WO2019047175A1 - 一种废旧涤棉混纺织物的复合脱色方法 - Google Patents

一种废旧涤棉混纺织物的复合脱色方法 Download PDF

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Publication number
WO2019047175A1
WO2019047175A1 PCT/CN2017/101110 CN2017101110W WO2019047175A1 WO 2019047175 A1 WO2019047175 A1 WO 2019047175A1 CN 2017101110 W CN2017101110 W CN 2017101110W WO 2019047175 A1 WO2019047175 A1 WO 2019047175A1
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Prior art keywords
decolorization
composite
polyester
treatment
cotton blend
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PCT/CN2017/101110
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English (en)
French (fr)
Inventor
葛仪文
姚磊
廖骁
刘洋
卓嘉良
陈学聪
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香港纺织及成衣研发中心
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Priority to PCT/CN2017/101110 priority Critical patent/WO2019047175A1/zh
Publication of WO2019047175A1 publication Critical patent/WO2019047175A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/06—Recovery or working-up of waste materials of polymers without chemical reactions
    • C08J11/08—Recovery or working-up of waste materials of polymers without chemical reactions using selective solvents for polymer components
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock
    • Y02P20/143—Feedstock the feedstock being recycled material, e.g. plastics
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the invention relates to the field of textile resource regeneration, in particular to a composite decolorization method of waste polyester-cotton blend fabric.
  • Polyester-cotton blended fabric not only highlights the style of polyester but also the strength of cotton fabric. It has good elasticity and wear resistance in dry and wet conditions, and also has dimensional stability, small shrinkage, straightness and wrinkle. It is easy to wash and quick-drying. It is the most common type of blended fabric in textiles, but it is also the largest proportion of waste textiles. It has a very high recycling value. If the polyester-cotton blend fabrics of different colors can be decolorized before being recycled, this will be an important way to reduce the manual sorting workload and increase the value of recycled products.
  • the two-bath method is generally used for dyeing, that is, dyeing the polyester fiber in the acid bath of the disperse dye, and then Then enter the reactive dye alkaline bath dyed cotton fiber.
  • the same bath dyeing of polyester and cotton under neutral conditions was also carried out, that is, an appropriate amount of pH adjuster was added to keep the dye bath in neutral condition, and the cotton was selected from reactive dyes which can be dyed under neutral conditions, and polyester was also used. Disperse dyes that can be dyed under neutral conditions are used.
  • the polyester-cotton blend fabric also needs to use a composite decolorization method to effectively remove the color and achieve true discoloration.
  • CN103374144A discloses a process for extracting polyester materials from polyester-containing non-textiles or similar waste materials, which involves the use of organic solvents to decontaminate textiles.
  • the decontaminating and decolorizing agent used is one or more of N-methylpyrrolidone, 1,4-butyrolactone, dimethylacetamide, dimethyl sulfoxide, diethylformamide, m-cresol and the like. They all have certain toxicity and are easy to cause damage to operators and the environment.
  • CN103603194B discloses a stripping treatment method for a polyester-cotton blend fabric, which is mainly carried out in a dyeing machine at a high temperature, first in a N, N-dimethylformamide, and then in a dimethyl sulfoxide. Dispersion treatment, and then reduction and stripping treatment in sodium hydroxide and sulfur dioxide aqueous solution, finally achieving stripping of polyester-cotton blended fabric.
  • the method is cumbersome, and the sample is washed and dried after each process step, so that the total time is more than 2.5 hours, especially the solution used is toxic and cannot be recycled and reused, for operators and the environment. Caused a hazard.
  • the purpose of the invention is to defy the decolorization technology of the polyester-cotton blend fabric, and the composite decoloring agent, that is, the combination of the ester decolorizer and the hydrogen peroxide decolorizer containing the stabilizer, is simple, fast, low cost and not
  • the way of polluting the environment makes the decolorization rate of polyester-cotton blended fabrics of different colors reach over 90%, which solves the problem of decolorization and reuse of polyester-cotton blended fabrics of different colors.
  • the present invention provides a composite decolorization method for a waste polyester-cotton blend fabric, comprising the following steps:
  • the washed waste polyester-cotton blend fabric is put into a hydrogen peroxide solution having a pH of 9-11 and containing a stabilizer, and subjected to a second decolorization treatment at a temperature of 90-100 ° C;
  • the waste polyester-cotton blended fabric subjected to the second decolorization treatment is subjected to a second cleaning treatment and drying using water.
  • the waste polyester-cotton blend fabric has a polyester content of from 5% to 95% by weight.
  • the ester decolorizer is selected from the group consisting of methyl benzoate, ethyl benzoate, propyl benzoate, isopropyl benzoate, butyl benzoate, benzene.
  • Isobutyl formate, dimethyl terephthalate, dimethyl isophthalate or a combination thereof is preferably butyl benzoate, dimethyl terephthalate or dimethyl isophthalate.
  • the weight ratio of the waste polyester-cotton blend fabric to the ester decolorizer is from 1:1.1 to 1:90, preferably from 1:1 to 1:30.
  • the first decolorization treatment is carried out for a period of from 3 to 30 minutes, preferably from 5 to 8 minutes.
  • the fatty alcohol wash is methanol or ethanol.
  • the first cleaning treatment is carried out at a temperature of 60 to 75 °C.
  • the stabilizer is selected from the group consisting of sodium silicate, magnesium silicate, magnesium salt of a fatty acid, polyacrylamide, trisodium phosphate, sodium tripolyphosphate, and alkali metal metaphosphate. Salt or polymetaphosphate, sodium polyphosphate, aminotrimethanephosphonic acid, ethylenediaminetetraacetic acid, acrylic acid, polyacrylamide or a combination of the foregoing, preferably sodium silicate or magnesium silicate.
  • the concentration of the hydrogen peroxide solution is from 2 g/L to 8 g/L.
  • the stabilizer is present in the hydrogen peroxide solution in an amount of from 0.01% to 2%, preferably from 0.5% to 1% by weight.
  • the weight ratio of the waste polyester-cotton blend fabric to the hydrogen peroxide solution is from 1:20 to 1:40, preferably from 1:30 to 1:35.
  • the second decolorization treatment is carried out for a period of 45 to 60 minutes, preferably at 95 to 98 ° C for 50 to 55 minutes.
  • the composite decolorization method of the present invention after the second cleaning treatment, further comprising mixing the ester decolorizing agent with the fatty alcohol washing solution, and cooling, crystallization, distillation or rectification
  • the ester decolorizer having a different boiling point is separated from the fatty alcohol lotion and purified.
  • the ester decolorizer is mixed with the fatty alcohol lotion, cooled to 20-40 ° C to crystallize the ester decolorizer, preferably 25-30 ° C to precipitate the ester. Decolorizing agent crystals and solid-liquid separation.
  • the method of solid-liquid separation is selected from the group consisting of filtration, high-speed centrifugation, precipitation, or a combination of the foregoing.
  • the ester decolorizer is mixed with the fatty alcohol lotion, and the fatty alcohol is distilled off by distillation, and the remainder is an ester decolorizer.
  • the composite decolorization method of the waste polyester-cotton blended fabric of the invention is simple, rapid, low in cost, and does not pollute the environment, and the decolorization rate of the polyester-cotton blend fabrics of different colors is more than 90%, and The ester decolorizer and the fatty alcohol lotion can be reused after purification. It is an ideal method for the composite decolorization of polyester-cotton blended fabrics. After decolorization, the polyester-cotton blend fabric can be re-stained and produced.
  • the composite decolorization method of the waste polyester-cotton blended fabric of the invention utilizes an ester solvent and hydrogen peroxide as a decolorizer to respectively perform composite decolorization of the polyester-cotton blend fabric, and mainly comprises the following steps:
  • the second cleaned cotton and cotton blended fabric after the second bleaching treatment is subjected to a second cleaning treatment and drying using water.
  • the polyester-cotton blended fabric is a fabric which is woven from polyester and cotton fibers into a yarn
  • the waste polyester-cotton blended fabric can be a waste polyester-cotton blend fabric containing any proportion of polyester content, by weight.
  • the waste polyester-cotton blended fabric treated by the present invention preferably has a polyester content of 5% to 95%, that is, it is suitable for most polyester-cotton blended fabrics.
  • the ester decolorizing agent is used as a decolorizing agent used in the first decolorizing treatment, and has good compatibility with polyester, and can be easily decolored.
  • the ester decolorizer may be selected from methyl benzoate, ethyl benzoate, propyl benzoate, isopropyl benzoate, butyl benzoate, isobutyl benzoate, dimethyl terephthalate, isophthalic acid.
  • the dimethyl formate or a combination of the foregoing is preferably butyl benzoate, dimethyl terephthalate or dimethyl isophthalate.
  • the ester decolorizer in the first decolorization treatment is in a molten state or a liquid state.
  • the weight ratio of the waste polyester-cotton blend fabric to the ester decolorizer is 1:1.1-1:90, preferably 1:10-1:30, and the amount of the ester decolorizer is much larger than the waste polyester.
  • the first decoloring treatment is carried out at a temperature of 145 to 160 ° C for a treatment time of 3 to 30 minutes, preferably 5 to 8 minutes.
  • the fatty alcohol washing liquid used in the first cleaning treatment is a lower alcohol having 1-3 carbon atoms (C1-C3), preferably methanol or ethanol, and at the same time, in order to achieve a better cleaning effect, It can be preheated as a hot fatty alcohol lotion, that is, the first cleaning treatment is carried out at a temperature of 60-75 ° C, and can be washed several times to further improve the decolorization effect.
  • the hydrogen peroxide solution containing the stabilizer is used as a decolorizing agent used in the second decoloring treatment, and the pH of the hydrogen peroxide solution is 9-11, which is slightly alkaline, thereby fully exerting the oxidizing agent.
  • the effect is that the concentration of hydrogen peroxide in the solution is from 2 g/L to 8 g/L.
  • the stabilizer used is selected from the group consisting of sodium silicate, magnesium silicate, magnesium salt of fatty acid, polyacrylamide, trisodium phosphate, sodium tripolyphosphate, alkali metal metaphosphate or polymetaphosphate Sodium polyphosphate, aminotrimethylene phosphonic acid, ethylenediaminetetraacetic acid, acrylic acid, polyacrylic acid amine or a combination of the foregoing, preferably sodium silicate or magnesium silicate.
  • the function of the stabilizer is that it can smoothly carry out the oxidation of hydrogen peroxide, and is not slow first and then slow, which is beneficial to fully exert the oxidation effect.
  • the stabilizer is present in the hydrogen peroxide solution in an amount of from 0.01% to 2%, preferably from 0.5% to 1% by weight.
  • the weight ratio of the waste polyester-cotton blended fabric to the hydrogen peroxide solution is from 1:20 to 1:40, preferably from 1:30 to 1:35, and the amount of the hydrogen peroxide solution is also large.
  • the second bleaching treatment is carried out at a temperature of from 90 to 100 ° C for a treatment time of from 45 to 60 minutes, preferably at a temperature of from 95 to 98 ° C for 50 to 55 minutes.
  • the washing liquid used in the second cleaning treatment is clean water, preferably deionized water, and the waste polyester-cotton blended fabric after the second decoloring treatment is washed several times, and then dried to obtain decolorized.
  • the waste polyester-cotton blend fabric can be re-stained and re-produced.
  • the decolorizing agent can be recovered, that is, the used ester decolorizing agent is mixed with the fatty alcohol washing liquid, and the ester decolorizing agent and fat having different boiling points are separated by means of temperature reduction, crystallization, distillation, rectification, and the like. The alcohol wash is separated.
  • the cooling and crystallization is to recover the crystal-decomposed ester decolorizer particles by solid-liquid separation method after cooling, and the fatty alcohol washing liquid is recovered by distillation, and the residue is an impurity such as a dye.
  • Distillation and rectification are carried out by distilling off the fatty alcohol by distillation, and the remainder is an ester decolorizer, and further purification is performed to separate impurities such as dyes.
  • the ester decolorizing agent is first mixed with the fatty alcohol washing solution, and then cooled to 20-40 ° C to crystallize the ester decolorizing agent, preferably 25-30 ° C, and then subjected to solid-liquid separation.
  • the solid-liquid separation method used in the recovery process may be a filtration method, a high-speed centrifugation method, a precipitation method, or a combination of the foregoing.
  • polyester cotton of different colors The decolorization rate of the blended fabric reached over 90%, and the appearance and feel of the fabric were almost the same as those of the original sample.
  • the process is simple, rapid, and the decolorization effect is good, and the reagents used (ester decolorizer and hydrogen peroxide solution containing stabilizer) are non-toxic.
  • the organic solvent can be recycled and reused, does not pollute the environment and helps reduce the cost of recycling, and meets the needs of recycling.
  • the polyester-cotton blended fabric was put into 350 ml of a 5 g/L hydrogen peroxide solution containing 1.75 g of sodium silicate as a stabilizer, heated to 98 ° C and kept for 50 min, filtered and washed with water, then the polyester cotton The blended fabric is close to white.
  • the X-rite Ci7600 benchtop spectrophotometer was used to determine the decolorization rate of the sample after decolorization was 94.2%, and the appearance and feel of the fabric were almost the same as those of the original sample, achieving the desired decolorization effect.
  • the used decolorizing agent butyl benzoate is mixed with the washing liquid methanol, and the methanol is distilled off by distillation, and the residue is butyl benzoate. After further purification, impurities such as dyes are separated for the next embodiment. use.
  • Example 1 After the butyl benzoate particles recovered in Example 1 were melted, they were used as an ester decolorizing agent in the first decoloring treatment, and the distilled methanol was also used as a washing liquid for the first cleaning treatment, and then in other materials, The procedure of Example 1 was repeated under the same conditions of temperature and time, and the decolorization ratio of the obtained polyester-cotton blended fabric was similar to that of Example 1.
  • ester decolorizer and the fatty alcohol lotion in the composite decolorization method of the present invention can be recycled, and the environmental pollution caused by the discharge of chemicals can be reduced while ensuring the decolorization effect.
  • the polyester-cotton blend fabric was put into 300 ml of a 8 g/L hydrogen peroxide solution containing 3 g of magnesium silicate as a stabilizer, heated to 95 ° C and kept for 55 min, filtered and washed with water, then the polyester-cotton blend was washed.
  • the fabric is close to white.
  • the X-rite Ci7600 benchtop spectrophotometer was used to determine the decolorization rate of the sample after decolorization was 91.6%, and the fabric morphology and The hand feel is close to the original sample to achieve the desired decolorization effect.
  • the used decolorizing agent dimethyl terephthalate is mixed with the washing liquid ethanol, and the temperature is lowered to 25 ° C, and the precipitated white dimethyl terephthalate particles are separated by high-speed centrifugation, and the waste liquid is used from the waste liquid.
  • the distilled ethanol was recovered for use in the next example.
  • Example 3 After the dimethyl terephthalate particles recovered in Example 3 are melted, they are used as an ester decolorizing agent in the first decoloring treatment, and the distilled ethanol can be further used as a washing liquid for the first cleaning treatment, and then The procedure of Example 3 was repeated under the same conditions of other materials, temperature and time, and the decolorization ratio of the obtained polyester-cotton blended fabric was similar to that of Example 3.
  • ester decolorizer and the fatty alcohol lotion in the composite decolorization method of the present invention can be recycled, and the environmental pollution caused by the discharge of chemicals can be reduced while ensuring the decolorization effect.
  • the composite decolorization method of the waste polyester-cotton blended fabric of the invention is simple, rapid, low in cost, and does not pollute the environment, and the decolorization rate of the polyester-cotton blended fabrics of different colors is more than 90%, which is ideal.
  • Composite decolorization method of polyester-cotton blend fabric is simple, rapid, low in cost, and does not pollute the environment, and the decolorization rate of the polyester-cotton blended fabrics of different colors is more than 90%, which is ideal.

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

提供一种废旧涤棉混纺织物的复合脱色方法，包括下述步骤：将废旧涤棉混纺织物浸入酯类脱色剂中，并在145-160℃的温度下进行第一脱色处理；利用C1-C3的脂肪醇洗液对经过所述第一脱色处理后的废旧涤棉混纺织物进行第一清洗处理；将清洗后的废旧涤棉混纺织物投入到pH为9-11、含有稳定剂的过氧化氢溶液中，在90-100℃的温度下进行第二脱色处理；以及利用水对经过所述第二脱色处理后的废旧涤棉混纺织物进行第二清洗处理并烘干。废旧涤棉混纺织物的复合脱色方法工艺过程简单、快速，成本低，不污染环境，对不同颜色的涤棉混纺织物的脱色率均达到90％以上，是十分理想的涤棉混纺织物的脱色方法。

Description

一种废旧涤棉混纺织物的复合脱色方法 技术领域
本发明涉及纺织资源再生领域，特别涉及一种废旧涤棉混纺织物的复合脱色方法。
背景技术
涤棉混纺织物既突出了涤纶的风格又有棉织物的长处，在干、湿情况下其弹性和耐磨性都较好，并且还具有尺寸稳定，缩水率小，具有挺拔、不易皱折、易洗、快干的特点，是目前纺织品中使用量最大，最常见的一种混纺织物，但同时也是废旧纺织品中比例最大的一种，具有极高的回收再利用价值。若能够将不同颜色的涤棉混纺织物在回收再利用之前，进行脱色处理，这将是减少手工分拣工作量和提高回收产品价值的重要途径。
由于涤棉混纺织物中的涤纶纤维和棉纤维具有不同的物理和化学性质，由此决定其染色机理也不同，一般使用两浴法进行染色，即先在分散染料酸性浴中染涤纶纤维，然后再进入活性染料碱性浴染棉纤维。之后也出现了将涤纶和棉在中性条件下进行同浴染色，即加入适量的PH值调节剂，使染浴保持在中性条件，棉选用可在中性条件染色的活性染料，涤纶也选用可在中性条件下染色的分散染料。总的来说，根据涤纶纤维与棉纤维上染机理的不同，涤棉混纺织物也需要使用一种复合的脱色方法才能有效地脱除颜色，达到真正的脱色。
CN103374144A公开了从含聚酯的非纺织品或类似废料中提取聚酯材料的方法，其中涉及使用有机溶剂对纺织品进行去污脱色。所用到的去污脱色剂有N-甲基吡咯烷酮、1，4-丁内脂、二甲基乙酰胺、二甲亚砜、二乙基甲酰胺、间甲酚等中的一种或几种，都具有一定的毒性，对操作人员和环境易造成伤害。
CN103603194B公开了一种涤棉混纺织物的剥色处理方法，其中主要是在染色机内在高温下，首先在N，N-二甲基甲酰胺中进行溶胀处理，之后在二甲基亚砜中进行分散处理，再在氢氧化钠和二氧化硫水溶液中进行还原剥色处理，最终实现对涤棉混纺织物的剥色。该方法工艺繁琐，在每个工艺步骤后都要对试样进行洗涤和干燥，使得总耗时长达2.5小时以上，特别是所使用的溶液具有毒性且均不能回收再利用，对操作人员和环境造成了危害。
发明内容
本发明的目的是针对涤棉混纺织物脱色技术的不足，采用复合的脱色剂，即经过酯类脱色剂和含稳定剂的过氧化氢脱色剂的复合作用，以简单、快速、成本低且不污染环境的方式，使不同颜色的涤棉混纺织物的脱色率达到90％以上，解决了对不同颜色的涤棉混纺织物的脱色再利用难题。
为了达到上述目的，本发明提供了一种废旧涤棉混纺织物的复合脱色方法，包括以下步骤：
将废旧涤棉混纺织物浸入酯类脱色剂中，在145-160℃的温度下进行第一脱色处理；
利用C1-C3的脂肪醇洗液对经过所述第一脱色处理后的废旧涤棉混纺织物进行第一清洗处理；
将清洗后的废旧涤棉混纺织物投入到pH为9-11、含有稳定剂的过氧化氢溶液中，在90-100℃的温度下进行第二脱色处理；以及
利用水对经过所述第二脱色处理后的废旧涤棉混纺织物进行第二清洗处理并烘干。
在本发明的复合脱色方法的一个实施方式中，按重量百分比计，所述废旧涤棉混纺织物的含涤量为5％-95％。
在本发明的复合脱色方法的另一个实施方式中，所述酯类脱色剂选自：苯甲酸甲酯、苯甲酸乙酯、苯甲酸丙酯、苯甲酸异丙酯、苯甲酸丁酯、苯甲酸异丁酯、对苯二甲酸二甲酯、间苯二甲酸二甲酯或前述的组合，优选为苯甲酸丁酯、对苯二甲酸二甲酯或间苯二甲酸二甲酯。
在本发明的复合脱色方法的另一个实施方式中，所述废旧涤棉混纺织物与所述酯类脱色剂的重量比为1：1.1-1：90，优选为1：10-1：30。
在本发明的复合脱色方法的另一个实施方式中，所述第一脱色处理的时间为3-30分钟，优选为5-8分钟。
在本发明的复合脱色方法的另一个实施方式中，所述脂肪醇洗液为甲醇或乙醇。
在本发明的复合脱色方法的另一个实施方式中，所述第一清洗处理在60-75℃的温度下进行。
在本发明的复合脱色方法的另一个实施方式中，所述稳定剂选自：硅酸钠、硅酸镁、脂肪酸镁盐、聚丙烯酰胺、磷酸三钠、三聚磷酸钠、碱金属偏磷酸盐或聚偏磷酸盐、多聚磷酸钠、氨基三甲叉膦酸、乙二胺四乙酸、丙烯酸、聚丙烯酸胺或前述的组合，优选为硅酸钠或硅酸镁。
在本发明的复合脱色方法的另一个实施方式中，所述过氧化氢溶液的浓度为2g/L-8g/L。
在本发明的复合脱色方法的另一个实施方式中，按重量百分比计，所述过氧化氢溶液中所述稳定剂的含量为0.01％-2％，优选为0.5％-1％。
在本发明的复合脱色方法的另一个实施方式中，所述废旧涤棉混纺织物与所述过氧化氢溶液的重量比为1：20-1：40，优选为1：30-1：35。
在本发明的复合脱色方法的另一个实施方式中，所述第二脱色处理的时间为45-60分钟，优选在95-98℃下脱色50-55分钟。
在本发明的复合脱色方法的另一个实施方式中，在所述第二清洗处理之后，还包括将所述酯类脱色剂与所述脂肪醇洗液混合，通过降温析晶、蒸馏或精馏将沸点不同的酯类脱色剂与脂肪醇洗液分离开来并提纯。
在本发明的复合脱色方法的一个实施方式中，所述酯类脱色剂与所述脂肪醇洗液混合，冷却至20-40℃使酯类脱色剂结晶，优选为25-30℃以析出酯类脱色剂晶体，并进行固液分离。
在本发明的复合脱色方法的另一个实施方式中，所述固液分离的方法选自：过滤法、高速离心法、沉淀法或前述的组合。
在本发明的复合脱色方法的一个实施方式中，所述酯类脱色剂与所述脂肪醇洗液混合，将脂肪醇通过蒸馏法蒸出，剩余物则为酯类脱色剂。
与现有技术相比，本发明的废旧涤棉混纺织物的复合脱色方法工艺过程简单、快速，成本低，不污染环境，对不同颜色的涤棉混纺织物的脱色率均达到90％以上，并且酯类脱色剂和脂肪醇洗液在提纯后可重复使用，是十分理想的涤棉混纺织物的复合脱色方法，脱色后可对涤棉混纺织物重新染色并生产。
具体实施方式
下面根据具体实施例对本发明的技术方案做进一步说明。本发明的保护范围不限于以下实施例，列举这些实例仅出于示例性目的而不以任何方式限制本发明。
本发明的废旧涤棉混纺织物的复合脱色方法，分别利用酯类溶剂和过氧化氢作为脱色剂对涤棉混纺织物进行复合脱色，主要包括以下步骤：
将废旧涤棉混纺织物浸入酯类脱色剂中，进行第一脱色处理；
利用C1-C3的脂肪醇洗液对经过第一脱色处理后的废旧涤棉混纺织物进行第一清洗 处理；
将清洗后的废旧涤棉混纺织物投入到含有稳定剂的过氧化氢溶液中，进行第二脱色处理；以及
利用水对经过第二脱色处理后的废旧涤棉混纺织物进行第二清洗处理并烘干。
本发明的复合脱色方法中，涤棉混纺织物是由涤纶和棉纤维混纺成纱线进而织成的织物，废旧涤棉混纺织物可以为含任意比例的涤纶含量的废旧涤棉混纺织物，按重量百分比计，本发明所处理的废旧涤棉混纺织物的含涤量优选为5％-95％，即适用于绝大部分的涤棉混纺织物。
本发明的复合脱色方法中，酯类脱色剂作为第一脱色处理中所使用的脱色剂，与涤纶的相容性好，能够很好地实现脱色。
酯类脱色剂可选自苯甲酸甲酯、苯甲酸乙酯、苯甲酸丙酯、苯甲酸异丙酯、苯甲酸丁酯、苯甲酸异丁酯、对苯二甲酸二甲酯、间苯二甲酸二甲酯或前述的组合，优选为苯甲酸丁酯、对苯二甲酸二甲酯或间苯二甲酸二甲酯。
为使废旧涤棉混纺织物与酯类脱色剂充分接触，第一脱色处理中酯类脱色剂处于熔融状态或液态。
本发明的复合脱色方法中，废旧涤棉混纺织物与酯类脱色剂的重量比为1：1.1-1：90，优选为1：10-1：30，酯类脱色剂的用量远大于废旧涤棉混纺织物的重量，以保证脱色效果达到预期。
第一脱色处理在145-160℃的温度下进行，处理时间为3-30分钟，优选为5-8分钟。
本发明的复合脱色方法中，第一清洗处理所用的脂肪醇洗液为含1-3个碳原子(C1-C3)的低级醇，优选甲醇或乙醇，同时为实现更好的清洗效果，加入前可预热为热的脂肪醇洗液，即第一清洗处理在60-75℃的温度下进行，同时可清洗若干次以进一步提高脱色效果。
本发明的复合脱色方法中，含有稳定剂的过氧化氢溶液作为第二脱色处理中所使用的脱色剂，该过氧化氢溶液的pH为9-11，处于微碱性，从而充分发挥氧化剂的效果，溶液中过氧化氢的浓度为2g/L-8g/L。
本发明的复合脱色方法中，所用的稳定剂选自：硅酸钠、硅酸镁、脂肪酸镁盐、聚丙烯酰胺、磷酸三钠、三聚磷酸钠、碱金属偏磷酸盐或聚偏磷酸盐、多聚磷酸钠、氨基三甲叉膦酸、乙二胺四乙酸、丙烯酸、聚丙烯酸胺或前述的组合，优选为硅酸钠或硅酸镁。稳定剂的作用在于其能够使过氧化氢的氧化作用平稳地实施，不至于先快后慢，有利于充分发挥氧化效果。
按重量百分比计，所述过氧化氢溶液中所述稳定剂的含量为0.01％-2％，优选为0.5％-1％。
本发明的复合脱色方法中，废旧涤棉混纺织物与所述过氧化氢溶液的重量比为1：20-1：40，优选为1：30-1：35，过氧化氢溶液的用量也远大于废旧涤棉混纺织物的重量，以保证脱色效果达到预期。
第二脱色处理在90-100℃的温度下进行，处理时间为45-60分钟，优选为在95-98℃的温度下脱色50-55分钟。
本发明的复合脱色方法中，第二清洗处理所用的洗液为清水，优选为去离子水，对经过第二脱色处理后的废旧涤棉混纺织物清洗若干次，之后烘干，即得到脱色后的废旧涤棉混纺织物，可对其重新染色并进行再次生产。
在第二清洗处理之后，可对脱色剂进行回收，即将使用过的酯类脱色剂与脂肪醇洗液混合，通过降温析晶、蒸馏、精馏等方式将沸点不同的酯类脱色剂与脂肪醇洗液分离开来。
降温析晶是冷却后利用固液分离法回收结晶析出的酯类脱色剂颗粒，并利用蒸馏法回收脂肪醇洗液，剩余物便是染料等杂质。蒸馏与精馏是将脂肪醇通过蒸馏法蒸出，剩余物则为酯类脱色剂，再进一步提纯后将分离出染料等杂质。
回收过程中先将酯类脱色剂与脂肪醇洗液混合后冷却至20-40℃使酯类脱色剂结晶，优选为25-30℃，再进行固液分离。
回收过程中所用的固液分离法可为过滤法、高速离心法、沉淀法或前述的组合。
在复合脱色处理后，对所得涤棉混纺织物的形貌、手感、脱色程度进行表征，其中，用X-rite Ci7600台式分光光度仪进行脱色程度分析，所得到结果为：对不同颜色的涤棉混纺织的脱色率达到90％以上，且织物形貌和手感与原始试样几乎无差别。
由此可见，本发明的复合脱色方法中没有副反应发生，工艺过程操作简单、快速、脱色效果好，同时所使用的试剂(酯类脱色剂和含有稳定剂的过氧化氢溶液)无毒无害，其中的有机溶剂可以回收重用，不会对环境造成污染且有助降低回收成本，符合再利用的需求。
除非另作限定，本发明所用术语均为本领域技术人员通常理解的含义。
下面结合实施例对本发明作进一步说明。
实施例
以下实施例所使用的化学试剂如无特别说明则为市售商品且为分析纯，以下实施例所使用的操作或仪器如无特别说明则为本领域常见的操作或仪器。以下实施例中所述的比 例、比值、含量等如无特别说明则为重量比。
实施例1
将涤/棉比例为65/35(重量比)的废旧蓝色涤棉混纺织物10g，浸入到150g苯甲酸丁酯中，升温至150℃并保持7min，然后将混纺织物滤出并放入热的甲醇中洗涤若干次，直到没有颜色被洗出，这时的混纺织物已经呈浅蓝色泛白而脱色剂苯甲酸丁酯则呈深蓝色。
再将该涤棉混纺织物投入到5g/L的过氧化氢溶液350ml中，其中含有1.75g硅酸钠作为稳定剂，升温至98℃并保持50min，过滤后用清水清洗，这时的涤棉混纺织物已接近白色。
使用X-rite Ci7600台式分光光度仪测定脱色后试样的脱色率为94.2％，且织物形貌和手感与原始试样几乎无差别，达到理想的脱色效果。
之后将使用过的脱色剂苯甲酸丁酯与洗液甲醇混合，通过蒸馏法将甲醇蒸出，剩余物则为苯甲酸丁酯，再进一步提纯后将分离出染料等杂质，供下一实施例使用。
实施例2
将实施例1中回收的苯甲酸丁酯颗粒熔融后，作为第一脱色处理中的酯类脱色剂使用，并且蒸馏出的甲醇也继续作为第一清洗处理的洗液使用，然后在其他物料、温度和时间等均同等的条件下，重复实施例1的步骤，最后得到的涤棉混纺织物的脱色率与实施例1接近。
由此可见，本发明的复合脱色方法中的酯类脱色剂和脂肪醇洗液是可以循环使用的，在保障脱色效果的同时可减少排放化学品造成对环境的污染。
实施例3
将涤/棉比例为20/80(重量比)的黑色涤棉混纺织物10g，浸入到300g对苯二甲酸二甲酯中，升温至160℃并保持5min，然后将过滤出的混纺织物放入热的乙醇中洗涤若干次，直到没有颜色被洗出，这时的混纺织物已经呈浅灰色而脱色剂对苯二甲酸二甲酯呈蓝黑色。
再将该涤棉混纺织物投入到8g/L的过氧化氢溶液300ml中，其中含有3g硅酸镁作为稳定剂，升温至95℃并保持55min，过滤后用清水清洗，这时的涤棉混纺织物已接近白色。
使用X-rite Ci7600台式分光光度仪测定脱色后试样的脱色率为91.6％，且织物形貌和 手感接近原始试样，达到理想的脱色效果。
之后将使用过的脱色剂对苯二甲酸二甲酯与洗液乙醇混合，降温至25℃，利用高速离心法将析出的白色对苯二甲酸二甲酯颗粒，以及利用蒸馏法从废液中蒸馏出的乙醇回收，供下一实施例使用。
实施例4
将实施例3中回收的对苯二甲酸二甲酯颗粒熔融后，作为第一脱色处理中的酯类脱色剂使用，并且蒸馏出的乙醇也可继续作为第一清洗处理的洗液使用，然后在其他物料、温度和时间等均同等的条件下，重复实施例3的步骤，最后得到的涤棉混纺织物的脱色率与实施例3接近。
由此可见，本发明的复合脱色方法中的酯类脱色剂和脂肪醇洗液是可以循环使用的，在保障脱色效果的同时可减少排放化学品造成对环境的污染。
综上所述，本发明的废旧涤棉混纺织物的复合脱色方法工艺过程简单、快速，成本低，不污染环境，对不同颜色的涤棉混纺织物的脱色率均达到90％以上，是十分理想的涤棉混纺织物的复合脱色方法。
上述对实施例的描述是为便于该技术领域的普通技术人员能理解和应用本发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改，并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此，本发明不限于这里的实施例，本领域技术人员根据本发明的揭示，不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。

Claims (15)

  1. 一种废旧涤棉混纺织物的复合脱色方法，其特征在于，包括下述步骤：
    将废旧涤棉混纺织物浸入酯类脱色剂中，在145-160℃的温度下进行第一脱色处理；
    利用C1-C3的脂肪醇洗液对经过所述第一脱色处理后的废旧涤棉混纺织物进行第一清洗处理；
    将清洗后的废旧涤棉混纺织物投入到pH为9-11、含有稳定剂的过氧化氢溶液中，在90-100℃的温度下进行第二脱色处理；以及
    利用水对经过所述第二脱色处理后的废旧涤棉混纺织物进行第二清洗处理并烘干。
  2. 根据权利要求1所述的复合脱色方法，其特征在于，按重量百分比计，所述废旧涤棉混纺织物的含涤量为5％-95％。
  3. 根据权利要求1所述的复合脱色方法，其特征在于，所述酯类脱色剂选自：苯甲酸甲酯、苯甲酸乙酯、苯甲酸丙酯、苯甲酸异丙酯、苯甲酸丁酯、苯甲酸异丁酯、对苯二甲酸二甲酯、间苯二甲酸二甲酯或前述的组合。
  4. 根据权利要求1所述的复合脱色方法，其特征在于，所述废旧涤棉混纺织物与所述酯类脱色剂的重量比为1：1.1-1：90。
  5. 根据权利要求1所述的复合脱色方法，其特征在于，所述第一脱色处理的时间为3-30分钟。
  6. 根据权利要求1所述的复合脱色方法，其特征在于，所述脂肪醇洗液为甲醇或乙醇。
  7. 根据权利要求1所述的复合脱色方法，其特征在于，所述第一清洗处理在60-75℃的温度下进行。
  8. 根据权利要求1所述的复合脱色方法，其特征在于，所述稳定剂选自：硅酸钠、硅酸镁、脂肪酸镁盐、聚丙烯酰胺、磷酸三钠、三聚磷酸钠、碱金属偏磷酸盐或聚偏磷酸盐、多聚磷酸钠、氨基三甲叉膦酸、乙二胺四乙酸、丙烯酸、聚丙烯酸胺或前述的组合。
  9. 根据权利要求1所述的复合脱色方法，其特征在于，所述过氧化氢溶液的浓度为2g/L-8g/L。
  10. 根据权利要求9所述的复合脱色方法，其特征在于，按重量百分比计，所述过氧化氢溶液中所述稳定剂的含量为0.01％-2％。
  11. 根据权利要求1所述的复合脱色方法，其特征在于，所述废旧涤棉混纺织物与所述过氧化氢溶液的重量比为1：20-1：40。
  12. 根据权利要求1所述的复合脱色方法，其特征在于，所述第二脱色处理的时间为45-60分钟。
  13. 根据权利要求1所述的复合脱色方法，其特征在于，在所述第二清洗处理之后，还包括将所述酯类脱色剂与所述脂肪醇洗液混合，通过降温析晶、蒸馏或精馏将沸点不同的酯类脱色剂与脂肪醇洗液分离开来并提纯。
  14. 根据权利要求13所述的复合脱色方法，其特征在于，所述酯类脱色剂与所述脂肪醇洗液混合，冷却至20-40℃以析出酯类脱色剂晶体，并进行固液分离，或将脂肪醇通过蒸馏法蒸出，剩余物则为酯类脱色剂。
  15. 根据权利要求14所述的复合脱色方法，其特征在于，所述固液分离的方法可为过滤法、高速离心法、沉淀法或前述的组合。
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WO2022161850A3 (en) * 2021-01-26 2022-09-15 Smart Coloring Gmbh Method for decolorizing a colored synthetic or non-synthetic polar-polymer material
TWI809650B (zh) * 2022-01-07 2023-07-21 遠東新世紀股份有限公司 經著色劑著色的高分子材的脫色方法、脫色處理液及再生高分子的製備方法

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