CN103741523B - A kind of supercritical CO 2fluid dispersion dye solubilization colouring method - Google Patents

Abstract

The present invention is applicable to field of dyeing process, provides a kind of supercritical CO ₂fluid dispersion dye solubilization colouring method, passes through supercritical CO ₂fluid dissolves DISPERSE DYES, and adds solubilizer, dyes, optimize the dyeing such as pressure, temperature and time condition simultaneously to fabric, improves DISPERSE DYES at supercritical CO ₂solubility in fluid, dye level etc.

Description

A kind of supercritical CO 2fluid dispersion dye solubilization colouring method

Technical field

The invention belongs to field of dyeing process, particularly relate to a kind of supercritical CO ₂fluid dispersion dye solubilization colouring method.

Background technology

Along with textile industry develops rapidly, the environmental pollution that process of textile production causes receives publicity day by day.Country has worked out a series of strict environmental legislation in succession, supervises the sewage disposal of industrial quarters and discharge etc.According to statistics, the fabric weight of textile printing and dyeing processing and the ratio of water consumption are up to 1:100 ~ 1:150, and national dyeing and printing process water consumption estimates annual 1600000000 tons.At present, the Treated sewage reusing ratio of the sector production process is very low, and sewage disposal and discharge account for production cost ratio increases gradually.

Traditional dyeing course, using water as medium, plays dispersion and dissolving dye and auxiliary agent, soaks and the important function such as swollen fiber, seem do not have water just cannot dye.But nature freshwater resources start shortage, water pollutions is very serious.Now, in order to reduce water consumption and the dyeing waste of Colour Difference, people carry out large quantity research, are devoted to exploitation water saving and anhydrous staining technique.

Adopt supercritical CO ₂fluid technique, utilizes reusable CO ₂, at supercritical conditions with CO ₂fluid is that medium carries out Colour Difference, and the integrated costs such as its energy resource consumption, lower than conventional dyeing process, achieve non-aqueous dyeing, energy-saving and emission-reduction, therefore, and supercritical CO ₂fluid staining technique have anhydrous, reduce discharging, energy-conservation technical advantage, be a suitability for industrialized production new technology with development prospect.

Supercritical CO ₂fluid refers to CO ₂in the density fluid state higher than the non-condensed property under critical-temperature (Tc=31 DEG C) and critical pressure (Pc=7.2MPa) condition, namely at more than Tc by CO2 gas compression to higher than more than Pc, CO ₂density can carry out consecutive variations significantly in the scope from gas to liquid.Supercritical CO ₂the character of fluid system, as gas, specifically has the high density as liquid and the low viscosity as liquid.By changing these two performance variables of temperature and pressure of system, the density of fluid, viscosity (intermolecular distance) can be regulated, make it have specific physical property.

Supercritical CO ₂the feature of fluid is as follows: 1, only slightly change pressure, its density is just more big changes, and due to its low viscosity and high diffusibility, is conducive to the movement of material; 2, because the temperature difference moves greatly, higher translational speed can be obtained.At present, supercritical CO is utilized ₂the advantage of fluid, it is used for extraction and is separated with chromatographic and refined substance etc., such as extracting hop, natural product extraction etc., have a wide range of applications future in light industry, food, chemical industry, medicine and other fields.

As everyone knows, Colour Difference water consumption is many, electric energy and consumption of heat energy large, the chemicals used is many, dyestuff containing non-set in the waste water of discharging after dyeing and auxiliary agent, reclaim difficulty, waste water treatmentntrol difficult, needs constantly to increase cost of water treatment to reach the sewage drainage standard improved gradually.Obviously, conventional colouring method more and more will be difficult to adapt to national energy-saving and reduce discharging industrial development strategy.

Summary of the invention

The object of the invention is to: a kind of supercritical CO is provided ₂fluid dispersion dye solubilization colouring method, is intended to solve the problem that existing water dyeing causes shortage of water resources and pollution.

The object of the present invention is achieved like this:

A kind of supercritical CO ₂fluid terylene DISPERSE DYES solubilising colouring method, passes through supercritical CO ₂fluid dissolves DISPERSE DYES, and adds solubilizer, dyes to fabric.

Described method is specially:

Put into dyestuff still by after DISPERSE DYES filter cake and solubilizer mixing, fabric is wound on dyeing axle and puts into dyeing caldron, input liquid carbon dioxide by booster pump, make by circulating pump the supercritical CO being dissolved with DISPERSE DYES ₂dyeing fluid circulates between curling fabric ectonexine;

Or, DISPERSE DYES filter cake is put into dyestuff still, fabric is wound on dyeing axle and puts into dyeing caldron, liquid carbon dioxide is inputted by booster pump, by circulating pump, the supercritical CO 2 dyeing fluid being dissolved with DISPERSE DYES is circulated between curling fabric ectonexine, meanwhile, at the dyestuff dyeing cycle process initial stage, solubilizer is injected dyeing system.

Described solubilizer is the composite solubilizer of perchloroethylene and 1-2 kind secondary solvent.

Described secondary solvent is selected from oxolane, chloroform, N, dinethylformamide, carrene, dimethyl sulfoxide (DMSO), absolute ethyl alcohol, normal propyl alcohol, isobutanol, heptane, n-hexane, benzene,toluene,xylene, acetone, the formula of described composite solubilizer is: perchloroethylene 50%-80%, secondary solvent A20%-50%, secondary solvent B0%-20%.

Described DISPERSE DYES and composite solubilizer solid-liquid ratio are 1:2-1:10; When described composite solubilizer injected at the dyestuff dyeing cycle process initial stage, inject with the speed of flow 1ml-10ml/ minute.

In dyeing course, system pressure keeps 20MPa-30MPa, and heating systems temperature keeps 100 DEG C-130 DEG C, and the dyeing cycle time is 40min-120min.

Described method also comprises:

After completing the dyeing cycle time, reduce system pressure to 3MPa-8MPa, reduce system temperature to 20 DEG C-50 DEG C, carry out dyestuff, solvent and carbon dioxide recovery by separating still; Input a certain amount of carbon dioxide by booster pump, reach certain super critical condition, the fabrics of polyester after wash cycles dyeing; Reclaim residue, carbon dioxide, last step-down cooling, takes out DYED FABRICS.

Outstanding advantages of the present invention is: the present invention passes through supercritical CO ₂fluid dissolves DISPERSE DYES, and adds solubilizer, dyes, save a large amount of water resources to fabric, meanwhile, by optimizing the dyeing such as pressure, temperature and time condition, improves DISPERSE DYES at supercritical CO ₂solubility in fluid, dye level etc., be applicable to the dyeing of polyster fibre and fabric, synthetic fiber and fabric etc.

Detailed description of the invention

In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.

Supercritical CO provided by the invention ₂fluid dispersion dye solubilization colouring method, by carrying solubilizer in dyeing course, optimizes the dyeing such as pressure, temperature and time condition simultaneously, improves DISPERSE DYES at supercritical CO ₂solubility in fluid, dye level etc., be applicable to the dyeing of polyster fibre and fabric, synthetic fiber and fabric etc.

Because polyster fibre is at supercritical CO ₂expanded in fluid, when temperature exceedes its glass transition temperature, polyster fibre is in elastomeric state, and molecule segment moves, and free volume increases, and is dissolved in supercritical CO ₂dISPERSE DYES in fluid can enter fibrous inside, selects to add a certain proportion of solubilizer and can improve DISPERSE DYES at supercritical CO ₂solubility in fluid.

The selection of solubilizer need meet following requirement: dyestuff dissolves, boiling point suitably, does not burn or burning-point is very high, it is easy to reclaim.Perchloroethylene, trichloro-ethylene and 1,1,1-trichloroethanes are proper, are wherein first-selection with perchloroethylene.But in actual applications, the dissolving of DISPERSE DYES in perchloroethylene is unsatisfactory.

The present invention adopts composite solubilizer, take perchloroethylene as main solvent, at oxolane, chloroform, N, select 1-2 kind to be secondary solvent in dinethylformamide (DMF), carrene, dimethyl sulfoxide (DMSO), absolute ethyl alcohol, normal propyl alcohol, isobutanol, heptane, n-hexane, benzene,toluene,xylene, acetone equal solvent, according to below with reference to formulated:

Perchloroethylene 50%-80%

Secondary solvent A20%-50%

Secondary solvent B0%-20%.

Supercritical CO ₂in fluid dyeing, adopt a certain amount of composite solubilizer can effectively improve DISPERSE DYES solubility, be conducive to optimizing dyeing condition, obtain good Color.

In the present invention, adding of solubilizer has two kinds of methods: one is before dyeing, according to dyestuff and solubilizer solid-liquid ratio 1:2-1:10, adds in dyestuff still after mixing; Two is at the dyestuff dyeing cycle process initial stage, utilizes a small-sized charge pump, according to dyestuff and solubilizer solid-liquid ratio 1:2-1:10, with the speed of flow 1ml-10ml/ minute, solubilizer is injected dyeing system.

Because composite solubilizer changes supercritical CO to a certain extent ₂fluid dyeing circumstances, comprises the solubility, dye level, dyeing kinetics, uniform dyeing property etc. of the degrees of expansion of fiber, vitrification point, dyestuff, therefore needs the techniques such as the pressure of optimizing regulation dyeing system, temperature and time.

Described supercritical CO ₂fluid dispersion dye solubilization colouring method can comprise two kinds according to the feed postition of solubilizer: one, according to dyestuff and solubilizer solid-liquid ratio 1:2-1:10, take pure DISPERSE DYES filter cake and composite solubilizer, put into dyestuff still after mixing; Take a certain amount of fabric to be entirely wound on dyeing axle, put into dyeing caldron; Input liquid carbon dioxide by booster pump, system pressure is increased to 20MPa-30MPa, heating systems temperature reaches 100 DEG C-130 DEG C; The supercritical CO being dissolved with DISPERSE DYES is made by circulating pump ₂dyeing fluid circulates between curling fabric ectonexine, and be conducive to dyestuff and adsorb equably, permeate, anchor at fibrous inside, the dyeing cycle time reaches 40min-120min; Two, pure DISPERSE DYES filter cake is put into dyestuff still; Take a certain amount of fabric to be entirely wound on dyeing axle, put into dyeing caldron; Input liquid carbon dioxide by booster pump, system pressure is increased to 20MPa-30MPa, heating systems temperature reaches 100 DEG C-130 DEG C; By circulating pump, the supercritical CO 2 dyeing fluid being dissolved with DISPERSE DYES is circulated between curling fabric ectonexine, simultaneously, at the dyestuff dyeing cycle process initial stage, utilize a small-sized charge pump, according to dyestuff and solubilizer solid-liquid ratio 1:2-1:10, with flow 1ml-10ml/ minute speed, solubilizer is injected dyeing system, keep pressure and temperature, the dyeing cycle time reaches 40min-120min.

After completing the dyeing cycle time, reduce system pressure to 3MPa-8MPa, reduce system temperature to 20 DEG C-50 DEG C, carry out dyestuff, solvent and carbon dioxide recovery by separating still; Input a certain amount of carbon dioxide by booster pump, reach certain super critical condition, the fabrics of polyester after wash cycles dyeing; Reclaim residue, carbon dioxide, last step-down cooling, takes out DYED FABRICS.

The K/S value of DYED FABRICS is measured with certain wavelength, more general supercritical CO by adopting DatacolorSF6OOX colour examining spectrometer (Datacolor company of the U.S.) ₂the textile dyeing degree of depth of fluid dyeing, result shows that the dye level of colouring method provided by the invention promotes 5%-60%.

According to GBT3920-1997 textiles _ COLOR FASTNESS test _ colour fastness to rubbing and GBT3921-2008 textiles _ COLOR FASTNESS test _ fastness to soaping standard, dyefastness detection is carried out to the dacron of the dyeing of colouring method provided by the invention, result shows that DYED FABRICS is up to state standards, its fastness to soaping 3-5 level, colour fastness to rubbing 3-4 level.

It is below above-mentioned supercritical CO ₂several specific embodiments of fluid dispersion dye solubilization colouring method.

Embodiment 1

Take after pure dispersed blue dye filter cake 1g and solubilizer 2ml-8ml mixes and put into dyestuff still; Take 100g fabrics of polyester to be entirely wound on dyeing axle, and put into dyeing caldron; Input liquid carbon dioxide by booster pump, make system pressure be increased to 20MPa-30MPa; Heating systems temperature reaches 100 DEG C-130 DEG C; The supercritical CO being dissolved with DISPERSE DYES is made by circulating pump ₂dyeing fluid circulates between curling fabrics of polyester ectonexine, is conducive to dyestuff and adsorbs equably, permeates, anchors at fibrous inside; Keep pressure 20MPa-30MPa, temperature 100 DEG C-130 DEG C, the dyeing cycle time reaches 40min-120min; After completing the dyeing cycle time, reduce system pressure and reach 3MPa-8MPa, reduce system temperature and reach 20 DEG C-50 DEG C, carry out dyestuff, solvent and carbon dioxide recovery by separating still; Input a certain amount of carbon dioxide by booster pump, reach certain super critical condition, the fabrics of polyester after wash cycles dyeing; Reclaim residue, carbon dioxide, step-down is lowered the temperature, and takes out DYED FABRICS.Obtain brightly painted blue dacron, its fastness to soaping 3-5 level, colour fastness to rubbing 3-4.5 level.

Embodiment 2

Take after pure dispersed blue dye filter cake 3g and solubilizer 10ml-25ml mixes and put into dyestuff still; Take 100g fabrics of polyester to be entirely wound on dyeing axle, and put into dyeing caldron; Input liquid carbon dioxide by booster pump, make system pressure be increased to 20MPa-30MPa; Heating systems temperature reaches 100 DEG C-130 DEG C; The supercritical CO being dissolved with DISPERSE DYES is made by circulating pump ₂dyeing fluid circulates between curling fabrics of polyester ectonexine, is conducive to dyestuff and adsorbs equably, permeates, anchors at fibrous inside; Keep pressure 20MPa-30MPa, temperature 100 DEG C-130 DEG C, the dyeing cycle time reaches 40min-120min; After completing the dyeing cycle time, reduce system pressure and reach 3MPa-8MPa, reduce system temperature and reach 20 DEG C-50 DEG C, carry out dyestuff, solvent and carbon dioxide recovery by separating still; Input a certain amount of carbon dioxide by booster pump, reach certain super critical condition, the fabrics of polyester after wash cycles dyeing; Reclaim residue, carbon dioxide, step-down is lowered the temperature, and takes out DYED FABRICS.Obtain the blue dacron of thick in color, its fastness to soaping 3-4.5 level, colour fastness to rubbing 3-4 level.

Embodiment 3

Take pure dispersive red dye filter cake 1g and put into dyestuff still; Take 100g fabrics of polyester to be entirely wound on dyeing axle, and put into dyeing caldron; Input liquid carbon dioxide by booster pump, make system pressure be increased to 20MPa-30MPa; Heating systems temperature reaches 100 DEG C-130 DEG C; The supercritical CO being dissolved with DISPERSE DYES is made by circulating pump ₂dyeing fluid circulates between curling fabrics of polyester ectonexine, is conducive to dyestuff and adsorbs equably, permeates, anchors at fibrous inside; At the dyestuff dyeing cycle process initial stage, utilize a small-sized charge pump, according to dyestuff and solubilizer solid-liquid ratio 1:2-1:10, with flow 1ml-10ml/ minute speed, solubilizer is injected dyeing system; Keep pressure 20MPa-30MPa, temperature 100 DEG C-130 DEG C, the dyeing cycle time reaches 40min-120min; After completing the dyeing cycle time, reduce system pressure and reach 3MPa-8MPa, reduce system temperature and reach 20 DEG C-50 DEG C, carry out dyestuff, solvent and carbon dioxide recovery by separating still; Input a certain amount of carbon dioxide by booster pump, reach certain super critical condition, the fabrics of polyester after wash cycles dyeing; Reclaim residue, carbon dioxide, step-down is lowered the temperature, and takes out DYED FABRICS.Obtain brightly painted red dacron, its fastness to soaping 3-5 level, colour fastness to rubbing 3-5 level.

Embodiment 4

Take pure dispersive red dye filter cake 3g and put into dyestuff still; Take 100g fabrics of polyester to be entirely wound on dyeing axle, and put into dyeing caldron; Input liquid carbon dioxide by booster pump, make system pressure be increased to 20MPa-30MPa; Heating systems temperature reaches 100 DEG C-130 DEG C; The supercritical CO being dissolved with DISPERSE DYES is made by circulating pump ₂dyeing fluid circulates between curling fabrics of polyester ectonexine, is conducive to dyestuff and adsorbs equably, permeates, anchors at fibrous inside; At the dyestuff dyeing cycle process initial stage, utilize a small-sized charge pump, according to dyestuff and solubilizer solid-liquid ratio 1:2-1:10, with flow 1ml-10ml/ minute speed, solubilizer is injected dyeing system; Keep pressure 20MPa-30MPa, temperature 100 DEG C-130 DEG C, the dyeing cycle time reaches 40min-120min; After completing the dyeing cycle time, reduce system pressure and reach 3MPa-8MPa, reduce system temperature and reach 20 DEG C-50 DEG C, carry out dyestuff, solvent and carbon dioxide recovery by separating still; Input a certain amount of carbon dioxide by booster pump, reach certain super critical condition, the fabrics of polyester after wash cycles dyeing; Reclaim residue, carbon dioxide, step-down is lowered the temperature, and takes out DYED FABRICS.Obtain the red dacron of thick in color, its fastness to soaping 3-5 level, colour fastness to rubbing 3-5 level.

Embodiment 5

Take after pure disperse yellow dye filter cake 2g and solubilizer 4ml-15ml mixes and put into dyestuff still; Take 100g fabrics of polyester to be entirely wound on dyeing axle, and put into dyeing caldron; Input liquid carbon dioxide by booster pump, make system pressure be increased to 20MPa-30MPa; Heating systems temperature reaches 100 DEG C-130 DEG C; The supercritical CO being dissolved with DISPERSE DYES is made by circulating pump ₂dyeing fluid circulates between curling fabrics of polyester ectonexine, is conducive to dyestuff and adsorbs equably, permeates, anchors at fibrous inside; Keep pressure 20MPa-30MPa, temperature 100 DEG C-130 DEG C, the dyeing cycle time reaches 40min-120min; After completing the dyeing cycle time, reduce system pressure and reach 3MPa-8MPa, reduce system temperature and reach 20 DEG C-50 DEG C, carry out dyestuff, solvent and carbon dioxide recovery by separating still; Input a certain amount of carbon dioxide by booster pump, reach certain super critical condition, the fabrics of polyester after wash cycles dyeing; Reclaim residue, carbon dioxide, step-down is lowered the temperature, and takes out DYED FABRICS.Obtain brightly painted yellow dacron, its fastness to soaping 3-5 level, colour fastness to rubbing 3-4.5 level.

Embodiment 6

Take pure disperse yellow dye filter cake 3g and put into dyestuff still; Put into dyestuff still; Take 100g fabrics of polyester to be entirely wound on dyeing axle, and put into dyeing caldron; Input liquid carbon dioxide by booster pump, make system pressure be increased to 20MPa-30MPa; Heating systems temperature reaches 100 DEG C-130 DEG C; The supercritical CO being dissolved with DISPERSE DYES is made by circulating pump ₂dyeing fluid circulates between curling fabrics of polyester ectonexine, is conducive to dyestuff and adsorbs equably, permeates, anchors at fibrous inside; At the dyestuff dyeing cycle process initial stage, utilize a small-sized charge pump, according to dyestuff and solubilizer solid-liquid ratio 1:2-1:10, with flow 1ml-10ml/ minute speed, solubilizer is injected dyeing system; Keep pressure 20MPa-30MPa, temperature 100 DEG C-130 DEG C, the dyeing cycle time reaches 40min-120min; After completing the dyeing cycle time, reduce system pressure and reach 3MPa-8MPa, reduce system temperature and reach 20 DEG C-50 DEG C, carry out dyestuff, solvent and carbon dioxide recovery by separating still; Input a certain amount of carbon dioxide by booster pump, reach certain super critical condition, the fabrics of polyester after wash cycles dyeing; Reclaim residue, carbon dioxide, step-down is lowered the temperature, and takes out DYED FABRICS.Obtain the yellow dacron of thick in color, its fastness to soaping 3-5 level, colour fastness to rubbing 3-5 level.

Embodiment 7

Take after the emerald green blue dyestuff filter-cakes 3g of pure dispersion and solubilizer 10ml-30ml mixes and put into dyestuff still; Put into dyestuff still; Take 100g fabrics of polyester to be entirely wound on dyeing axle, and put into dyeing caldron; Input liquid carbon dioxide by booster pump, make system pressure be increased to 20MPa-30MPa; Heating systems temperature reaches 100 DEG C-130 DEG C; The supercritical CO being dissolved with DISPERSE DYES is made by circulating pump ₂dyeing fluid circulates between curling fabrics of polyester ectonexine, is conducive to dyestuff and adsorbs equably, permeates, anchors at fibrous inside; Keep pressure 20MPa-30MPa, temperature 100 DEG C-130 DEG C, the dyeing cycle time reaches 40min-120min; After completing the dyeing cycle time, reduce system pressure and reach 3MPa-8MPa, reduce system temperature and reach 20 DEG C-50 DEG C, carry out dyestuff, solvent and carbon dioxide recovery by separating still; Input a certain amount of carbon dioxide by booster pump, reach certain super critical condition, the fabrics of polyester after wash cycles dyeing; Reclaim residue, carbon dioxide, step-down is lowered the temperature, and takes out DYED FABRICS.Obtain the blue dacron of kingfisher of thick in color, its fastness to soaping 3-5 level, colour fastness to rubbing 3-5 level.

The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.

Claims (5)

1. a supercritical CO ₂fluid dispersion dye solubilization colouring method, is characterized in that, pass through supercritical CO ₂fluid dissolves DISPERSE DYES, and adds solubilizer, dyes to fabric, and described solubilizer is the composite solubilizer of perchloroethylene and 1-2 kind secondary solvent, and described DISPERSE DYES and composite solubilizer solid-liquid ratio are 1:2-1:10; When described composite solubilizer injected at the dyestuff dyeing cycle process initial stage, inject with the speed of flow 1ml-10ml/ minute.

2. supercritical CO as claimed in claim 1 ₂fluid dispersion dye solubilization colouring method, it is characterized in that, described secondary solvent is selected from oxolane, chloroform, N, dinethylformamide, carrene, dimethyl sulfoxide (DMSO), absolute ethyl alcohol, normal propyl alcohol, isobutanol, heptane, n-hexane, benzene,toluene,xylene, acetone, the formula of described composite solubilizer is: perchloroethylene 50%-80%, secondary solvent A20%-50%, secondary solvent B0%-20%.

3. supercritical CO as claimed in claim 1 ₂fluid dispersion dye solubilization colouring method, is characterized in that, described method is:

DISPERSE DYES filter cake is put into dyestuff still, fabric is wound on dyeing axle and puts into dyeing caldron, input liquid carbon dioxide by booster pump, make by circulating pump the supercritical CO being dissolved with DISPERSE DYES ₂dyeing fluid circulates between curling fabric ectonexine, and at the dyestuff dyeing cycle process initial stage, solubilizer is injected dyeing system.

4. supercritical CO as claimed in claim 3 ₂fluid dispersion dye solubilization colouring method, is characterized in that, in dyeing course, system pressure keeps 20MPa-30MPa, and heating systems temperature keeps 100 DEG C-130 DEG C, and the dyeing cycle time is 40min-120min.

5. supercritical CO as claimed in claim 3 ₂fluid dispersion dye solubilization colouring method, is characterized in that, described method also comprises:

After completing the dyeing cycle time, reduce system pressure to 3MPa-8MPa, reduce system temperature to 20 DEG C-50 DEG C, carry out dyestuff, solvent and carbon dioxide recovery by separating still; Input a certain amount of carbon dioxide by booster pump, reach certain super critical condition, the fabrics of polyester after wash cycles dyeing; Reclaim residue, carbon dioxide, last step-down cooling, takes out DYED FABRICS.