1. The document discusses supercritical carbon dioxide (CO2) dyeing as an alternative to conventional water-based dyeing.
2. Supercritical CO2 dyeing eliminates the use of water, chemicals, and auxiliaries in the dyeing process. It also reduces energy requirements compared to conventional dyeing.
3. The key advantages are that it produces no wastewater, reduces costs, and is more environmentally friendly than conventional dyeing.
2. Prepared By : Mazadul Hasan sheshir
ID: 2010000400008
13th Batch (session 2009-2013)
Department : Wet Processing Technology
Email: mazadulhasan@yahoo.com
Blog : www. Textilelab.blogspot.com (visit)
Southeast University
Department Of Textile Engineering
I/A 251,252 Tejgaon Dhaka Bangladesh
Prepared By :
4. Introduction
The textile industry is believed to be one of the biggest consumers of water. In
conventional textile dyeing, large amounts of water are used both in terms of intake of
fresh water and disposal of wastewater. On average, an estimated 100â150 litres of
water is needed to process 1 kg of textile material, with some 28 billion kilos of textiles
being dyed annually. Water is used as a solvent in many pretreatment and finishing
processes, such as washing, scouring, bleaching and dyeing.
Hence, the elimination of process-water and chemicals would be a real breakthrough
for the textile dyeing industry, and it seems this has now come to fruition , with the
launch of the worldâs first ever industrial dyeing machines that uses super carbon
dioxide (CO2) as a replacement for water. The manufacturer behind thissystem is the
Dutch company, DyeCooTextile Systems BV. Years of extensiveresearch and
development has goneinto producing the novel, completelywater-free dyeing process
which hasconsiderable lower operational costscompared to conventional
dyeingprocesses.
5. Principle
âThe principle of dyeing with CO2 was invented in Germany twenty-five years ago. Developing a
well functioning machine, however, turned out to be too expensive.â DyeCoo Textile Systemsâ
parent company, Feyecon, began tackling this issue ten years ago in partnership with the Delft
University of Technology and Stork. This ultimately resulted in DyeCoo (which was formed in
2008), which literally means dyeing with CO2.
7. Supercritical Fluid
A supercritical fluid is any substance at a temperature and pressure above its critical point, where
distinct liquid and gas phases do not exist. It can effuse(spill,shed) through solids like a gas, and
dissolve materials like a liquid.
In addition, close to the critical point, small changes in pressure or temperature result in large
changes in density, allowing many properties of a supercritical fluid to be "fine-tuned". Supercritical
fluids are suitable as a substitute for organicsolvents in a range of industrial and laboratory
processes. Carbon dioxide and water are the most commonly used supercritical fluids, being used
for decaffeination and power generation, respectively.
PropertiesPropertiesProperties
Solvent
Molecular
weight
Critical
temperature
Critical
pressure
Critical
density
g/mol K MPa (atm) g/cm3
Carbon dioxide (CO2) 44.01 304.1 7.38 (72.8) 0.469
Water (H2O) (acc.
IAPWS)
18.015 647.096 22.064
(217.755)
0.322
Methane (CH4) 16.04 190.4 4.60 (45.4) 0.162
Ethane (C2H6) 30.07 305.3 4.87 (48.1) 0.203
Propane (C3H8) 44.09 369.8 4.25 (41.9) 0.217
Ethylene (C2H4) 28.05 282.4 5.04 (49.7) 0.215
Propylene (C3H6) 42.08 364.9 4.60 (45.4) 0.232
Methanol (CH3OH) 32.04 512.6 8.09 (79.8) 0.272
Ethanol (C2H5OH) 46.07 513.9 6.14 (60.6) 0.276
Acetone (C3H6O) 58.08 508.1 4.70 (46.4) 0.278
Critical properties of various solvents
8. shows density, diffusivity and viscosity for typical liquids, gases and supercritical fluids
Comparison of Gases, Supercritical Fluids and Liquids
Density
(kg/m3)
Viscosity
(ÂľPaâs)
Diffusivity
(mm²/s)
Gases 1 10 1â10
Supercritical
Fluids
100â1000 50â100 0.01â0.1
Liquids 1000 500â1000 0.001In addition, there are:
⢠No surface tension in a supercritical fluid
⢠No liquid/gas phase boundary
⢠By changing the pressure and temperature of the fluid, can be "tuned" to be more
liquid- or more gas
⢠Soluble in material in the fluid
⢠Solubility in a supercritical fluid tends to increase with density of the fluid (at
constant temperature)
⢠Density increases with pressure, solubility tends to increase with pressure
⢠Relationship with temperature is a little more complicated
⢠At constant density, solubility will increase with temperature
All supercritical fluids are completely miscible with each other so for a mixture a single phase can be
guaranteed if the critical point of the mixture is exceeded. The critical point of a binary mixture can be estimated as
the arithmetic mean of the critical temperatures and pressures of the two components,
Tc(mix) = (mole fraction A) x TcA + (mole fraction B) x TcB.
For greater accuracy, the critical point can be calculated using equations of state, such as the Peng
Robinson, or group contribution methods. Other properties, such as density, can also be calculated using
equations of state.
9. Supercritical Carbon Dioxide(CO2)
Carbon dioxide is a readily available, cheap, recyclable and is non-toxic and non-
flammable. Above the temperature of 31.6 oC and pressure of 73 atm carbon dioxide
exhibits physical properties, which are intermediate between those of gases and
liquids.
These conditions are called supercritical conditions and are readily achievable using
commercially available equipment. Supercritical carbon dioxide is able to dissolve a
range of chemical substances including organic substrates, catalysts, and light gases. Its
main advantage however comes from the fact that this solvent can be easily turned
into a gas by simply releasing the pressure leaving no solvent residues and requiring no
evaporation or separation.
Benefits
â˘Applied a clean solvent
â˘Improved control and fine-tuning of process
â˘Developed a remarkably selective synthetic process
â˘Minimised waste & Increased atom utilization
â˘Minimised handling and purification procedures
10. Supercritical Carbon Dioxide(CO2)
Properties
â˘Low cost
â˘Non-Toxic
â˘Density: liquid
â˘Viscosity: Gas
â˘Recycling up to 90%
â˘Inert
â˘Non-explosive
â˘Low critical point
â˘Pressure: 73.858 Âą 0.005 bar
â˘Temperature: 31.05 Âą 0.05 ÂşC
12. Investigation of Dye-Fiber Reactions in SC-CO2
Chemistry of Dyes
â˘Reactive dyes for cotton, rayon, silk, and wool form stable chemical links with textile materials
to produce colored fabrics with excellent overall fastness, other dyestuffs only form loose bonds
with fibers (VS-dye)
â˘Acetate, nylon, and polyester fibers colored with dispersed dyes retain their color even after
repeated exposure to sunlight and washing (ES-dye)
Conventional aqueous-based dye-fiber reaction
14. Dyeing Procedure
Dyeing Procedure
1. Add fiber and dye to vessel
2. Pressurize system (with CO2) up to 800 psi and stir at approximately 850 rpm
3. Heat to required temperature (100 -180 ÂşC)
4. Pressurize to 3500 psi; hold for 2 hours
5. Release pressure, remove fabric
15. Dyeing Procedure
CO2 Dyeing System
(1) Gas cylinder of CO2,
(2) High pressure pump,
(3) Autoclave reactor vessel with stirrer, V = 1000 ml,
(4) Circulation pump- acquisition in future
(5) Electrical heating jacket
1
2
3
4
5
19. Dyeing Procedure
Initial Conclusions
â˘Color depth improved with increasing temperature
â˘Strong evidence for dye-fiber bond formation using vinylsulfone-based dye on nylon and wool
â˘ES-dyeing on wool fibers showed extremely low color yields after extraction (no reaction)
â˘94% fixation at 180 oC/ 3500 psi on wool
20. Dyeing Procedure
Dyeing polyester with disperse dyes in supercritical CO2
Supercritical fluids are highly compressed gases which possess valuable properties of both a liquid and gas.
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. The properties which are intermediate between
gases and liquids are controlled by pressure.
Other attributes of carbon dioxide are
â˘It is virtually an inexhaustible resource (atmosphere, combustion processes, and natural
geologic deposits).
â˘It is not only biodegradable as a nutrient promoting the growth of plants, but is an essential
element of natural processes.
â˘It does not affect the edibility of foodstuffs and will only have toxic effects at extremely high
concentrations.
â˘It has no disposal problems. It is recovered from the process in the form of an uncontaminated
gas and can be reused.
â˘It is easy to handle and combustible.
â˘It has a critical point within the range which is readily manageable by technical means (31C and
73 bar).
â˘It is non-toxic, non-hazardous and low cost.
â˘It is nonflammable and non-corrosive.
21. Dyeing Procedure
Advantage
No waste water (problem in textile industry)
No require additives
No final drying
Recycling
Solvent
Colorants
Environmental friendly
Both economic and ecological
Having a low critical temperature
Disadvantage
Investment
Solve colorants
Time of process
22. Dyeing Procedure
Supercritical CO2dyeings were performed using an SFE 400 supplied by SUPELCO, equipped with
a 50 cm3 internal volume vessel. The operating pressure could be set up to 6000 psi, managed in
100 psi increments. The oven temperature range (30 2000C) was controlled at 100C increments.
The polyester fabrics (1 g) were suspended on a stainless steel net inside the vessel and the
solid, pure dye was placed on the bottom of the vessel. A ratio of 1.5% dye omf was used. When
the system reached the desired temperature and pressure, the liquid was let into the vessel.
After 30 min under constant conditions, the system was expanded to atmospheric pressure and
the dry samples were removed. Dyeings in aqueous medium were produced also in which
polyester samples were dyed in a thermostatted bath (Linitest) using a 40:1 liquor ratio, at
1200C for 1 h (1.5% omf pure dye, 0.25% omf Na2SO4, 0.5% omfDispersogen-A, 40% omfLenol-
O); Dispersogen-A and Lenol-O were Hoechst auxiliary products. 2.4.
Dyeing of polyester
23. Dyeing Procedure
âWhen carbon dioxide is heated to above 31 C and pressurised to above 74 bar, it becomes
supercritical, a state of matter that can be seen as an expanded liquid, or a heavily compressed
gas. In short, above the critical point, carbon dioxide has properties of both a liquid and a gas. In
this way supercritical CO2, has liquid-like densities, which is advantageous for dissolving
hydrophobic dyes, and gas-like low viscosities and diffusion properties, which can lead to
shorter dyeing times compared to water. Compared to water dyeing, the extraction of spinning
oils, the dyeing and the removal of excess dye can all be carried out in one plant in the carbon
dioxide dyeing process which involves only changing the temperature and pressure conditions;
drying is not required because at the end of the process CO2 is released in the gaseous state.
The CO2 can be recycled easily, up to 90% after precipitation of the extracted matter in a
separator.â To read more about supercritical fluid dyeing technology.
Dyeing with CO2
24. Dyeing Procedure
Fastness assessment
1. Wet fastness was determined according to UNI 7638 (ISO 105-C 01/03/04).
2. For the determination of fastness to artificial light, a Xenotest Hanau 150S
(Heraeus)
3. apparatus was employed, equipped with a 1500 W xenon arc lamp,
4. according to UNI 7639 (ISO 105-B02).
26. The results show that the concentration of dye absorbed by the fibre increased initially on
increasing the pressure to 3500 psi, but was practically constant between 3500 and 4000 psi.
Similar results were obtained when the study was carried out at 100 and 1200C. The data
reported in
Fig. 1. Variations in dye uptake (Df) by the fibre as a function of pressure at constant temp(800C).
Results
27. Table 1 Variation in dye uptake by the fibre as a function of pressure at constant temp (1000C)
Fiber from the dyed packages was woven into a âsockâ and evaluated for uniformity.
28. 1.In conventional method of dyeing textiles undergo multiple processes.
2. In these processes water, dyes, and other auxiliaries are used to enhance the
efficiency of dyeing process.
3. After dyeing a subsequent drying process with high energy consumption is
necessary.
4.The cost of waste water treatment and of arranging water of acceptable quality
is becoming serious concerns. Either the water available is too hard or not
available in sufficient amount or therefore dyeing plants cannot be set up at some
places.
5.By using scCO2 dyeing machine we can overcome all these problems of
conventional machine.
Problems with Conventional Water-Dyeing Machine
Problems
29. 1. Elimination of usage of water, water treatment and water pollution
2. Elimination of a drying step, thus reduces energy cost
3. Elimination of auxiliaries, such as, dispersing agent, leveling agent
4. Rapid diffusion and potential for high degree of dye exhaustions
5. Dyeing occurs with high degree of levelness
6. No after treatment is required
7. Time required for dyeing is very less
8. Gives good rubbing fastness
9. Dyeing houses may be started on sites where there is water scarcity
10. No air pollution due to recycling of CO2 is accomplished
11. Economical and environmentally friendly.
Advantages of scCO2 Dyeing Machine
30. 1. Initial investment is high.
2. High pressure and high temperature are required for dye solubility during the
process.
3. It is a batch process. So processing of long length fabric (continuous) is not
possible.
4. During polyester dyeing, the trimer is produced. This is removed using aqueous
cleaning waterless scCO2 as a problem to eliminate.
5. There is little data available about dyestuff solubility in scCO2.
6. At present, scCO2 dyeing is confined to synthetic fibers.
Disadvantages/Limitations
31. Benefits of scCO2 M/C over Conventional M/C: An Overall Comparison
Conventional Water-Dyeing Dyeing in Supercritical CO2
High volume of water required Completely avoids the use of water
Produces huge effluent No waste water at all
Wastage of valuable dyestuffs Unreacted dye remains as powder
Requires huge chemicals and auxiliaries No need for dispersing and leveling agents
High energy requirements Requires only 20% energy of conventional
dyeing
Dyeing, washing and drying times are 3-4
hours per batch
Only 2 to 2.5 hours per batch
Drying is required after dyeing process Not required as CO2 is released in gaseous
state
After treatment is a compulsory step No after treatment is required.
Water treatment (ETP) and recycling is
difficult and costly
CO2 can be easily recycled upto 95%
Dyeing factory need to establish where
water is sufficiently available
Dyeing factory can be established where
water is not available
Overall cost comparing to scCO2 is high Machine cost is high
32. The machine is not suitable for dyeing natural (hydrophilic) fibers in its current
arrangement. For natural fibers the diffusion of scCO2 is hampered by its inability to
break the hydrogen bonds present in many natural fibers, including cotton, wool and
silk. A further problem is that reactive dyes, direct dyes and acid dyes which are
suitable for dyeing of natural fibers are insoluble in scCO2 and also dye may be
damaged at such high pressure and temperature. However, Investigators are trying to
find out a solution for dyeing natural fibers in scCO2. Some possible approaches are
chemically treating/modifying the fiber before dyeing or using improved dyestuffs,
such as, disperse reactive dye.
Challenges
33. We can take all the advantages mentioned above if we go forward
with this machine. It will reduce the usage of chemicals & auxiliaries,
dyeing time, waste-water treatment cost and ultimately saves the
capital. It will also save the environment. Again this will improve the
companyâs reputation and increases the future possibilities to get
potential/more orders.
How we will be benefited?
34. 1. At this moment, the scCO2 dyeing machine is only suitable for open-width dyeing
of scoured polyester fabric with disperse dyes.
2. DyeCoo in cooperation with another dye manufacturer Triade, are producing,
marketing and distributing specially developed disperse dyes for this machine
under the CooDye brand name.
3. Nike, the global sportswear giant, has entered into a strategic partnership with
DyeCoo in order to produce textiles dyed without water.
4. Yeh group dyeing the fabrics with this machine branded as DryDye⢠Fabrics.
Present situation
35. Conventional scCO2
Pretreatment 4555 4555
Dyeing 45250 30625
Post Treatment 3800 0
Total 53605 35180
Energy Savings 34.37%
Comparative Energy Requirements* (kJ):
38. Production machine
The final partner of DyeCoo to make history is Tong Siang Co. Ltd (Thailand), part of the Yeh
Group. The polyester textile producer will become the first textile mill to implement the
commercial-scale supercritical fluid CO2 machine into production, branding the process as
DryDye. Supercritical fluid CO2 enables polyester to be dyed with modified disperse dyes. It
causes the polymer fibre to swell, allowing the disperse dye to diffuse and penetrate the pore
and capillary structure of the fibres. The viscosity of the dye solution is lower, making the
circulation of the dye solutions easier and less energy intensive. This deep penetration also
provides effective coloration of polymers. Furthermore, dyeing and removing excess dye can be
carried out in the same vessel; and residue dye is minimal and may be extracted and recycled.
Currently, the process is limited to dyeing of scoured polyester fabric run in batches of 100â150
kg, although DyeCoo and its partners are developing reactive dyes for cellulosics to be available
for use in this process in the not too distant future.
39. Supercritical dyeing using supercritical CO2, the ideal dyeing technology that uses no water at
all.
No wastewater, environmentally friendly, futuristic dyeing technology. HISAKA has built the
largest dyeing equipment in the world, envisioned for actual production.
Not only CO2 supercritical technology dyes, but also washing and additional functions are
among the special treatment uses we expect to see.
Super-critical Dyeing and Treatment
40.
41. 1. Yarn Manufacturing Technology
Link : http://www.facebook.com/pages/Yarn-Manufacturing-Technology/485014954866808
2. Fabric Manufacturing Technology
Link : http://www.facebook.com/pages/Fabric-Manufacturing-Technology/459520217425605
3. Garments Manufacturing Technology
Link : http://www.facebook.com/pages/Garments-Manufacturing-
Technology/472364799463126
3. Wet processing Technology
Link : http://www.facebook.com/pages/Wet-Processing-Technology-Dyeing-/468645219825404
4. Fashion-Design-and-Technology
Link : http://www.facebook.com/pages/Fashion-Design-and-
Technology/587655294583875?ref=ts&fref=ts
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