CN110835818A

CN110835818A - Sizing and desizing method for supercritical anhydrous dyeing and finishing and high-pressure device used in sizing and desizing method

Info

Publication number: CN110835818A
Application number: CN201911130429.1A
Authority: CN
Inventors: 莫崧鹰; 田永平
Original assignee: Zhijiang College of ZJUT
Current assignee: Zhijiang College of ZJUT
Priority date: 2019-11-18
Filing date: 2019-11-18
Publication date: 2020-02-25

Abstract

The invention relates to a sizing and desizing method for supercritical anhydrous dyeing and finishing and a high-pressure device used by the method, belonging to the field of textile printing and dyeing. The supercritical carbon dioxide fluid is a nontoxic, easily available, low-cost and pollution-free substance, and can be applied to dyeing and finishing industry to replace water, so that the degree of environmental pollution can be effectively reduced. The invention introduces the process of sizing and desizing by adopting the waxy sizing agent as the supercritical anhydrous dyeing and finishing, the whole desizing process only uses the supercritical carbon dioxide fluid to dissolve the sizing agent, after the process is finished, the waste liquid does not need to be treated, the carbon dioxide can be changed into the original gas state only by reducing the working pressure, the carbon dioxide can be recycled for the next dyeing and finishing, and the residual sizing agent can also be recycled and reused. The whole process is completely environment-friendly. The high-voltage device related by the invention has simple design and low equipment cost. In process development, a small test device is needed in the aspect of product board beating, and the high-voltage device provided by the invention provides a low-cost and efficient solution.

Description

Sizing and desizing method for supercritical anhydrous dyeing and finishing and high-pressure device used in sizing and desizing method

Technical Field

The invention relates to a sizing and desizing method for supercritical anhydrous dyeing and finishing and a high-pressure device used by the method, belonging to the field of textile printing and dyeing.

Background

The dyeing and finishing industry not only consumes much water, but also is extremely difficult to treat due to complex and variable wastewater components, deep chromaticity and high alkalinity. And 20 tons of water bodies are polluted by 1 ton of printing and dyeing wastewater. From the sustainable development of dyeing and finishing industry, the reform of the traditional dyeing and finishing industry is imperative.

The supercritical carbon dioxide fluid is a nontoxic, easily available, low-cost and pollution-free substance, and can be applied to the printing and dyeing industry to replace water, so that the degree of environmental pollution can be effectively reduced. The whole printing and dyeing process is the same as that of the traditional method, only the supercritical carbon dioxide fluid is used for replacing the hydrosolvent to dissolve the dye, after the printing and dyeing is finished, waste liquid does not need to be treated, only the working pressure needs to be reduced, the carbon dioxide can become the original gas state, the carbon dioxide can be recycled for next printing and dyeing, and the remaining dye can also be recycled. The whole process is completely environment-friendly.

The supercritical anhydrous dyeing process is mature, but the matched pretreatment process needs to be perfected. The sizing and desizing are a main preorder work. Since conventional size for textile cloth cannot be directly dissolved in carbon dioxide fluid. There is a need for a targeted study using slurries that can be dissolved in carbon dioxide fluid. Perfluoroalkanols and fluorine-containing polymers have been reported in the past. Sucrose octaacetate and the like have also been reported to be used, and these materials are relatively expensive, increasing the production cost.

In order to solve the problem and reduce the ecological environmental pollution problem of printing and dyeing enterprises, the invention hopes to introduce a sizing and desizing method for supercritical anhydrous dyeing and finishing, and simultaneously provides a new printing and dyeing sizing agent and a high-pressure device used when the method is utilized.

Disclosure of Invention

In order to solve the problem of sewage in the printing and dyeing process from the source, the invention provides a sizing and desizing method for supercritical anhydrous dyeing and finishing and a high-pressure device used by the method. The specific technical scheme is as follows:

a sizing and desizing method for supercritical anhydrous dyeing and finishing comprises the following steps:

(1) heating the waxy slurry to 50-100 ℃, allowing the yarns to pass through the waxy slurry, cooling the sized yarns to room temperature, and weaving the sized yarns into cloth;

(2) precooling the high-pressure kettle, and taking out the high-pressure kettle after the high-pressure kettle is cooled to below-20 ℃;

(3) opening the autoclave cover, putting the cloth subjected to wax sizing, and covering the autoclave cover;

(4) weighing the autoclave in a weighing device, and slowly introducing carbon dioxide into the autoclave to make the density of the carbon dioxide be 0.4-0.8g/cm³Closing the inflation valve and covering an anti-blocking cover;

(5) placing the high-pressure autoclave in an oil bath tub, immersing the high-pressure autoclave by using an oil bath medium, and fixing the high-pressure autoclave by using a high-pressure autoclave clamp;

(6) heating to above 50 deg.C, starting oil bath, stirring for above 0.5 hr, and cooling to room temperature;

(7) taking out the autoclave, unscrewing the anti-blocking cover, and slowly opening the inflation valve to reduce the pressure to be balanced;

(8) and opening the autoclave cover, and taking out the treated materials.

In the step (6), the temperature of the oil bath medium is raised to 50-120 ℃, the temperature is high, the slurry is easy to dissolve, but the energy consumption and the pressure of the autoclave are increased, and the burden of equipment is increased.

In the step (4), when the temperature is set to be 50-60 ℃ after the temperature is raised, the density of the carbon dioxide is 0.7-0.8g/cm³(ii) a When the temperature is set to 60-80 ℃ after the temperature is raised, the density of the carbon dioxide is 0.6-0.7g/cm³(ii) a When the temperature is set to 80-120 ℃ after the temperature is raised, the density of the carbon dioxide is 0.4-0.6g/cm³The temperature increases and the vessel pressure increases. The carbon dioxide density is properly reduced, and the pressure parallelism can be ensured to be lower than the use pressure of the high-pressure autoclave.

In the step (5), the oil bath medium is glycerol, the heat ratio of the glycerol is high, and the heat preservation effect is excellent.

The temperature rise speed of the oil bath medium in the step (6) is 1-5 ℃/min, preferably 3 ℃/min, and proper treatment time and pressure parallelism are ensured.

The waxy slurry in the step (1) comprises waxy materials and silicone oil diluent, and the waxy materials are dissolved in the diluent by heating.

The waxy material is one of paraffin wax, beeswax, vegetable wax, wood wax, bayberry wax, candelilla wax, Japan wax, palm wax, rice bran wax, jojoba oil, castor wax, animal wax, insect wax, wool wax, spermaceti wax, mineral wax, montan wax, ozokerite, petroleum wax, microcrystalline wax, petroleum jelly, synthetic wax, Fischer-Tropsch wax or polyethylene wax.

A high-pressure device used in a sizing and desizing method of supercritical waterless finishing dyeing comprises an oil bathtub and an autoclave; a stirring shaft groove is formed in the inner wall of the oil bath, a first Z-shaped stirring shaft is arranged in the stirring shaft groove in a matched mode, a first autoclave clamp is arranged at the other end of the first Z-shaped stirring shaft, one end of an autoclave is fixed on the first autoclave clamp, a second autoclave clamp is fixed at the other end of the autoclave, a second Z-shaped stirring shaft is fixedly connected to the second autoclave clamp, the second Z-shaped stirring shaft passes through a through hole formed in the wall of the oil bath cylinder in a sealed mode, and a rocker is connected to the outer portion of the oil bath cylinder; a plurality of cooling pipes and a plurality of heating pipes are also arranged in the oil bathtub; the autoclave comprises a safety valve, an autoclave core, an autoclave cover and an inflation valve which are connected in sequence, wherein the inflation valve is provided with an inflation nozzle.

The autoclave core is provided with a plurality of handles, and the handles are convenient for the installation and the disassembly of the autoclave from the autoclave clamp.

The first autoclave clamp and the second autoclave clamp are adjustable autoclave clamps, and the autoclave clamps are set to be adjustable, so that autoclaves of different sizes can be conveniently installed and used.

When using the high pressure apparatus, the contents were charged into an autoclave, the autoclave was mounted on an autoclave holder, the oil bath was heated to an appropriate temperature, and the rocker was shaken to uniformly mix and heat the contents in the autoclave. After the reaction is finished, cooling the oil bath medium through a cooling water circulating pipe, and finally taking out the material.

Has the advantages that:

1. the slurry adopted by the method has low cost, wide source, good effect and easy adoption, can be effectively dissolved by the supercritical carbon dioxide fluid, can complete desizing, and is suitable for the pretreatment of anhydrous supercritical carbon dioxide fluid dyeing;

2. the wax sizing agent is adopted in the sizing and desizing method of the supercritical anhydrous dyeing and finishing, and the anhydrous supercritical carbon dioxide fluid dyeing and finishing process is further perfected.

Drawings

FIG. 1 is a schematic diagram of a detailed structure of an autoclave;

FIG. 2 is a schematic structural diagram of a small supercritical carbon dioxide experimental apparatus;

FIG. 3 is a schematic sectional structure view of a small supercritical carbon dioxide experimental system;

FIG. 4 is a schematic view of the structure of a first and a second autoclave clamps;

FIG. 5 is a schematic view of a sizing and desizing process for supercritical anhydrous dyeing and finishing.

Description of reference numerals: 1. an inflation valve; 2. an inflation inlet; 3. an anti-blocking cover; 4. an autoclave cover; 5. a high-pressure autoclave core; 6. a handle; 7. a safety valve; 8. heating a tube; 9. a cooling tube; 10. a first Z-shaped stirring shaft; 11. a first autoclave clamp; 12. an autoclave; 13. a second Z-shaped stirring shaft; 14. a rocker; 15. a second autoclave clamp; 16. a cooling tube water inlet; 17. a water outlet of the cooling pipe; 18. an oil bath tub; 19. the (mixing) shaft recess.

Detailed Description

The following is further described with reference to the accompanying drawings.

Example 1

The paraffin and the silicone oil are diluted and dissolved in a metal container according to the volume ratio of 1:1, the paraffin and the silicone oil are heated to 60 ℃ and then dissolved, and the cotton or polyester yarn passes through a winding device and rapidly passes through the waxy sizing agent. After sizing, the yarn was cooled to room temperature and finally woven into a fabric with a sizing percentage of 8% (by weight).

And after sizing is finished, desizing the cloth. A supercritical carbon dioxide pilot plant system for desizing includes an oil bath 18 and an autoclave 12. Two U-shaped heating pipes 8 are arranged in the oil bath 18 for heating. And a cooling pipe 9 is further arranged along the inner wall of the oil bath cylinder 18, the liquid level of the oil bath medium (glycerol) is exposed from a water inlet 16 and a water outlet 17 of the cooling pipe, and the oil bath medium (glycerol) in the oil bath cylinder 18 is cooled along with the circulation of cold water in the cooling pipe 9. The inner wall of the oil bath 18 is provided with a stirring shaft groove 19 for matching with a first Z-shaped stirring shaft 10, the first Z-shaped stirring shaft 10 sinks into the stirring shaft groove, the other end of the first Z-shaped stirring shaft 10 is provided with a U-shaped adjustable first autoclave clamp 11, the U-shaped first autoclave clamp 11 is adjusted to clamp one end of an autoclave 12, the other end of the autoclave 12 is clamped by a second autoclave clamp 15 which is the same as the first autoclave clamp 11, and the second autoclave clamp 15 is connected with a second Z-shaped stirring shaft 13. A through hole which is at the same height as the groove of the stirring shaft and is opposite to the groove of the stirring shaft is arranged on the wall of the oil bath cylinder 18, the second Z-shaped stirring shaft 13 passes through the through hole in a sealing way, and a rocker 14 is connected outside the oil bath cylinder 18. Rocking the rocker 14 rotates the stationary autoclave 12. The autoclave 12 with the capacity of 0.3L comprises a safety valve 7, an autoclave core 5, an autoclave cover 4 and an inflation valve 1 which are sequentially connected by screw threads, and is placed in an ultra-low temperature freezer for precooling before the autoclave 12 is used, and is cooled to the temperature below minus 20 ℃ and taken out. Placing the sized cloth into a high-pressure kettle, tightly covering a high-pressure kettle cover 4, placing the high-pressure kettle on a weighing device, zeroing the scales, arranging an inflation inlet 2 on an inflation valve 1, unscrewing an anti-blocking cover 3 on the inflation inlet 2, and connecting a carbon dioxide gas cylinder with the inflation inlet 2 by using a high-pressure pipe. Opening the valve of the charging valve 1, and introducing 210g of carbon dioxide gas with the density of 0.7g/cm³(the volume of the autoclave is 0.3 liter), after the aeration is finished, the inflation valve 1 is closed, the high-pressure pipe is disconnected, and the anti-blocking cover 3 is covered. The autoclave 12 was immersed in an oil bath medium (glycerol) and secured with a first autoclave clamp 11 and a second autoclave clamp 15. The temperature rise rate of the oil bath medium (glycerin) was 3 ℃ per minute, the temperature of the oil bath medium (glycerin) was measured using a thermometer, and the temperature of the oil bath medium (glycerin) was 50 ℃ after reachingAnd intermittently switching the two U-shaped heating pipes 8 to ensure that the temperature is kept near 50 ℃ for 30min, and simultaneously shaking the rocker 14 to stir, so that the slurry is dissolved to desize the cloth. And (3) starting a cooling pipe 9 for water circulation to cool the oil bath medium (glycerol), cooling to room temperature, taking the high-pressure kettle 12 from the first high-pressure kettle clamp 11 and the second high-pressure kettle clamp 15, unscrewing the anti-blocking cover 3, opening the inflation valve 1, and releasing the pressure in the high-pressure kettle 12 to atmospheric pressure for balance. Finally, the desized cloth was taken out, weighed, and calculated to have a desizing rate (1-difference before and after desizing per square area/difference before and after sizing per square area) of 99.7%.

Examples 2 to 10

The sizing rate of the wax material at the temperature of heated dissolution was measured and the remainder of the examples were the same as example 1:

temperature (. degree.C.)	Sizing percentage (% w/w)
		40	0 (paste not dissolved)
50	9.5
		65	6.8
75	5.3
		85	5.0
90	5.4
		100	4.1
110	3.6
		120	3.1

After comparing the sizing rates, it was found that: the slurry failed to dissolve below 50 ℃ or was too thin above 100 ℃. The temperature is preferably 50-100 deg.C.

Examples 11 to 19

The desizing rate corresponding to the heating and heat preservation temperature required by desizing is tested, and the rest of the examples are the same as the example 1:

temperature (. degree.C.)	Percent desizing (%)
		40	98.2
55	99.9
		65	99.9
75	99.9
		85	99.9
90	99.9
		100	99.9
110	99.9
		120	99.9

After comparing the desizing rates, it was found that: the desizing rate is reduced when the temperature is lower than 50 ℃, and the energy consumption is large when the temperature is overhigh. When the temperature is between 50 and 120 ℃, the temperature is ideal, and the low temperature can save energy on the premise of achieving the required desizing rate.

Examples 20 to 23

We tested the desizing rates corresponding to different stirring times, and the rest was the same as in example 1:

stirring time (min) keeping warm	Percent desizing (%)
		15	85.7
20	90.5
		25	98.9
35	99.9

After comparing the desizing rates, it was found that: when the heat preservation stirring time is less than 30min, the desizing rate is not ideal; when the heat preservation stirring time reaches 30min or more, the desizing rate can reach more than 99.9 percent.

Examples 24 to 30

We tested the desizing rates corresponding to different heating rates, and the rest was the same as example 1:

temperature rise rate (DEG C/min)	Percent desizing (%)
		0.5	99.9
1	99.9
		2	99.9
4	99.9
		5	99.9
5.5	98.7
		6	98.5

After comparing the desizing rate, the following results are found: the heating rate is too small, the treatment period is long, the treatment is too fast, and when the temperature is higher than 5 ℃, the desizing rate is slightly reduced; the temperature rise speed is recommended to be 1-5 ℃, the temperature rise speed is preferably 3 ℃, and certain efficiency can be considered.

Examples 31 to 34

We tested the desizing rates corresponding to the different carbon dioxide densities, all the other things being the same as in example 1 (the holding temperature was set at 50 ℃):

carbon dioxide Density (g/cm)³）	Percent desizing (%)
		0.4	97.5
0.6	98.9
		0.7	99.9
0.8	99.9

After comparing the desizing rate, the following results are found: the temperature is set to 50 ℃ when the density of the carbon dioxide is lower than 0.7g/cm³Its desizing rate decreased slightly. The suggested density is 0.7-0.8g/cm^3，And the pressure of the system is increased, so that the requirement of equipment is increased.

Examples 35 to 39

We tested the desizing rates corresponding to the different carbon dioxide densities, and the rest was the same as in example 1 (the holding temperature was set at 70 ℃):

carbon dioxide Density (g/cm)³）	Percent desizing (%)
		0.4	98.7
0.5	99.3
		0.6	99.9
0.8	99.9

After comparing the desizing rate, the following results are found: the temperature is set to 70 ℃ when the density of the carbon dioxide is lower than 0.6g/cm³Its desizing rate decreased slightly. The suggested density is 0.6-0.7g/cm^3，And the pressure of the system is increased, so that the requirement of equipment is increased.

Examples 40 to 42

We tested the desizing rates corresponding to the different carbon dioxide densities, the rest being the same as in example 1 (the holding temperature was set at 120 ℃):

carbon dioxide Density (g/cm)³）	Percent desizing (%)
		0.3	97.8
0.4	99.9
		0.6	99.9

After comparing the desizing rate, the following results are found: the temperature is set to 120 ℃, when the density of carbon dioxide is lower than 0.3g/cm³Its desizing rate decreased slightly. The suggested density is 0.4-0.5 g/cm^3，And the pressure of the system is increased, so that the requirement of equipment is increased.

To summarize:

1. combining example 1 with examples 2-10, it was found that the wax material is preferably dissolved by heating at a temperature of 50-100 ℃;

2. combining example 1 and examples 11-19, it was found that the desizing effect of the cloth was best when the holding temperature was 50-100 ℃;

3. by combining the embodiment 1 and the embodiments 20 to 23, the desizing effect of the cloth material reaches more than 99.9% when the heat preservation stirring time reaches 30min, and the longer the heat preservation stirring time is, the better the desizing effect is, so that the best the desizing effect of the cloth material can be inferred when the heat preservation stirring time reaches more than 30 min;

4. combining example 1 and examples 24-30, it was found that when the temperature rise rate was controlled at 1-5 ℃/min, the desizing rate of the cloth reached 99.9% or more, wherein when the temperature rise rate was controlled at 3 ℃, the desizing rate was the best;

5. combining example 1 and examples 31-42, it was found that when the temperature was set to 50-60 ℃ after warming, carbon dioxide was denseThe degree may preferably be 0.7 to 0.8g/cm³(ii) a When the temperature is set to 60 to 80 ℃ after the temperature rise, the carbon dioxide density may preferably be 0.6 to 0.7g/cm³(ii) a When the temperature is set to 80 to 120 ℃ after the temperature rise, the carbon dioxide density may preferably be 0.4 to 0.6g/cm³。

Claims

1. A sizing and desizing method for supercritical anhydrous dyeing and finishing is characterized by comprising the following steps:

heating the waxy slurry to 50-100 ℃, allowing the yarns to pass through the waxy slurry, cooling the yarns after sizing to room temperature, and weaving the yarns into cloth;

precooling the high-pressure kettle, and taking out the high-pressure kettle after the high-pressure kettle is cooled to below-20 ℃;

opening the autoclave cover, putting the cloth subjected to wax sizing, and covering the autoclave cover;

weighing the autoclave in a weighing device, and slowly introducing carbon dioxide into the autoclave to make the density of the carbon dioxide be 0.4-0.8g/cm³Closing the inflation valve and covering an anti-blocking cover;

placing the high-pressure autoclave in an oil bath tub, immersing the high-pressure autoclave by using an oil bath medium, and fixing the high-pressure autoclave by using a high-pressure autoclave clamp;

heating to above 50 deg.C, starting oil bath, stirring for above 0.5 hr, and cooling to room temperature;

taking out the autoclave, unscrewing the anti-blocking cover, and slowly opening the inflation valve to reduce the pressure to be balanced;

and opening the autoclave cover, and taking out the treated materials.

2. The sizing and desizing method for supercritical anhydrous dyeing and finishing as claimed in claim 1, characterized in that: in the step (6), the temperature of the oil bath medium is raised to 50-100 ℃.

3. The sizing and desizing method for supercritical anhydrous dyeing and finishing as claimed in claim 2, characterized in that: in the step (4), when the temperature is set to be 50-60 ℃ after the temperature is raised, the density of the carbon dioxide is 0.7-0.8g/cm³(ii) a When the temperature is 60-80 deg.C after heating, the density of carbon dioxide is setIs 0.6-0.7g/cm³(ii) a When the temperature is set to 80-100 ℃ after the temperature is raised, the density of the carbon dioxide is 0.4-0.6g/cm³。

4. The sizing and desizing method for supercritical anhydrous dyeing and finishing as claimed in claim 1, characterized in that: in the step (5), the oil bath medium is glycerol.

5. The sizing and desizing method for supercritical anhydrous dyeing and finishing as claimed in claim 1, characterized in that: the temperature rise speed of the oil bath medium in the step (6) is 1-5 ℃/min.

6. The sizing and desizing method for supercritical anhydrous dyeing and finishing as claimed in claim 1, characterized in that: the waxy slurry in the step (1) comprises waxy materials and silicone oil diluents, and the waxy materials are dissolved in the diluents by heating.

7. The method of claim 5, wherein said step of removing said slurry from said supercritical anhydrous dyeing and finishing step comprises: the waxy material is one of paraffin wax, beeswax, vegetable wax, wood wax, bayberry wax, candelilla wax, Japan wax, palm wax, rice bran wax, jojoba oil, castor wax, animal wax, insect wax, wool wax, spermaceti wax, mineral wax, montan wax, ozokerite, petroleum wax, microcrystalline wax, petroleum jelly, synthetic wax, Fischer-Tropsch wax or polyethylene wax.

8. A high pressure apparatus for a method of sizing and desizing a supercritical anhydrous dye finish as recited in claim 1 wherein: including oil bathtubs and autoclaves; a stirring shaft groove is formed in the inner wall of the oil bath, a first Z-shaped stirring shaft is arranged in the stirring shaft groove in a matched mode, a first autoclave clamp is arranged at the other end of the first Z-shaped stirring shaft, one end of an autoclave is fixed on the first autoclave clamp, a second autoclave clamp is fixed at the other end of the autoclave, a second Z-shaped stirring shaft is fixedly connected to the second autoclave clamp, the second Z-shaped stirring shaft passes through a through hole formed in the wall of the oil bath cylinder in a sealed mode, and a rocker is connected to the outer portion of the cylinder; a plurality of cooling pipes and a plurality of heating pipes are also arranged in the oil bathtub; the autoclave comprises a safety valve, an autoclave core, an autoclave cover and an inflation valve which are connected in sequence, wherein an inflation nozzle is arranged on the inflation valve.

9. The high pressure apparatus for the sizing and desizing process of supercritical anhydrous dyeing and finishing as claimed in claim 8, wherein: and a plurality of handles are arranged on the high-pressure autoclave core.

10. The high pressure apparatus for the sizing and desizing process of supercritical anhydrous dyeing and finishing as claimed in claim 8, wherein: the first autoclave clamp and the second autoclave clamp are both adjustable autoclave clamps.