
autoclave in condensed form, weighing the filled-in quantity. As soon as the autoclave has
reached room temperature again, poly glycol, a heat carrier, is added to the tempering bath. The
pressure rises to 250 bars within about 7 minutes, an isochoric process achieved by heating the
glycol bath to 130 C. Following a dye time of 10 minutes the pressure within the autoclave is
reduced to atmospheric temperature within about 2-3 minutes, the carbon dioxide being routed
through a separating vessel in order to recuperate precipitated residual dye stuff. Dyestuff order
is placed in the bottom of the vessel; the apparatus is sealed, purged with gaseous carbon
dioxide, and preheated. When it reaches working temperature, carbon dioxide is isothermally
compressed to the chosen working pressure under constant stirring. Pressure is maintained for a
dyeing period of 0-60 minutes and after wards released.
The fabric sample to be dyed (size= 10 to 25cm) is wrapped around a perforated stainless steel
tube and mounted inside the auto clave around the stirrer. Dyestuff without auxiliary chemicals
was placed on the bottom of the vessel and closed & purged with gaseous CO2 and preheated.
On reaching working temperature CO2 was compressed to the working pressure under constant
stirring. Pressure maintained during the dyeing period of 0 to 60 min and afterwards the fabric is
rinsed with acetone to remove residual dyestuff. Technical parameters are given in Table 2.
The process developed for the yarn package dyeing as shown in table 3. Dyeing temperatures
and volume flow rates are similar with conventional dyeing while actual time required is
typically less.
Advantages of Dyeing in Supercritical Carbon
Dioxide:
The possible advantages to be claimed of this process are:
3) Solubilities are controllable by pressure, allowing control of the dyeing intensity and colour.
4) Diffusivities in the fluid are higher, making mass transfer in the fluid faster.
5) Take up of carbon dioxide by the polymer fibre causes it to swell slightly giving faster
diffusion within the polymer.
6) Viscosities are lower making the circulation of the dye solutions easier.
7) Penetration of voids between fibres is fast because of the absence of the surface tension and
the miscibility of air with carbon dioxide under pressure.
9) No effluents.
11)Energy preservation because drying processes are no longer required (conventional dyeing
processes consume about 3,800 kJ per Kg of water evaporated).
12) No air pollution due to recycling of the carbon dioxide (the gas is not contaminated by the
processes).
17)Reductive after treatments can be dispensed with, i.e. a whole processing step consuming
water and energy can be eliminated.
4)During polyester dyeing ,the trimer is produced .this is removed using aqueous
cleaning ,waterless SC-CO2 as a problem to eliminate
Since autoclaves required for " supercritical dyeing processes ", i.e. equipment permitting
operation at the require temperature and pressures with holding capacities up to one
cu.m., are considered state of the art and the employed for high pressure extraction
processes, many step towards an industrial-scale application in textile plant already being
accomplished. The overwhelming international resonance gained by the new method has
emphasized the high, existential significance of problem met with the treatment of waste
waters in the textile finishing industries. Esp. smaller units allowing short setting-up and
dyeing times, i.e. assuring the high degree of flexibility, were in the center of interest.
Other field for application of supercritical fluid system such as extraction processes is at
present being considered, for instance preparation plants for the removal of spinning oils
etc. In other words the use of carbon dioxide in textile finishing plants is by no means
limited to the dyeing of synthetic fibres. It might, for instance be possible to use
supercritical ammonia for mercerizing operation, or super critical carbon dioxide could
be employed to replace chlorinated hydrocarbons in dry cleaning processes.
Conclusion:
Dyeing in super critical carbon dioxide has been identified as one of the best alternatives to
water-based dyeing and the same has been dealt in detail in this paper. But, this favourable
concept is waiting for its commercial implementation. The Successful commercialization of the
above said concept will definitely improve the economics of dyeing by the way of elimination of
wastewater discharges.