Ozone pretreatment process for textile printing and dyeing

Abstract

The invention discloses an ozone pretreatment process for textile printing and dyeing, and relates to the technical field of textile printing and dyeing, the pretreatment process comprises the following steps: mixing hydrogen peroxide, a copper complex catalyst, glycerol triacetate, a compound enzyme, sodium pyrophosphate and a penetrant to prepare a pretreatment solution, immersing a textile fabric in the pretreatment solution, soaking the pretreated textile fabric in the finishing liquid, placing the textile fabric subjected to fabric treatment in a dyeing jar, and introducing ozone gas. According to the method, by introducing the glycerol triacetate and the copper complex catalyst, the glycerol triacetate generates peracetic acid under the action of the hydrogen peroxide and the copper complex catalyst, and pigment molecules, slurry residues, other impurities and the like on the textile fabric are oxidized and decomposed.

Description

Technical Field

[0001] The invention relates to the technical field of textile printing and dyeing, in particular to an ozone pretreatment process for textile printing and dyeing. Background Art

[0002] With the increasing global environmental awareness, there are higher requirements for the emission of harmful substances in the textile printing and dyeing industry. The traditional textile printing and dyeing process requires a large amount of chemical additives to achieve desizing, scouring, bleaching and other processes, which has problems such as long processing time, high energy consumption, and large wastewater discharge.

[0003] Ozone pretreatment technology can shorten the processing time, improve production efficiency, and reduce wastewater discharge, which has led to an increasing application of ozone pretreatment technology in the textile printing and dyeing industry. The ozone pretreatment process mainly uses the strong oxidizing property of ozone to treat textiles and oxidize and decompose various impurities on the textiles. Therefore, an ozone pretreatment process for textile printing and dyeing is extremely important.

[0004] Patent CN105177979B discloses an ozone-ultrasonic coordinated textile scouring and dyeing method and device. The above patent realizes the desizing, scouring and bleaching of cotton fabrics, polyester-cotton blended fabrics, chemical fiber fabrics, etc., reduces or eliminates the discharge of polluted wastewater, shortens the process flow and time, and reduces the consumption of chemical agents.

[0005] The above patent solves the energy, water and chemical consumption problems of conventional pre-treatment methods by adding an ultrasonic co-processing device, but there is still room for optimization in simplifying the process flow. The present application solves the problem of requiring other devices for co-processing while ensuring the pre-treatment effect by immersing the textile in pre-treatment liquid and finishing liquid in turn.

[0006] To this end, the present application proposes an ozone pretreatment process for textile printing and dyeing to achieve desizing and bleaching of textiles. Summary of the invention

[0007] The object of the present invention is to provide an ozone pretreatment process for textile printing and dyeing, so as to solve the technical problem proposed in the above background technology that other devices are needed for coordinated treatment while ensuring the pretreatment effect.

[0008] To achieve the above object, the present invention provides the following technical solution: an ozone pretreatment process for textile printing and dyeing, the pretreatment process comprising the following steps: S1. Pretreatment: hydrogen peroxide, copper complex catalyst, triacetin, complex enzyme, sodium pyrophosphate and penetrant are mixed to prepare a pretreatment solution, and the textile is immersed in the pretreatment solution at a bath ratio of 1:10; S2. Fabric treatment: immerse the pretreated textile into the finishing solution at a bath ratio of 1:20, place it in a constant temperature oscillating dyeing machine, and heat it to 100°C; S3. Ozone treatment: Place the fabric-treated textile in a dyeing vat, add deionized water and a heterogeneous catalyst, use an ozone generator to generate and pass ozone gas into the dyeing vat to ozonate the deionized water.

[0009] Preferably, the amount of hydrogen peroxide is 2-10 g / L, the amount of copper complex catalyst is 20-45 μmol / L, the amount of triacetin is 20-30 mmol / L, the amount of sodium pyrophosphate is 1-5 g / L, and the amount of finishing liquid is 1-5 g / L.

[0010] Preferably, the method for preparing the copper complex catalyst comprises the following steps: Adding iminodiacetic acid to deionized water to prepare an iminodiacetic acid aqueous solution, slowly dropping the iminodiacetic acid aqueous solution into an aqueous solution of copper sulfate pentahydrate, stirring, and obtaining a mixture; 4-dimethylaminopyridine is dissolved in deionized water to obtain a 4-dimethylaminopyridine aqueous solution, and the 4-dimethylaminopyridine aqueous solution is slowly added dropwise to the mixture and stirred to obtain a copper complex catalyst.

[0011] Preferably, the composite enzyme is a mixture of desizing enzyme DL, scouring enzyme BP and cutinase S, the dosage of desizing enzyme DL is 1-5 g / L, the dosage of scouring enzyme BP is 1-10 g / L, and the dosage of cutinase S is 1-5 g / L.

[0012] Preferably, the method for preparing the finishing liquid comprises the following steps: Deionized water was added to a reaction container, and 20 wt % of sorbitan monolaurate and 25 wt % of polyoxyethylene sorbitan fatty acid ester were poured into the reaction container, and stirred using a mechanical stirring device to obtain a mixed solution; The reaction container is placed under an emulsifier to emulsify the mixed solution. During the emulsification process, 2,4,6-trichloropyrimidine is added dropwise to obtain a finishing solution.

[0013] Preferably, the heterogeneous catalyst is a cerium-manganese composite catalyst or a ternary catalyst, and the preparation method of the cerium-manganese composite catalyst comprises the following steps: Dissolve cerium nitrate hexahydrate and manganese nitrate in distilled water respectively, slowly pour the dissolved cerium nitrate hexahydrate solution and manganese nitrate solution into the sodium hydroxide solution, and stir with a magnetic stirrer for 1 hour to obtain a uniform mixed solution; The mixed solution was placed in a polytetrafluoroethylene-lined hydrothermal reactor, the hydrothermal reactor was placed in an oven, kept at 120° C. for 16 h, and cooled to room temperature to obtain a reaction mixture; The reaction mixture was centrifugally washed twice with distilled water and ethanol respectively, the washed reaction mixture was placed in a drying oven, dried at 80° C. for 12 h, and the dried reaction mixture was calcined at 500° C. for 5 h to obtain a cerium-manganese composite catalyst.

[0014] Preferably, the preparation method of the three-way catalyst comprises the following steps: Mixing a manganese nitrate solution, an iron nitrate solution and a cerium nitrate solution, stirring with a magnetic stirrer to obtain a metal nitrate solution, and adding the purified nano-alumina to the metal nitrate solution to form an impregnation solution; The impregnation liquid was placed on a shaker, reciprocated and oscillated for 12 hours, and allowed to stand for 6 hours. The solid phase was separated and washed with distilled water. The washed solid phase was placed in an oven and dried at 80°C for 12 hours. The dried solid phase was calcined at 500°C for 5 hours to obtain a ternary catalyst.

[0015] Preferably, the penetrant is selected from one of penetrant JFC, penetrant JS, and penetrant AP800, and the dosage of the penetrant is 0-3 g / L.

[0016] Preferably, the pre-treatment process further comprises washing the fabric, and the washing of the fabric comprises the following steps: The ozone-treated textile was washed twice with hot water at 50-60°C, and then washed twice with cold water, each washing for 10 minutes. The washed textile was placed in an oven at 55°C for drying.

[0017] Preferably, the pre-treatment process further includes fabric dyeing and wastewater treatment, and the fabric dyeing and wastewater treatment includes the following steps: Fabric dyeing: Add the reactive dye into the infrared dyeing machine with a bath ratio of 1:30, put in the treated textile, heat it to 60℃, add sodium glauber powder and sodium bicarbonate; Wastewater treatment: Collect the waste liquid generated in the production process into the waste liquid tank, and use an ozone generator to introduce ozone gas into the bottom of the waste liquid tank.

[0018] Compared with the prior art, the present invention has the following beneficial effects: 1. The present invention introduces triacetin and a copper complex catalyst, and triacetin generates peracetic acid under the action of hydrogen peroxide and the copper complex catalyst, which oxidizes and decomposes pigment molecules, slurry residues and other impurities on the textile; 2. The present invention introduces chloropyrimidine molecules through the finishing liquid, and a cross-linked structure is formed between the chloropyrimidine molecules and the textile fiber molecular chains, thereby improving the wrinkle resistance of the textile. The chloropyrimidine molecules are adsorbed on the surface of the impurity particles to form an emulsion film, thereby solving the problem of reaggregation of the impurity particles. 3. The present invention introduces a heterogeneous catalyst, and ozone is decomposed into strong oxidizing free radicals at the active sites on the catalyst surface, which rapidly oxidizes and decomposes the residual pigments, impurities, etc. on the textile, thereby improving the bleaching efficiency; 4. The present invention introduces sodium pyrophosphate and complex enzyme. Sodium pyrophosphate provides a favorable reaction environment for the copper complex catalyst, generates more active substances with bleaching effect, and various components constituting the complex enzyme work synergistically to jointly remove various impurities and sizing agents on the textile, thereby improving the desizing effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 This is a schematic diagram of the ozone pre-treatment process of the present invention; Figure 2 This is a schematic diagram of the preparation process of the copper complex catalyst of the present invention; Figure 3 It is a schematic diagram of the preparation process of the finishing liquid of the present invention; Figure 4 This is a schematic diagram of the preparation process of the cerium-manganese composite catalyst of the present invention; Figure 5 It is a schematic diagram of the preparation process of the three-way catalyst of the present invention; Figure 6 It is a schematic diagram of the penetrant of the present invention; Figure 7 It is a schematic diagram of the heterogeneous catalyst of the present invention; Figure 8 Schematic diagram of the composite enzyme of the present invention. DETAILED DESCRIPTION

[0020] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0021] Example 1, please refer to Figure 1 and Figure 6 , an ozone pretreatment process for textile printing and dyeing, the pretreatment process comprising the following steps: S1. Pretreatment: 10 g / L hydrogen peroxide, 45 μmol / L copper complex catalyst, 30 mmol / L triacetin, complex enzyme, 5 g / L sodium pyrophosphate, and 3 g / L penetrant were mixed to prepare a pretreatment solution, and the textile was immersed in the pretreatment solution at a bath ratio of 1:10. The complex enzyme was a mixture of 5 g / L desizing enzyme DL, 10 g / L scouring enzyme BP, and 5 g / L cutinase S. S2. Fabric treatment: immerse the pretreated textile into 5 g / L finishing solution with a bath ratio of 1:20, place it in a constant temperature oscillating dyeing machine, and heat it to 100°C; S3. Ozone treatment: Place the fabric-treated textile in a dyeing vat, add deionized water and a cerium-manganese composite catalyst, use an ozone generator to generate and pass ozone gas into the dyeing vat to ozonate the deionized water, wash the ozone-treated textile twice with 50-60°C hot water, and then wash the textile twice with cold water, each washing for 10 minutes, and place the washed textile in a 55°C oven for drying.

[0022] Furthermore, the ester bond in the triacetin molecule is broken under the action of hydrogen peroxide and the copper complex catalyst to generate a corresponding carboxylic acid, which further reacts with hydrogen peroxide to generate peracetic acid. As a strong oxidant, peracetic acid has a strong oxidizing property. Peracetic acid decomposes colored substances on the textile by oxidation to make them colorless or light-colored substances, thereby quickly oxidizing pigment molecules, slurry residues and other impurities on the textile. In addition, peracetic acid can penetrate into the fiber of the textile to remove impurities and pigments inside the fiber, thereby indirectly enhancing the bleaching effect and allowing the textile to achieve a more ideal whiteness. Triacetin helps to improve the wettability of the surface of the textile fiber, making it easier for the pretreatment liquid and ozone to penetrate into the fiber of the textile, so that the pretreatment liquid and ozone can fully contact and react with the pigment molecules and other impurities on the surface of the textile fiber.

[0023] Example 2, please refer to Figure 1 , Figure 2 and Figure 6 , an ozone pretreatment process for textile printing and dyeing, the pretreatment process comprising the following steps: S1. Pretreatment: adding iminodiacetic acid to deionized water to prepare an iminodiacetic acid aqueous solution, slowly dropping the iminodiacetic acid aqueous solution into a copper sulfate pentahydrate aqueous solution, stirring to obtain a mixture, dissolving 4-dimethylaminopyridine in deionized water to obtain a 4-dimethylaminopyridine aqueous solution, slowly dropping the 4-dimethylaminopyridine aqueous solution into the mixture, stirring to obtain a cerium-manganese composite catalyst, mixing 8 g / L of hydrogen peroxide, 40 μmol / L of a copper complex catalyst, 28 mmol / L of triacetin, a composite enzyme, 4 g / L of sodium pyrophosphate, and 3 g / L of a penetrant to prepare a pretreatment solution, immersing the textile in the pretreatment solution, the bath ratio is 1:10, and the composite enzyme is a mixture of 4 g / L of desizing enzyme DL, 8 g / L of scouring enzyme BP, and 4 g / L of cutinase S; S2. Fabric treatment: immerse the pretreated textile into 4 g / L finishing liquid with a bath ratio of 1:20, place it in a constant temperature oscillating dyeing machine, and heat it to 100°C; S3. Ozone treatment: Place the fabric-treated textile in a dyeing vat, add deionized water and a cerium-manganese composite catalyst, use an ozone generator to generate and pass ozone gas into the dyeing vat to ozonate the deionized water, wash the ozone-treated textile twice with 50-60°C hot water, and then wash the textile twice with cold water, each washing for 10 minutes, and place the washed textile in a 55°C oven for drying.

[0024] Furthermore, under the catalytic action, hydrogen peroxide molecules are activated into ions with higher reactivity, thereby oxidizing pigment molecules, slurry residues and other impurities in the textile. In the catalytic process, copper ions in the copper complex catalyst combine with hydrogen peroxide molecules to form a copper-hydrogen peroxide complex, and the complex further reacts to generate copper-oxygen active substances with strong oxidizing properties. The active substances have high reactivity and can quickly react with impurities in the textile to oxidize and decompose the impurities, further removing pigment molecules, slurry residues and other impurities. At the same time, the cottonseed hulls in the textile contain impurities such as lignin, which will affect the whiteness of the textile. The copper-oxygen active substances can oxidize and decompose lignin and convert it into soluble substances, which are then removed through a water washing process. The copper complex catalyst, hydrogen peroxide, triacetin, complex enzymes, etc. work synergistically and act on the textile together to effectively remove pigments, pectin, slurry residues and other impurities in the textile.

[0025] Example 3, please refer to Figure 1 , Figure 3 and Figure 6 , an ozone pretreatment process for textile printing and dyeing, the pretreatment process comprising the following steps: S1. Pretreatment: 6 g / L hydrogen peroxide, 35 μmol / L copper complex catalyst, 26 mmol / L triacetin, composite enzyme, 3 g / L sodium pyrophosphate, and 3 g / L penetrant were mixed to prepare a pretreatment solution, and the textile was immersed in the pretreatment solution at a bath ratio of 1:10. The composite enzyme was a mixture of 3 g / L desizing enzyme DL, 8 g / L scouring enzyme BP, and 3 g / L cutinase S. S2, fabric treatment: deionized water is added to a reaction container, 20wt% of sorbitan monolaurate and 25wt% of polyoxyethylene sorbitan fatty acid ester are poured into the reaction container, and a mechanical stirring device is used to stir to obtain a mixed solution, the reaction container is placed under an emulsifier, and the mixed solution is emulsified. During the emulsification process, 2,4,6-trichloropyrimidine is added dropwise to obtain a finishing solution, and the pretreated textile is immersed in the finishing solution of 3g / L, the bath ratio is 1:20, and the textile is placed in a constant temperature oscillation dyeing machine and heated to 100°C; S3. Ozone treatment: Place the fabric-treated textile in a dyeing vat, add deionized water and a cerium-manganese composite catalyst, use an ozone generator to generate and pass ozone gas into the dyeing vat to ozonate the deionized water, wash the ozone-treated textile twice with 50-60°C hot water, and then wash the textile twice with cold water, each washing for 10 minutes, and place the washed textile in a 55°C oven for drying.

[0026] Furthermore, the finishing liquid introduces chloropyrimidine molecules. The electron-withdrawing effect produced by the N atom and the halogen substituent -Cl on the pyrimidine ring in the chloropyrimidine molecule reduces the electron cloud density on the N atom, thereby enhancing its electrophilicity. When the chloropyrimidine molecule contacts the nucleophilic group -OH on the textile fiber, the nucleophilic group attacks the N atom, causing a nucleophilic substitution reaction, resulting in the formation of a covalent bond between the chloropyrimidine molecule and the fiber molecular chain, thereby forming a cross-linked structure. This cross-linking effect can restrain the movement between the fiber macromolecular chains, thereby improving the anti-wrinkle performance of the fiber; the chloropyrimidine molecules in the finishing liquid have good emulsification and dispersion properties, It can effectively emulsify and disperse the impurities such as grease, wax, and slurry remaining in the pretreated textiles, separate them from the textile surface and the inside of the fiber, further remove impurities in the textiles, and improve the cleanliness and whiteness of the fabrics. The chloropyrimidine molecules in the finishing liquid have special hydrophilic and lipophilic groups. When the textiles are immersed in the finishing liquid, the chloropyrimidine molecules can be adsorbed on the surface of the impurity particles, thereby forming a stable emulsion film. This emulsion film can prevent the impurity particles from reaggregating, thereby effectively dispersing the impurities during the finishing process. As the subsequent washing process proceeds, these dispersed impurity particles will be gradually removed.

[0027] Example 4, please refer to Figure 1 , Figure 4 and Figure 6 , an ozone pretreatment process for textile printing and dyeing, the pretreatment process comprising the following steps: S1. Pretreatment: 4 g / L hydrogen peroxide, 30 μmol / L copper complex catalyst, 24 mmol / L triacetin, complex enzyme, 2 g / L sodium pyrophosphate, and 3 g / L penetrant are mixed to prepare a pretreatment solution, and the textile is immersed in the pretreatment solution at a bath ratio of 1:10. The complex enzyme is a mixture of 2 g / L desizing enzyme DL, 4 g / L scouring enzyme BP, and 2 g / L cutinase S. S2. Fabric treatment: immerse the pretreated textile into 2 g / L finishing liquid with a bath ratio of 1:20, place it in a constant temperature oscillating dyeing machine, and heat it to 100°C; S3. Ozone treatment: dissolve cerium nitrate hexahydrate and manganese nitrate in distilled water respectively, slowly pour the dissolved cerium nitrate hexahydrate solution and manganese nitrate solution into sodium hydroxide solution, stir with a magnetic stirrer for 1 hour to obtain a uniform mixed solution, place the mixed solution in a polytetrafluoroethylene-lined hydrothermal reactor, place the hydrothermal reactor in an oven, keep it warm at 120°C for 16 hours, cool to room temperature, obtain a reaction mixture, centrifuge and wash the reaction mixture twice with distilled water and ethanol respectively, and place the washed reaction mixture in a drying oven. The reaction mixture was dried at 80°C for 12h, and the dried reaction mixture was calcined at 500°C for 5h to obtain a cerium-manganese composite catalyst. The fabric-treated textile was placed in a dyeing vat, deionized water and the cerium-manganese composite catalyst were added, and an ozone generator was used to generate and introduce ozone gas into the dyeing vat to ozonate the deionized water. The ozone-treated textile was washed twice with hot water at 50-60°C, and then washed twice with cold water, each washing for 10 minutes, and the washed textile was placed in an oven at 55°C for drying.

[0028] Furthermore, the cerium-manganese composite catalyst has a large specific surface area and numerous active sites, which enable the catalyst to efficiently adsorb and catalyze the decomposition of ozone. Ozone is decomposed into hydroxyl free radicals with stronger oxidizing properties at the active sites on the catalyst surface. These free radicals have extremely high reactivity and can quickly react with pigments, impurities, etc. on textiles to oxidize and decompose the pigments, impurities, etc. into colorless or light-colored small molecules, thereby achieving the purpose of bleaching and purification. Through the catalytic action of the cerium-manganese composite catalyst, the decomposition rate and oxidation capacity of ozone are significantly improved, thereby accelerating the bleaching process; the synergistic effect between cerium and manganese can promote the generation of oxygen vacancies, and oxygen vacancies can adsorb and activate ozone molecules, promote the decomposition of ozone, and further improve the catalytic performance of the catalyst.

[0029] Example 5, please refer to Figure 1 , Figure 5 and Figure 6 , an ozone pretreatment process for textile printing and dyeing, the pretreatment process comprising the following steps: S1. Pretreatment: 2 g / L hydrogen peroxide, 25 μmol / L copper complex catalyst, 22 mmol / L triacetin, composite enzyme, 1 g / L sodium pyrophosphate, and 3 g / L penetrant are mixed to prepare a pretreatment solution, and the textile is immersed in the pretreatment solution at a bath ratio of 1:10. The composite enzyme is a mixture of 1 g / L desizing enzyme DL, 2 g / L scouring enzyme BP, and 1 g / L cutinase S. S2. Fabric treatment: immerse the pretreated textile in 1 g / L finishing solution with a bath ratio of 1:20, place it in a constant temperature oscillating dyeing machine, and heat it to 100°C; S3. Ozone treatment: mix manganese nitrate solution, iron nitrate solution and cerium nitrate solution, stir with a magnetic stirrer to obtain a metal nitrate solution, add the purified nano-alumina into the metal nitrate solution to form an impregnation solution, place the impregnation solution on a shaker, reciprocate and oscillate for 12 hours, let stand for 6 hours, separate and wash the solid phase with distilled water, put the washed solid phase into an oven, dry at 80°C for 12 hours, calcine the dried solid phase at 500°C for 5 hours to obtain a ternary catalyst, place the fabric-treated textile in a dyeing vat, add deionized water and the ternary catalyst, use an ozone generator to generate and pass ozone gas into the dyeing vat to ozonate the deionized water, wash the ozone-treated textile twice with 50-60°C hot water, wash the textile twice with cold water, each washing for 10 minutes, place the washed textile in an oven at 55°C for drying.

[0030] Furthermore, the three-way catalyst uses alumina with high specific surface area and stable chemical properties as a carrier. The pore structure on the alumina carrier provides abundant active sites for the loading of metal ions. Manganese, iron and cerium metal ions are loaded on the alumina carrier to form a catalyst with high catalytic performance. Manganese, iron and cerium metal ions serve as active sites and can efficiently catalyze the decomposition of ozone. Ozone is decomposed into hydroxyl radicals with stronger oxidizing properties at the active sites on the catalyst surface, thereby quickly oxidizing residual impurities on textiles, etc., to achieve bleaching and purification effects; manganese, iron and cerium metal ions have different electronic structures and chemical properties, and can synergistically promote the decomposition of ozone. In the catalytic process, ozone molecules are first adsorbed on the metal ions on the catalyst surface, and then decomposed into free radicals through steps such as electron transfer and breaking of chemical bonds, thereby oxidizing and decomposing residual impurities on textiles and improving the whiteness of textiles.

[0031] Example 6, please refer to Figure 1 , Figure 6 , Figure 7 and Figure 8 , an ozone pretreatment process for textile printing and dyeing, the pretreatment process comprising the following steps: S1. Pretreatment: 2 g / L hydrogen peroxide, 20 μmol / L copper complex catalyst, 20 mmol / L triacetin, composite enzyme, 5 g / L sodium pyrophosphate, and 3 g / L penetrant are mixed to prepare a pretreatment solution, and the textile is immersed in the pretreatment solution at a bath ratio of 1:10. The composite enzyme is a mixture of 1 g / L desizing enzyme DL, 1 g / L scouring enzyme BP, and 1 g / L cutinase S. S2. Fabric treatment: immerse the pretreated textile in 1 g / L finishing solution with a bath ratio of 1:20, place it in a constant temperature oscillating dyeing machine, and heat it to 100°C; S3. Ozone treatment: Place the fabric-treated textile in a dyeing vat, add deionized water and a cerium-manganese composite catalyst, use an ozone generator to generate and pass ozone gas into the dyeing vat to ozonate the deionized water, wash the ozone-treated textile twice with 50-60°C hot water, and then wash the textile twice with cold water, each washing for 10 minutes, and place the washed textile in a 55°C oven for drying.

[0032] Furthermore, phosphate ions are introduced through sodium pyrophosphate, and the phosphate ions can form multidentate coordination bonds with metal ions, thereby generating stable chelates, which effectively adsorb and fix metal ions in the bleaching solution; the copper complex catalyst can promote the decomposition of hydrogen peroxide and generate active substances with bleaching effects, and sodium pyrophosphate reduces the interference of other metal ions, thereby providing a more favorable reaction environment for the copper complex catalyst, so that the copper complex catalyst can more effectively promote the decomposition of hydrogen peroxide and generate more active substances with bleaching effects; Desizing enzyme, scouring enzyme and cutinase are mixed to form a composite enzyme, which works synergistically to remove various impurities and sizing agents on the textile and improve the desizing effect; the penetrant can significantly reduce the surface tension of the pretreatment liquid, promote the penetration of the treatment liquid, make it easier to penetrate into the fibers of the textile, and help other components in the pretreatment liquid to be more evenly distributed on the textile, thereby improving the desizing effect.

[0033] Comparative Example 1, an ozone pretreatment process for textile printing and dyeing, the pretreatment process comprises the following steps: S1. Pretreatment: 2 g / L hydrogen peroxide, 20 mmol / L triacetin, compound enzyme, 5 g / L sodium pyrophosphate and 3 g / L penetrant were mixed to prepare a pretreatment solution, and the textile was immersed in the pretreatment solution at a bath ratio of 1:10. The compound enzyme was a mixture of 1 g / L desizing enzyme DL, 1 g / L scouring enzyme BP and 1 g / L cutinase S. S2. Fabric treatment: immerse the pretreated textile in 1 g / L finishing solution with a bath ratio of 1:20, place it in a constant temperature oscillating dyeing machine, and heat it to 100°C; S3. Ozone treatment: Place the fabric-treated textile in a dyeing vat, add deionized water and a cerium-manganese composite catalyst, use an ozone generator to generate and pass ozone gas into the dyeing vat to ozonate the deionized water, wash the ozone-treated textile twice with 50-60°C hot water, and then wash the textile twice with cold water, each washing for 10 minutes, and place the washed textile in a 55°C oven for drying.

[0034] Comparative Example 2, an ozone pretreatment process for textile printing and dyeing, the pretreatment process comprises the following steps: S1, prepare a pretreatment solution by mixing 2g / L hydrogen peroxide, 25μmol / L copper complex catalyst, 22mmol / L triacetin, composite enzyme, 1g / L sodium pyrophosphate, and 3g / L penetrant, immerse the textile in the pretreatment solution, the bath ratio is 1:10, and the composite enzyme is a mixture of 1g / L desizing enzyme DL, 2g / L scouring enzyme BP, and 1g / L cutinase S; S2. Fabric treatment: immerse the pretreated textile in 1 g / L finishing solution with a bath ratio of 1:20, place it in a constant temperature oscillating dyeing machine, and heat it to 100°C; S3. Ozone treatment: Place the fabric-treated textile in a dyeing vat, add deionized water and a cerium-manganese composite catalyst, use an ozone generator to generate and pass ozone gas into the dyeing vat to ozonate the deionized water, wash the ozone-treated textile twice with 50-60°C hot water, and then wash the textile twice with cold water, each washing for 10 minutes, and place the washed textile in a 55°C oven for drying.

[0035] Comparative Example 3, an ozone pretreatment process for textile printing and dyeing, the pretreatment process comprises the following steps: S1. Pretreatment: 2 g / L hydrogen peroxide, 20 μmol / L copper complex catalyst, 20 mmol / L triacetin, composite enzyme, 5 g / L sodium pyrophosphate, and 3 g / L penetrant are mixed to prepare a pretreatment solution, and the textile is immersed in the pretreatment solution at a bath ratio of 1:10. The composite enzyme is a mixture of 1 g / L desizing enzyme DL, 1 g / L scouring enzyme BP, and 1 g / L cutinase S. S2. Fabric treatment: immerse the pretreated textile in 1 g / L finishing solution with a bath ratio of 1:20, place it in a constant temperature oscillating dyeing machine, and heat it to 100°C; S3. Ozone treatment: Place the fabric-treated textile in a dyeing vat, add deionized water, use an ozone generator to generate and pass ozone gas into the dyeing vat to ozonate the deionized water, wash the ozone-treated textile twice with 50-60°C hot water, and then wash the textile twice with cold water, each washing for 10 minutes, and place the washed textile in a 55°C oven for drying.

[0036] Performance Testing Test 1 Whiteness performance test: The samples treated in Examples 1-6 and Comparative Examples 1-3 were tested according to the standard ISO 105-J02:1997 method, the samples were folded twice, tested 4 times at different positions, and the whiteness values ​​were averaged; Test 2 Fabric bursting strength performance test: The samples treated in Examples 1-6 and Comparative Examples 1-3 were tested according to the national standard GB / T 7742.1-2005 method to determine the bursting strength of the samples; Test 3 Fabric capillary performance test: The samples treated in Examples 1-6 and Comparative Examples 1-3 were cut into 25 cm × 3 cm fabric samples, and the capillary effects of the fabric samples were measured according to AATCC TS017-2007 standard. Pure water was used as the test liquid, and the height of the liquid rising along the fabric sample within 30 minutes was recorded.

[0037] Test 4 Anti-wrinkle performance test: The samples treated with Examples 1-6 and Comparative Examples 1-3 were tested according to the national standard GB / T 3819-2010 method, and the warp and weft directions were measured 5 times. The average values ​​of the warp and weft directions were calculated, and the sum of the average values ​​was recorded.

[0038]

[0039] Working principle: Triacetin reacts with hydrogen peroxide to generate peracetic acid, which oxidizes and decomposes colored substances on the textile, improves the wettability of the textile fiber surface, and makes it easier for the pretreatment liquid and ozone to penetrate into the textile fiber, so that the pretreatment liquid and ozone can fully contact and react with the pigment molecules and other impurities on the textile fiber surface; The copper ions in the copper complex catalyst react with hydrogen peroxide to generate copper-oxygen active substances, which oxidatively decompose impurities in textiles. Sodium pyrophosphate reduces the interference of other metal ions, provides a favorable reaction environment for the copper complex catalyst, effectively promotes the decomposition of hydrogen peroxide, generates more active substances, and effectively removes impurities in textiles. During the fabric treatment process, the chloropyrimidine molecules in the finishing liquid form a cross-linked structure with the textile fiber molecular chains, restraining the movement between the fiber macromolecular chains, thereby improving the fiber's wrinkle resistance. During the ozone treatment process, the catalytic action of the heterogeneous catalyst promotes the decomposition of ozone and achieves the bleaching effect.

[0040] It will be apparent to those skilled in the art that the invention is not limited to the details of the exemplary embodiments described above and that the invention can be implemented in other specific forms without departing from the spirit or essential features of the invention. Therefore, the embodiments should be considered exemplary and non-limiting in all respects, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations falling within the meaning and scope of the equivalent elements of the claims be included in the invention. Any reference numeral in a claim should not be considered as limiting the claim to which it relates.

Claims

1. An ozone pretreatment process for textile printing and dyeing, characterized in that: The pre-treatment process comprises the following steps: S1. Pretreatment: hydrogen peroxide, copper complex catalyst, triacetin, complex enzyme, sodium pyrophosphate and penetrant are mixed to prepare a pretreatment solution, and the textile is immersed in the pretreatment solution at a bath ratio of 1:10; S2. Fabric treatment: immerse the pretreated textile into the finishing solution at a bath ratio of 1:20, place it in a constant temperature oscillating dyeing machine, and heat it to 100°C; S3. Ozone treatment: Place the fabric-treated textile in a dyeing vat, add deionized water and a heterogeneous catalyst, use an ozone generator to generate and pass ozone gas into the dyeing vat to ozonate the deionized water.

2. The ozone pretreatment process for textile printing and dyeing according to claim 1, characterized in that: The dosage of hydrogen peroxide is 2-10 g / L, the dosage of copper complex catalyst is 20-45 μmol / L, the dosage of triacetin is 20-30 mmol / L, the dosage of sodium pyrophosphate is 1-5 g / L, and the dosage of finishing liquid is 1-5 g / L.

3. The ozone pretreatment process for textile printing and dyeing according to claim 1, characterized in that: The preparation method of the copper complex catalyst comprises the following steps: Adding iminodiacetic acid to deionized water to prepare an iminodiacetic acid aqueous solution, slowly dropping the iminodiacetic acid aqueous solution into a copper sulfate pentahydrate aqueous solution, stirring, and obtaining a mixture; 4-dimethylaminopyridine is dissolved in deionized water to obtain a 4-dimethylaminopyridine aqueous solution, and the 4-dimethylaminopyridine aqueous solution is slowly added dropwise to the mixture and stirred to obtain a copper complex catalyst.

4. The ozone pretreatment process for textile printing and dyeing according to claim 1, characterized in that: The composite enzyme is a mixture of desizing enzyme DL, scouring enzyme BP and cutinase S, wherein the dosage of desizing enzyme DL is 1-5 g / L, the dosage of scouring enzyme BP is 1-10 g / L and the dosage of cutinase S is 1-5 g / L.

5. The ozone pretreatment process for textile printing and dyeing according to claim 1, characterized in that: The preparation method of the finishing liquid comprises the following steps: Deionized water was added to a reaction container, and 20 wt % of sorbitan monolaurate and 25 wt % of polyoxyethylene sorbitan fatty acid ester were poured into the reaction container, and stirred using a mechanical stirring device to obtain a mixed solution; The reaction container is placed under an emulsifier to emulsify the mixed solution. During the emulsification process, 2,4,6-trichloropyrimidine is added dropwise to obtain a finishing solution.

6. The ozone pretreatment process for textile printing and dyeing according to claim 1, characterized in that: The heterogeneous catalyst is a cerium-manganese composite catalyst or a ternary catalyst, and the preparation method of the cerium-manganese composite catalyst comprises the following steps: Dissolve cerium nitrate hexahydrate and manganese nitrate in distilled water respectively, slowly pour the dissolved cerium nitrate hexahydrate solution and manganese nitrate solution into the sodium hydroxide solution, and stir with a magnetic stirrer for 1 hour to obtain a uniform mixed solution; The mixed solution was placed in a polytetrafluoroethylene-lined hydrothermal reactor, the hydrothermal reactor was placed in an oven, kept at 120° C. for 16 h, and cooled to room temperature to obtain a reaction mixture; The reaction mixture was centrifugally washed twice with distilled water and ethanol respectively, the washed reaction mixture was placed in a drying oven, dried at 80° C. for 12 h, and the dried reaction mixture was calcined at 500° C. for 5 h to obtain a cerium-manganese composite catalyst.

7. The ozone pretreatment process for textile printing and dyeing according to claim 6, characterized in that: The preparation method of the three-way catalyst comprises the following steps: Mixing a manganese nitrate solution, an iron nitrate solution and a cerium nitrate solution, stirring with a magnetic stirrer to obtain a metal nitrate solution, and adding the purified nano-alumina to the metal nitrate solution to form an impregnation solution; The impregnation liquid was placed on a shaker, reciprocated and oscillated for 12 hours, and allowed to stand for 6 hours. The solid phase was separated and washed with distilled water. The washed solid phase was placed in an oven and dried at 80°C for 12 hours. The dried solid phase was calcined at 500°C for 5 hours to obtain a ternary catalyst.

8. The ozone pretreatment process for textile printing and dyeing according to claim 1, characterized in that: The penetrant is selected from one of penetrant JFC, penetrant JS and penetrant AP800, and the dosage of the penetrant is 0-3 g / L.

9. The ozone pretreatment process for textile printing and dyeing according to claim 1, characterized in that: The pre-treatment process also includes washing the fabric, and the washing of the fabric includes the following steps: The ozone-treated textile was washed twice with hot water at 50-60°C, and then washed twice with cold water, each washing for 10 minutes. The washed textile was placed in an oven at 55°C for drying.

10. The ozone pretreatment process for textile printing and dyeing according to claim 1, characterized in that: The pre-treatment process also includes fabric dyeing and wastewater treatment, and the fabric dyeing and wastewater treatment include the following steps: Fabric dyeing: Add the reactive dye into the infrared dyeing machine with a bath ratio of 1:30, put in the treated textile, heat it to 60℃, add sodium glauber powder and sodium bicarbonate; Wastewater treatment: Collect the waste liquid generated in the production process into the waste liquid tank, and use an ozone generator to introduce ozone gas into the bottom of the waste liquid tank.

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