CN105601507A - Method for catalytically degrading polyester waste textile with sodium hydroxide at low temperature - Google Patents
Method for catalytically degrading polyester waste textile with sodium hydroxide at low temperature Download PDFInfo
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 title claims abstract description 90
- 238000000034 method Methods 0.000 title claims abstract description 47
- 239000002699 waste material Substances 0.000 title claims abstract description 35
- 229920000728 polyester Polymers 0.000 title claims abstract description 29
- 239000004753 textile Substances 0.000 title claims abstract description 28
- 230000000593 degrading effect Effects 0.000 title claims abstract description 7
- 230000015556 catabolic process Effects 0.000 claims abstract description 34
- 238000006731 degradation reaction Methods 0.000 claims abstract description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 30
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000006184 cosolvent Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 230000003197 catalytic effect Effects 0.000 claims description 8
- 238000006136 alcoholysis reaction Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 2
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 claims 3
- 150000002148 esters Chemical class 0.000 claims 1
- 239000012453 solvate Substances 0.000 claims 1
- 238000005303 weighing Methods 0.000 claims 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 4
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 52
- 239000005020 polyethylene terephthalate Substances 0.000 description 52
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 14
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 8
- 239000000835 fiber Substances 0.000 description 7
- -1 Polyethylene terephthalate Polymers 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 4
- 229960001826 dimethylphthalate Drugs 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 238000005903 acid hydrolysis reaction Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- QPKOBORKPHRBPS-UHFFFAOYSA-N bis(2-hydroxyethyl) terephthalate Chemical compound OCCOC(=O)C1=CC=C(C(=O)OCCO)C=C1 QPKOBORKPHRBPS-UHFFFAOYSA-N 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- BTVWZWFKMIUSGS-UHFFFAOYSA-N dimethylethyleneglycol Natural products CC(C)(O)CO BTVWZWFKMIUSGS-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical group [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
本发明公开了一种低温条件下氢氧化钠催化降解聚酯类废旧纺织品方法。所述方法以氢氧化钠为催化剂、以甲醇为溶剂、以四氢呋喃为助溶剂，在低温反应条件下降解PET类废旧纺织品。所述方法中催化剂用量为溶剂质量的0.01-1.5%。与现有的催化降解聚酯类废旧纺织品方法相比，本发明所述方法具有催化剂原料廉价、催化剂无毒无害、催化剂用量少、反应温度低、对设备要求低、有利于节能环保和降解率高等优势。
The invention discloses a method for catalytically degrading polyester waste textiles under low temperature conditions by sodium hydroxide. The method uses sodium hydroxide as a catalyst, methanol as a solvent and tetrahydrofuran as a co-solvent to degrade PET waste textiles under low-temperature reaction conditions. The amount of catalyst used in the method is 0.01-1.5% of the solvent mass. Compared with the existing method for catalytically degrading polyester waste textiles, the method of the present invention has the advantages of cheap catalyst raw materials, non-toxic and harmless catalyst, less catalyst consumption, low reaction temperature, low equipment requirements, and is conducive to energy saving and environmental protection. Advantages of high degradation rate.
Description
技术领域technical field
本发明属于绿色、清洁催化技术领域，涉及一种低温条件下氢氧化钠催化降解聚酯类废旧纺织品方法，具体涉及一种在低温条件下用氢氧化钠催化醇解聚酯类废旧纺织品生产对苯二甲酸二甲酯（DMT）的方法。The invention belongs to the technical field of green and clean catalysis, and relates to a method for catalytically degrading polyester waste textiles under low temperature conditions by sodium hydroxide, in particular to a method for producing polyester waste textiles by catalyzing alcoholysis with sodium hydroxide under low temperature conditions. Method for dimethyl phthalate (DMT).
背景技术Background technique
聚对苯二甲酸乙二醇酯，化学式为： Polyethylene terephthalate, the chemical formula is:
英文名称为：Polyethyleneterephthalate，简称PET，由对苯二甲酸二甲酯与乙二醇酯交换或以对苯二甲酸与乙二醇酯化先合成对苯二甲酸双羟乙酯，然后再进行缩聚反应制得，属结晶型饱和聚酯，为乳白色或浅黄色、高度结晶的聚合物，表面平滑有光泽，是生活中常见的一种树脂。The English name is: Polyethyleneterephthalate, referred to as PET, which synthesizes bishydroxyethyl terephthalate by transesterification of dimethyl terephthalate and ethylene glycol or esterification of terephthalic acid and ethylene glycol, and then polycondenses Prepared by reaction, it is a crystalline saturated polyester. It is a milky white or light yellow, highly crystalline polymer with a smooth and shiny surface. It is a common resin in daily life.
PET分为纤维级聚酯切片和非纤维级聚酯切片。纤维级聚酯用于制造涤纶短纤维和涤纶长丝，是供给涤纶纤维企业加工纤维及相关产品的原料。涤纶作为化纤中产量最大的品种，广泛应用于生产纺织品和服装。非纤维级聚酯还有生产瓶类、薄膜等用途，广泛应用于包装业、电子电器、医疗卫生、建筑、汽车等领域，其中包装是聚酯最大的非纤维应用市场，同时也是PET增长最快的领域。PET is divided into fiber-grade polyester chips and non-fiber-grade polyester chips. Fiber-grade polyester is used to manufacture polyester staple fiber and polyester filament, and is a raw material for polyester fiber enterprises to process fibers and related products. Polyester, as the most productive variety among chemical fibers, is widely used in the production of textiles and clothing. Non-fiber grade polyester is also used for the production of bottles and films, and is widely used in the packaging industry, electronic appliances, medical and health care, construction, automobiles and other fields. Among them, packaging is the largest non-fiber application market for polyester, and it is also the fastest growing market for PET. fast field.
随着社会经济的发展，全球范围内的聚对苯二甲酸乙二酯(PET)消费用量在逐年增加，排入自然界的废聚酯越来越多，尽管废聚酯对环境不会产生直接的污染，但因PET有酯键，只有在强酸、强碱和水蒸汽作用下才会发生分解，耐有机溶剂、耐候性好，具有极强的化学惰性，所以很难被空气或微生物降解，会占据大量的空间，从而对环境造成很大的影响。因此，对PET进行回收和再利用既能够减轻环境污染，又能够实现资源的循环利用，利国利民。With the development of society and economy, the consumption of polyethylene terephthalate (PET) in the world is increasing year by year, and more and more waste polyester is discharged into nature, although waste polyester has no direct impact on the environment. pollution, but because PET has ester bonds, it can only be decomposed under the action of strong acid, strong alkali and water vapor. It is resistant to organic solvents, weather resistance, and has strong chemical inertness, so it is difficult to be degraded by air or microorganisms. It will take up a lot of space and have a great impact on the environment. Therefore, the recycling and reuse of PET can not only reduce environmental pollution, but also realize the recycling of resources, which is beneficial to the country and the people.
水解法是报道较早的PET解聚方法，是指在不同的酸碱介质中将废PET水解为对苯二甲酸（TPA）和乙二醇，因为二者是合成PET的主要原料，所以使得PET水解法日益受到重视，目前已有澳大利亚Smorgon公司、美国Oxid公司等实现了中小规模的商业化生产。其方法可以分为3类：即酸性水解、碱性水解和中性水解。The hydrolysis method is an earlier PET depolymerization method, which refers to the hydrolysis of waste PET into terephthalic acid (TPA) and ethylene glycol in different acid-base media, because the two are the main raw materials for the synthesis of PET, so that The PET hydrolysis method has been paid more and more attention. At present, Smorgon Company in Australia and Oxid Company in the United States have realized small and medium-sized commercial production. The methods can be divided into three categories: acidic hydrolysis, alkaline hydrolysis and neutral hydrolysis.
酸性水解法酸耗量较大，易腐蚀设备，在实际应用中具有一定的局限性。中性水解避免了酸碱废液的环境污染问题，使其日后必将更受欢迎，但其缺点在于降解产物的回收纯度要低于酸性水解和碱性水解，因此对产物的提纯尤显重要。所以，在实际应用中，通常采用碱性水解PET的方法。The acidic hydrolysis method consumes a lot of acid and is easy to corrode equipment, which has certain limitations in practical application. Neutral hydrolysis avoids the environmental pollution of acid-base waste liquid, making it more popular in the future, but its disadvantage is that the recovery purity of degradation products is lower than that of acid hydrolysis and alkaline hydrolysis, so the purification of products is particularly important . Therefore, in practical applications, the method of alkaline hydrolysis of PET is usually used.
碱性水解废旧聚酯通常在浓度为4-20%（质量分数）的NaOH、KOH的水溶液中进行，温度大约在200-250℃，产物为对苯二甲酸盐。但是上述方法仍存在着不利因素：反应温度相对较高，对设备要求高，回收利用成本高，能耗相对较高，碱的用量较高，既不利于节约能源，又不利于提高废旧资源回收利用的经济效益，不属于绿色环保的回收再利用方法。Alkaline hydrolysis of waste polyester is usually carried out in an aqueous solution of NaOH and KOH with a concentration of 4-20% (mass fraction), at a temperature of about 200-250°C, and the product is terephthalate. However, there are still unfavorable factors in the above method: the reaction temperature is relatively high, the requirements for equipment are high, the recycling cost is high, the energy consumption is relatively high, and the amount of alkali is high, which is not conducive to saving energy and improving the recovery of waste resources. The economic benefit of utilization does not belong to the recycling method of green environmental protection.
发明内容Contents of the invention
为了解决现有碱性水解废旧PET聚酯方法存在的缺陷，本发明提供一种低温条件下氢氧化钠催化降解聚酯类废旧纺织品的方法，本发明所述方法采用氢氧化钠做催化剂降解PET类废旧纺织品，催化剂的用量仅占溶剂质量的0.1-1.5%，减少了碱的用量，同时降低降解温度，减少了能耗。In order to solve the defects existing in the existing method of alkaline hydrolysis of waste PET polyester, the present invention provides a method for catalytically degrading polyester waste and old textiles with sodium hydroxide under low temperature conditions. The method of the present invention uses sodium hydroxide as a catalyst to degrade PET For waste textiles, the amount of catalyst only accounts for 0.1-1.5% of the mass of the solvent, which reduces the amount of alkali, reduces the degradation temperature, and reduces energy consumption.
本发明解决其技术问题采用的技术方案为：The technical scheme that the present invention solves its technical problem adopts is:
以氢氧化钠为催化剂、以甲醇为溶剂、以四氢呋喃为助溶剂，在低温反应条件下降解PET类废旧纺织品。Using sodium hydroxide as a catalyst, methanol as a solvent, and tetrahydrofuran as a co-solvent, PET waste textiles were degraded under low temperature reaction conditions.
具体地，所述反应为在甲醇和四氢呋喃存在条件下，以氢氧化钠为催化剂降解聚对苯二甲酸乙二醇酯。Specifically, the reaction is to degrade polyethylene terephthalate with sodium hydroxide as a catalyst in the presence of methanol and tetrahydrofuran.
每20mL甲醇溶剂中添加0.1-3gPET类废旧纺织品原料、1-5mL四氢呋喃助溶剂，催化剂用量为溶剂质量的0.01-1.5%。Add 0.1-3g PET waste textile raw materials and 1-5mL tetrahydrofuran co-solvent to every 20mL methanol solvent, and the catalyst dosage is 0.01-1.5% of the solvent mass.
氢氧化钠催化醇解聚对苯二甲酸乙二醇酯的反应温度为40℃至80℃，氢氧化钠催化醇解聚对苯二甲酸乙二醇酯的反应时间为1h-48h。The reaction temperature of sodium hydroxide catalyzed alcoholysis of polyethylene terephthalate is 40°C to 80°C, and the reaction time of sodium hydroxide catalyzed alcoholylysis of polyethylene terephthalate is 1h-48h.
本发明的反应通式为：General reaction formula of the present invention is:
所用聚对苯二甲酸乙二醇酯的分子量为2.3-2.6×106。The polyethylene terephthalate used has a molecular weight of 2.3-2.6×10 6 .
反应结束后，PET的转化率按下列公式计算:After the reaction finished, the conversion rate of PET was calculated by the following formula:
本发明所述方法包括以下步骤：The method of the present invention comprises the following steps:
1）在反应釜中依次加入PET类废旧纺织品、甲醇、四氢呋喃和氢氧化钠；1) Add PET waste textiles, methanol, tetrahydrofuran and sodium hydroxide in sequence in the reactor;
2）在40℃至80℃条件下保温1h-48h后冷却至室温，分离出未降解的PET；2) Incubate at 40°C to 80°C for 1h-48h and then cool to room temperature to separate undegraded PET;
3）产物经盐酸酸化得DMT；3) The product was acidified with hydrochloric acid to obtain DMT;
4）对未降解的PET经洗涤、干燥、称量得到未降解的PET的质量，并计算PET的降解率。4) Wash, dry and weigh the undegraded PET to obtain the mass of the undegraded PET, and calculate the degradation rate of PET.
本发明的优点和有益效果体现在以下方面：Advantages and beneficial effects of the present invention are embodied in the following aspects:
l催化剂原料廉价易得，且容易储存；l Catalyst raw materials are cheap and easy to obtain, and easy to store;
l此类催化剂无毒无害，是绿色催化剂；l This type of catalyst is non-toxic and harmless, and is a green catalyst;
l催化活性高，催化剂用量少；l High catalytic activity, less catalyst consumption;
l使用温度低，对设备要求低，有利于节能；l The operating temperature is low, and the requirements for equipment are low, which is conducive to energy saving;
l反应降解率高；l High reaction degradation rate;
l利用四氢呋喃促进溶解降解。l Utilize tetrahydrofuran to promote dissolution and degradation.
附图说明Description of drawings
下面结合附图和实施例对本发明作进一步说明。The present invention will be further described below in conjunction with drawings and embodiments.
图1为本发明所述低温条件下氢氧化钠催化降解聚酯类废旧纺织品方法流程图。Fig. 1 is a flow chart of the method for catalytically degrading polyester waste textiles by sodium hydroxide under low temperature conditions according to the present invention.
具体实施方式detailed description
实施例1Example 1
实施方法：在50ml反应釜中依次加入0.5gPET类废旧纺织品、20ml甲醇、2ml四氢呋喃和0.016g氢氧化钠。在50℃下保温4h后冷却至室温，分离出未降解的PET，经洗涤、干燥、称量得到未降解的PET的质量，产物经盐酸酸化得DMT。在此条件下的PET降解率为4%。Implementation method: Add 0.5g of PET waste textiles, 20ml of methanol, 2ml of tetrahydrofuran and 0.016g of sodium hydroxide into a 50ml reactor in sequence. Incubate at 50°C for 4 hours, then cool to room temperature, separate undegraded PET, wash, dry, and weigh to obtain the mass of undegraded PET, and acidify the product with hydrochloric acid to obtain DMT. The degradation rate of PET under this condition was 4%.
实施例2Example 2
实施方法同实施例1，加入0.24g氢氧化钠，在此条件下，PET降解率为77.52%。The implementation method is the same as in Example 1, adding 0.24g of sodium hydroxide, and under these conditions, the degradation rate of PET is 77.52%.
实施例3Example 3
实施方法同实施例1，加入1ml四氢呋喃，在此条件下，PET降解率为63.24%。The implementation method is the same as in Example 1, adding 1ml of tetrahydrofuran, under this condition, the degradation rate of PET is 63.24%.
实施例4Example 4
实施方法同实施例1，加入5ml四氢呋喃，在此条件下，PET降解率为83.36%。The implementation method is the same as in Example 1, adding 5ml of tetrahydrofuran, under this condition, the degradation rate of PET is 83.36%.
实施例5Example 5
实施方法同实施例1，加入0.1gPET类废旧纺织品，在此条件下，PET降解率为100%。The implementation method is the same as in Example 1, adding 0.1g of PET waste textiles. Under this condition, the PET degradation rate is 100%.
实施例6Example 6
实施方法同实施例1，加入3.0gPET类废旧纺织品，在此条件下，PET降解率为40.37%。The implementation method is the same as in Example 1, adding 3.0g of PET waste textiles. Under this condition, the PET degradation rate is 40.37%.
实施例7Example 7
实施方法同实施例1，在40℃下保温1h，在此条件下，PET降解率为18.50%。The implementation method is the same as in Example 1, and it is incubated at 40° C. for 1 hour. Under this condition, the PET degradation rate is 18.50%.
实施例8Example 8
实施方法同实施例1，在40℃下保温48h，在此条件下，PET降解率为100%。The implementation method is the same as in Example 1, and it is incubated at 40° C. for 48 hours. Under this condition, the PET degradation rate is 100%.
实施例9Example 9
实施方法同实施例1，在40℃下保温2h，在此条件下，PET降解率为39.24%。The implementation method is the same as in Example 1, and the temperature is kept at 40° C. for 2 hours. Under this condition, the degradation rate of PET is 39.24%.
实施例10Example 10
实施方法同实施例1，在50℃下保温2h，在此条件下，PET降解率为42.74%。The implementation method is the same as in Example 1, and the temperature is kept at 50° C. for 2 hours. Under this condition, the degradation rate of PET is 42.74%.
实施例11Example 11
实施方法同实施例1，在50℃下保温8h，在此条件下，PET降解率为100%。The implementation method is the same as in Example 1, and it is incubated at 50° C. for 8 hours. Under this condition, the PET degradation rate is 100%.
实施例12Example 12
实施方法同实施例1，在60℃下保温2h，在此条件下，PET降解率为82.82%。The implementation method is the same as in Example 1, and the temperature is kept at 60° C. for 2 hours. Under this condition, the degradation rate of PET is 82.82%.
实施例13Example 13
实施方法同实施例1，在70℃下保温2h，在此条件下，PET降解率为94.28%。The implementation method is the same as in Example 1, and the temperature is kept at 70° C. for 2 hours. Under this condition, the degradation rate of PET is 94.28%.
实施例14Example 14
实施方法同实施例1，在80℃下保温2h，在此条件下，PET降解率为100%。The implementation method is the same as in Example 1, and it is incubated at 80° C. for 2 hours. Under this condition, the PET degradation rate is 100%.
由实施例1和实施例2对比可知，催化剂氢氧化钠的用量对PET降解率有影响。由实施例1和实施例3、4对比可知，助溶剂四氢呋喃的用量对PET降解率有影响。由实施例1和实施例5、6对比可知，PET的加入量对降解率有影响。由实施例1和实施例7-14对比可知，反应时间和反应温度对PET降解率有影响。By comparing Example 1 and Example 2, it can be known that the amount of catalyst sodium hydroxide has an impact on the degradation rate of PET. From the comparison of Example 1 and Examples 3 and 4, it can be seen that the amount of cosolvent tetrahydrofuran has an impact on the degradation rate of PET. From the comparison of Example 1 and Examples 5 and 6, it can be known that the amount of PET added has an impact on the degradation rate. From the comparison of Example 1 and Examples 7-14, it can be seen that the reaction time and reaction temperature have an impact on the PET degradation rate.
下面通过常用的以醋酸盐为催化剂的降解方法作为对比例，进一步说明本发明所述方法的优越性。Below, the method of the present invention is further illustrated as a comparative example by using the degradation method commonly used as a catalyst with acetate.
对比例comparative example
将乙二醇200份与0.2份醋酸锌混合，开启搅拌器，转速设置为150r/min，再加热至醋酸锌完全溶解，然后加入100份洗净的废弃聚酯纤维，并缓缓通入氮气，避免氧化反应。缓慢升温直到196℃，乙二醇开始发生回流，反应5小时后停止加热。将反应液冷却到140℃，停止搅拌和通入氮气。然后进行洗涤、过滤、提纯等步骤，重复进行3次，得到BHET单体96份。Mix 200 parts of ethylene glycol with 0.2 parts of zinc acetate, turn on the agitator, set the speed at 150r/min, heat until the zinc acetate is completely dissolved, then add 100 parts of washed waste polyester fibers, and slowly blow in nitrogen , to avoid oxidation reactions. The temperature was raised slowly until 196°C, ethylene glycol began to reflux, and the heating was stopped after 5 hours of reaction. The reaction solution was cooled to 140°C, the stirring was stopped and nitrogen gas was blown in. Then, the steps of washing, filtering, and purification were repeated three times to obtain 96 parts of BHET monomer.
对比例分析comparative analysis
本发明实施例1中所降解的物质是PET类废旧纺织品，是以废旧纺织品的回收利用为目的。与对比例相比，所用催化剂是无毒无害绿色环保且更为廉价易得的氢氧化钠，所用温度为40℃-80℃，属于低温范围，且反应时间更短，降解率更高，操作简单，对设备要求低，同时降低能耗有利于节能和降低成本。The material degraded in Example 1 of the present invention is PET waste textiles, and the purpose is to recycle waste textiles. Compared with the comparative example, the catalyst used is non-toxic, harmless, environmentally friendly, and cheaper and easier to obtain sodium hydroxide. The temperature used is 40°C-80°C, which belongs to the low temperature range, and the reaction time is shorter and the degradation rate is higher. The operation is simple, the requirements for equipment are low, and the reduction of energy consumption is conducive to energy saving and cost reduction.
最后应说明的是：显然，上述实施例仅仅是为清楚地说明本发明所作的举例，而并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明的保护范围之中。Finally, it should be noted that obviously, the above-mentioned embodiments are only examples for clearly illustrating the present invention, rather than limiting the implementation. For those of ordinary skill in the art, other changes or changes in different forms can be made on the basis of the above description. It is not necessary and impossible to exhaustively list all the implementation manners here. However, the obvious changes or changes derived therefrom still fall within the scope of protection of the present invention.
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| US10640442B2 (en) | 2015-07-09 | 2020-05-05 | Loop Industries, Inc. | Polyethylene terephthalate depolymerization |
| US10793508B2 (en) | 2017-09-15 | 2020-10-06 | 9449710 Canada Inc. | Terephthalic acid esters formation |
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| US12071519B2 (en) | 2017-09-15 | 2024-08-27 | 9449710 Canada Inc. | Terephthalic acid esters formation |
| US10808096B2 (en) | 2018-06-25 | 2020-10-20 | 9449710 Canada Inc. | Terephthalic acid esters formation |
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