CN101812809A - Supercritical carbon dioxide dyeing method for bulk fibers - Google Patents

Abstract

The invention relates to a supercritical carbon dioxide dyeing method for bulk fibers. The process flow comprises the following steps: placing dyes and bulk fiber materials in a supercritical carbon dioxide dyeing device, and dyeing under the condition of 70-150 DEG C and 20-30 MPa for 50-120 minutes; then releasing the pressure, and reclaiming carbon dioxide and the dyes under the condition of 4-5 MPa; and returning to the normal state to obtain stock-dyed fibers, wherein the bulk fibers are natural cellulose fibers, natural protein fibers and chemical fibers. The outstanding characteristics of the invention are as follows: the dyes directly carry out the supercritical waterless dyeing on the bulk fibers, and enable the fabric to obtain a special effect; the fabric is enabled to have the characteristics of good dyeing quality, cleaning production without waste products and environmental pollution, low comprehensive cost and obvious economic benefits and environmental benefits, especially waterless dyeing which conforms to the current low-carbon economic policy calling for water saving and energy saving; and the product comes up to GB18401-2003, National General Safety Technical Code for Textile Products.

Description

Supercritical Carbon Dioxide Dyeing Method for Loose Fiber

technical field

The invention belongs to the field of textile printing and dyeing. It specifically relates to the textile printing and dyeing technology using dyes dissolved in supercritical carbon dioxide, especially relates to the supercritical dyeing technology of loose fibers with plants containing natural pigments.

Background technique

The problem of resources and environment is a fundamental and strategic issue faced by human society in pursuit of sustainable development in the 21st century. Scientific research in the field of water resources and environment has attracted much attention from the international community and governments. my country is a country seriously short of water. Water pollution has made the problem of resource shortage more prominent. The pollution of the textile dyeing and finishing industry is one of the main sources of water pollution. The traditional loose fiber dyeing process is complicated and consumes a lot of water resources. produce serious pollution. Improper treatment of printing and dyeing wastewater in the textile industry has seriously polluted the environment.

Matter exists in three phases—gas, liquid, and solid. The point where the three phases coexist in equilibrium is called the triple point. The point at which the liquid and gas phases are in equilibrium is called the critical point. The term "supercritical state" refers to a state exceeding the critical temperature and critical pressure inherent in each compound. Substances in this state are called supercritical fluids, which have intermediate properties between gases and liquids. The viscosity of supercritical fluid is close to that of gas, and the diffusion coefficient is between gas and liquid. Its permeability is large, and the penetration of substances is faster than that of liquid. After compression, supercritical fluid can obtain almost the same density as liquid. It has a strong dissolving ability and has the property of dissolving non-polar or low-polar substances well. The critical temperature of carbon dioxide is 31.1°C, and the critical pressure is 7.39MPa, which can be in a supercritical state under relatively safe conditions. Using supercritical carbon dioxide as the dyeing medium truly realizes anhydrous dyeing, completely eliminates the generation of printing and dyeing wastewater, fundamentally solves the problem of printing and dyeing wastewater treatment, and protects water resources; process, reducing energy consumption; carbon dioxide is non-toxic, non-explosive, cheap and easy to obtain, and can be recycled, so there is no harmful gas emission during the dyeing process; residual dyes can be reused, which greatly improves the utilization rate of dyes. It is an environmentally friendly dyeing process with high technical content, representing the development direction of the dyeing and finishing industry ^[1-5] .

Since 1988, supercritical carbon dioxide dyeing has gone through the following stages: chemical fiber disperse dyeing; natural fiber disperse dyeing; natural fiber or dye modification, in order to obtain the best effect of natural fiber supercritical carbon dioxide dyeing ^{[6～ 11]} . Since natural fibers are polar fibers, and disperse dyes are non-polar, the binding force between each other is very small. Therefore, the current research on the supercritical carbon dioxide dyeing process of natural fibers still needs to undergo a modification process to make the natural fibers and dyes There is a certain affinity between them. Such as quaternary ammonium salt surfactant modification, cellulase modification, organic silicon finishing agent FK-220C modification, CTA-705 modification and plasma modification, etc. Various modification processes can improve the fixation rate and dye uptake rate of dyes, but increase the dyeing time, process flow or sewage treatment costs ^[11-17] .

Traditional loose fiber dyeing generally uses an open dyeing vat. Before dyeing, the loose fiber is put into the dyeing cage, and after compaction, the dyeing cage is hoisted into the main vat, and the main circulation pump is directly started for dyeing. However, after dyeing, it needs to be released. For the residual liquid, add multiple channels of clear water to wash or soap to remove the floating color on the fiber, then hang out the dyeing cage to take out the fiber and then dehydrate and dry. It has caused great pollution to the environment, wasted huge water resources, and does not comply with the latest environmental policies for water conservation and emission reduction.

references

[1] Saus W et al. Water2free Dyeing of Synthetic Material Dyeing in Supercritical CO ₂ . International Textile Bulletin Dyeing/Printing/Finishing, 1993(1): 20～22.

[2] Knitte D E et al. Application of Supercritical Carbon Dioxide in Finishing Processes. Text. Inst., 1993 (4): 534～552.

[3] Gorgi R D et al. Dyeing Polyester Fibers with Disperse Dyes in Supercritical CO _{2 .} Dyes and Pigments, 2000(1): 75～79.

[4] Scholmeyer E, Knittel D, Buschmann H-J, Chneider GM, Poulakis K. Farbecerfahren. DE 39 06 724 A1, D 06P1/100; Germany: 13.09.1990.

[5] Gebert B, Saus W, Knittel D, Buschmann H-J, Scholmeyer E. Dyeing natural fibers with disperse dyes in supercritical carbon dioxide. Text ResJ, 1994, 64(7): 371～374.

[6] Andreas Schmidt, Elke Bach, and Eckhard Schollmeyer. Damage to Natural and Synthetic Fibers Treated in Supercritical Carbon Dioxide at 300bar and Temperatures up to 160℃. Textile Res, 2002, 72(11): 1023～1032.

[7] Pier Liugi Beltrame, Antonella Castelli, Elena Selli, Andrea Mossa, Giovanni Testa, Anna Maria Bonfatti & Alberto Seves. Dying of Cotton in Supercritical Carbon Dioxide. Dyes and Pigments, 1998, 39(4): 335～340.

[8] A.Schmidt, E.Bach, E.Scholmeyer. The dyeing of natural fibers with reactive disperse dyes in supercritical carbon dioxide. Dyes and Pihments, 2003, 56: 27～35.

[9] Ma Dongxia, Zheng Laijiu. Research on Supercritical CO ₂ Dyeing Technology of Natural Fibers. Shanghai Textile Science and Technology, 2005, 33(3): 13～16.

[10] Ma Dongxia, Zheng Laijiu, Jia Chunxue. Discussion on supercritical carbon dioxide anhydrous dyeing of linen fabrics. Textile Herald, 2005, 1:51～54.

[11] Wu Minghua, Chen Shuilin. Supercritical carbon dioxide dyeing technology [J]. Silk, 2001, (10): 23-25.

[12] Dyeing kettle in supercritical carbon dioxide device. Application number: 200510136782.2.

[13] Supercritical carbon dioxide dyeing device. Chinese patent application number: 200520093701.0.

[14] Supercritical carbon dioxide dyeing device and its process. Chinese patent application number: 200510047767.0.

[15] Chinese Patent Publication No. for New Technology of Natural Fiber Supercritical Carbon Dioxide Dyeing: CN 1467338A.

[16] Liu Zhiwei, Zheng Laijiu. Research on supercritical carbon dioxide dyeing of wool fabrics. Wool Technology, 2005, 3: 9-12.

[17] Zheng Laijiu, Liu Zhiwei, Ji Ting, etc. Supercritical CO ₂ Dyeing Technology. Chemical Engineering, 2006, 34(9): 71～74.

Contents of the invention

Aiming at the problems and defects in the above-mentioned prior art, the purpose of the present invention is to provide a technique for directly dyeing loose fibers with supercritical fluid.

The technical solution adopted by the present invention to solve the technical problem is: place the pulverized natural pigment-containing plants and loose fibers in the dye kettle and the dye kettle of the supercritical carbon dioxide device respectively, and realize supercritical dyeing under the set process conditions. Carbon dioxide extraction, dyeing, followed by decompression to recover carbon dioxide and dye. The technological process is as follows: put the crushed natural pigment-containing plants and loose fiber raw materials into the dyeing cage of the supercritical carbon dioxide device and the dyeing kettle in sequence; The pressure is 18-30MPa, extraction and dyeing are carried out under this condition, and the time is 50-120min; then release the pressure and keep it at 4-5MPa, 25-40°C to recover carbon dioxide and dyes; release the pressure, Cool down to the normal state to get the dyed fiber, and perform performance analysis test on it. After testing and practice, the effect of optimizing the following process conditions is better: temperature: 80-120°C; pressure: 22-27MPa; time: 50-90min; separation pressure: 4-5MPa; mass ratio between dye and fiber It is 1:20～1:5. The bulk fibers are natural cellulose fibers, natural protein fibers and chemical fibers.

According to GB/T.3921.1-1997 Textile Color Fastness Test Color Fastness to Washing, GB7565-87 Textile Color Fastness Test Cotton and Viscose Standard Lining Fabric Specifications and GB6151-857 Textile Color Fastness Test Color Fastness Evaluation , for fabric color fastness testing and analysis. The results show that the color fastness to rubbing and color fastness to washing of the dyed fabric can both reach GB18401-2003 "National Basic Safety Technical Specifications for Textile Products", the color fastness to rubbing can reach grade 3-4, and the color fastness to washing can reach grade 3-4. The color fastness can reach grade 3-5.

Compared with the prior art, the outstanding feature of the present invention is that it changes the traditional process of weaving fibers into fabrics and then dyeing the fabrics, and also improves the process for some shortcomings of the existing traditional loose fiber dyeing, The direct dyeing of loose fibers with plants containing natural pigments under supercritical conditions has been realized. It has the characteristics of good fiber dyeing quality, short process flow, clean production with no waste products and no environmental pollution, low comprehensive cost, significant economic and environmental benefits.

Detailed ways

Embodiment 1: The pulverized indigo with a quality of 15g is placed in a dye kettle located in a supercritical carbon dioxide dyeing device. Get 350g cotton fiber and place in the dyeing cage in the dyeing kettle. Turn on the heating system and refrigeration system to make the device reach the required temperature condition of 120°C for extraction and dyeing; turn on the high-pressure system to make the device reach the required pressure condition of 28Mpa for extraction and dyeing; separation pressure: 5MPa. Dyeing was completed in 100 minutes. The dyed fiber is blue, and the color fastness to rubbing is grade 4 and the color fastness to washing can reach grade 5.

Embodiment 2: the pulverized indigo with a quality of 20g is placed in a dye kettle located in a supercritical carbon dioxide dyeing device. Get 350g hemp fiber and place in the dyeing cage in the dyeing kettle. Turn on the heating system and refrigeration system to make the device reach the required temperature condition of 110°C for extraction and dyeing; turn on the high-pressure system to make the device reach the required pressure condition of 28Mpa for extraction and dyeing; separation pressure: 5MPa. Dyeing was completed in 90 minutes. The dyed fiber is blue, and the color fastness to rubbing is grade 4 and the color fastness to washing can reach grade 5.

Embodiment 3: the pulverized indigo with a quality of 25g is placed in a dye kettle located in a supercritical carbon dioxide dyeing device. Get 350g wool fiber and place in the dyeing cage in the dyeing kettle. Turn on the heating system and refrigeration system to make the device reach the required temperature of 100°C for extraction and dyeing; turn on the high-pressure system to make the device reach the required pressure of 28Mpa for extraction and dyeing; separation pressure: 5MPa. Dyeing was completed in 90 minutes. The dyed fiber is blue, and the color fastness to rubbing is grade 4 and the color fastness to washing can reach grade 5.

Embodiment 4: The pulverized indigo with a quality of 30g is placed in a dye kettle located in a supercritical carbon dioxide dyeing device. Get 350g soybean protein fiber and place in the dyeing cage in the dyeing kettle. Turn on the heating system and refrigeration system to make the device reach the required temperature of 80°C for extraction and dyeing; turn on the high-pressure system to make the device reach the required pressure of 25Mpa for extraction and dyeing; separation pressure: 5MPa. After 70 minutes, the dyeing is completed in one step. The dyed fiber is blue, the color fastness to rubbing is 3.5 and the color fastness to washing can reach 4.5.

Embodiment 5: The pulverized indigo with a quality of 35g is placed in a dye kettle located in a supercritical carbon dioxide dyeing device. Get 350g tencel fiber and place in the dyeing cage in the dyeing kettle. Turn on the heating system and refrigeration system to make the device reach the required temperature of 100°C for extraction and dyeing; turn on the high-pressure system to make the device reach the required pressure of 25Mpa for extraction and dyeing; separation pressure: 5MPa. Dyeing was completed in 80 minutes. The dyed fiber is blue, the color fastness to rubbing is grade 3 and the color fastness to washing can reach grade 4.

Embodiment 6: The pulverized indigo with a quality of 30 g is placed in a dye kettle located in a supercritical carbon dioxide dyeing device. Get 350g polyester fiber and place in the dyeing cage in the dyeing kettle. Turn on the heating system and refrigeration system to make the device reach the required temperature of 100°C for extraction and dyeing; turn on the high-pressure system to make the device reach the required pressure of 26Mpa for extraction and dyeing; separation pressure: 5MPa. Dyeing was completed in 100 minutes. The fiber is blue after dyeing, the color fastness to rubbing is grade 4 and the color fastness to washing can reach grade 4.

Example 7: The pulverized madder with a mass of 15 g was placed in a dye kettle located in a supercritical carbon dioxide dyeing device. Get 350g cotton fiber and place in the dyeing cage in the dyeing kettle. Turn on the heating system and refrigeration system to make the device reach the required temperature condition of 110°C for extraction and dyeing; turn on the high-pressure system to make the device reach the required pressure condition of 28Mpa for extraction and dyeing; separation pressure: 5MPa. After 100 minutes, the dyeing is completed in one step. The dyed fiber is red, the color fastness to rubbing is 3.5 and the color fastness to washing can reach 4.5.

Embodiment 8: Place the pulverized madder with a mass of 20 g in a dye kettle located in a supercritical carbon dioxide dyeing device. Get 350g hemp fiber and place in the dyeing cage in the dyeing kettle. Turn on the heating system and refrigeration system to make the device reach the required temperature of 100°C for extraction and dyeing; turn on the high-pressure system to make the device reach the required pressure of 27Mpa for extraction and dyeing; separation pressure: 5MPa. Dyeing is completed in one step after 90 minutes. The dyed fiber is red, the color fastness to rubbing is 3.5 and the color fastness to washing can reach 3.5.

Embodiment 9: The pulverized madder with a mass of 25 g is placed in a dye kettle located in a supercritical carbon dioxide dyeing device. Get 350g wool fiber and place in the dyeing cage in the dyeing kettle. Turn on the heating system and refrigeration system to make the device reach the required temperature of 90°C for extraction and dyeing; turn on the high-pressure system to make the device reach the required pressure of 26Mpa for extraction and dyeing; separation pressure: 5MPa. After 80 minutes, the dyeing is completed in one step. The dyed fiber is red, the color fastness to rubbing is 3 and the color fastness to washing can reach 4.5.

Example 10: The pulverized madder with a mass of 30 g was placed in a dye kettle located in a supercritical carbon dioxide dyeing device. Get 350g soybean protein fiber and place in the dyeing cage in the dyeing kettle. Turn on the heating system and refrigeration system to make the device reach the required temperature of 80°C for extraction and dyeing; turn on the high-pressure system to make the device reach the required pressure of 25Mpa for extraction and dyeing; separation pressure: 5MPa. After 70 minutes, the dyeing is completed in one step. The dyed fiber is red, the color fastness to rubbing is 3.5 and the color fastness to washing can reach 4.5.

Example 11: The pulverized madder with a mass of 35 g was placed in a dye kettle located in a supercritical carbon dioxide dyeing device. Get 350g tencel fiber and place in the dyeing cage in the dyeing kettle. Turn on the heating system and refrigeration system to make the device reach the required temperature of 70°C for extraction and dyeing; turn on the high-pressure system to make the device reach the required pressure of 24Mpa for extraction and dyeing; separation pressure: 5MPa. Dyeing is completed in one step after 60 minutes. The dyed fiber is red, the color fastness to rubbing is grade 3 and the color fastness to washing can reach grade 4.

Example 12: The pulverized madder with a mass of 30 g was placed in a dye kettle located in a supercritical carbon dioxide dyeing device. Get 350g polyester fiber and place in the dyeing cage in the dyeing kettle. Turn on the heating system and refrigeration system to make the device reach the required temperature of 90°C for extraction and dyeing; turn on the high-pressure system to make the device reach the required pressure of 26Mpa for extraction and dyeing; separation pressure: 5MPa. After 100 minutes, the dyeing is completed in one step. The dyed fiber is red, the color fastness to rubbing is 4.5 and the color fastness to washing can reach 4.5.

Embodiment 13: Place the pulverized bamboo yellow with a mass of 15 g in a dye kettle located in a supercritical carbon dioxide dyeing device. Get 350g cotton fiber and place in the dyeing cage in the dyeing kettle. Turn on the heating system and refrigeration system to make the device reach the required temperature condition of 120°C for extraction and dyeing; turn on the high-pressure system to make the device reach the required pressure condition of 28Mpa for extraction and dyeing; the separation pressure is 5MPa. After 100 minutes, the dyeing is completed in one step. The fiber is yellow after dyeing, the color fastness to rubbing is grade 4 and the color fastness to washing can reach grade 4.

Example 14: The pulverized bamboo yellow with a mass of 20 g was placed in a dye kettle located in a supercritical carbon dioxide dyeing device. Get 350g hemp fiber and place in the dyeing cage in the dyeing kettle. Turn on the heating system and refrigeration system to make the device reach the required temperature condition of 110°C for extraction and dyeing; turn on the high-pressure system to make the device reach the required pressure condition of 27Mpa for extraction and dyeing; separation pressure: 5MPa. Dyeing is completed in one step after 90 minutes. The dyed fiber is yellow, the color fastness to rubbing is 4.5 and the color fastness to washing can reach 5.

Example 15: The pulverized bamboo yellow with a mass of 25 g was placed in a dye kettle located in a supercritical carbon dioxide dyeing device. Get 350g wool fiber and place in the dyeing cage in the dyeing kettle. Turn on the heating system and refrigeration system to make the device reach the required temperature of 100°C for extraction and dyeing; turn on the high-pressure system to make the device reach the required pressure of 26Mpa for extraction and dyeing; separation pressure: 5MPa. After 80 minutes, the dyeing is completed in one step. The dyed fiber is yellow, the color fastness to rubbing is 3.5 and the color fastness to washing can reach 4.5.

Embodiment 16: Place the pulverized bamboo yellow with a mass of 30 g in a dye kettle located in a supercritical carbon dioxide dyeing device. Get 300g soybean protein fiber and place in the dyeing cage in the dyeing kettle. Turn on the heating system and refrigeration system to make the device reach the required temperature condition of 90°C for extraction and dyeing; turn on the high-pressure system to make the device reach the required pressure condition of 25Mpa for extraction and dyeing; separation pressure: 5MPa. After 70 minutes, the dyeing is completed in one step. The fiber is yellow after dyeing, the color fastness to rubbing is 3.5 and the color fastness to washing can reach 3.5.

Example 17: The pulverized bamboo yellow with a mass of 35 g was placed in a dye kettle located in a supercritical carbon dioxide dyeing device. Get 300g tencel fiber and place in the dyeing cage in the dyeing kettle. Turn on the heating system and refrigeration system to make the device reach the temperature condition of 100°C required for extraction and dyeing; turn on the high-pressure system to make the device reach

The pressure required for extraction and dyeing is 19Mpa; separation pressure: 5MPa. After 70 minutes, the dyeing is completed in one step. The dyed fiber is yellow, the color fastness to rubbing is 4 and the color fastness to washing can reach 4.5.

Example 18: The pulverized bamboo yellow with a mass of 30 g was placed in a dye kettle located in a supercritical carbon dioxide dyeing device. Get 300g polyester fiber and place in the dyeing cage in the dyeing kettle. Turn on the heating system and refrigeration system to make the device reach the required temperature condition of 110°C for extraction and dyeing; turn on the high-pressure system to make the device reach the required pressure condition of 20Mpa for extraction and dyeing; separation pressure: 5MPa. After 100 minutes, the dyeing is completed in one step. The dyed fiber is yellow, the color fastness to rubbing is 4 and the color fastness to washing can reach 4.5.

Claims (3)

1. supercritical carbon dioxide dyeing method for bulk fibers, its characteristics are that with plant that contains natural colouring matter and bulk fibre be raw material, use supercritical carbon dioxide to realize the bulk fibre direct dyeing; The plant and the bulk fibre mass ratio that wherein contain natural colouring matter are: 1: 5～1: 20; The described plant that contains natural colouring matter is indigo, madder, tabasheer;

Technological process is: natural after will pulverizing successively contains the pigment plant, the bulk fibre raw material is inserted in the supercritical CO 2 dyeing device; It is 70～150 ℃ that heating makes its temperature, and it is 20～30MPa that the unlatching high-pressure system makes its pressure, extract with this understanding, and dyeing, the time is 60～100min; Release of pressure and make it remain on the recovery of carrying out carbon dioxide and dyestuff under the 4～5MPa, 25～40 ℃ then; Release of pressure, be cooled to normality and get coloured fibre.

2. according to the described supercritical carbon dioxide dyeing method for bulk fibers of claim 1, it is characterized in that in the described technological process that it is 80～120 ℃ that heating makes its temperature; Pressure is 22～27MPa; Dyeing time is 50～90min.

3. according to supercritical carbon dioxide dyeing method for bulk fibers described in claim 1 or 2, it is characterized in that described bulk fibre is native cellulose fibre, natural protein fibre and chemical fibre.