JP2001151934A - Recovering method of valuable components from polyester waste - Google Patents
Recovering method of valuable components from polyester wasteInfo
- Publication number
- JP2001151934A JP2001151934A JP2000112093A JP2000112093A JP2001151934A JP 2001151934 A JP2001151934 A JP 2001151934A JP 2000112093 A JP2000112093 A JP 2000112093A JP 2000112093 A JP2000112093 A JP 2000112093A JP 2001151934 A JP2001151934 A JP 2001151934A
- Authority
- JP
- Japan
- Prior art keywords
- depolymerization
- terephthalate
- polyester
- reaction
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000002699 waste material Substances 0.000 title claims abstract description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 60
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 51
- WOZVHXUHUFLZGK-UHFFFAOYSA-N terephthalic acid dimethyl ester Natural products COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 claims abstract description 46
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000005886 esterification reaction Methods 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000012691 depolymerization reaction Methods 0.000 claims abstract description 18
- 238000006467 substitution reaction Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000032050 esterification Effects 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 7
- -1 polybutylene terephthalate Polymers 0.000 claims description 51
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 21
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 20
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 20
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 20
- 238000011084 recovery Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 6
- BTVWZWFKMIUSGS-UHFFFAOYSA-N dimethylethyleneglycol Natural products CC(C)(O)CO BTVWZWFKMIUSGS-UHFFFAOYSA-N 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910052784 alkaline earth metal Chemical class 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- QPKOBORKPHRBPS-UHFFFAOYSA-N bis(2-hydroxyethyl) terephthalate Chemical compound OCCOC(=O)C1=CC=C(C(=O)OCCO)C=C1 QPKOBORKPHRBPS-UHFFFAOYSA-N 0.000 claims description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 150000002484 inorganic compounds Chemical class 0.000 claims description 2
- 229910010272 inorganic material Inorganic materials 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 150000002739 metals Chemical class 0.000 claims 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical group OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 abstract description 8
- 229920000642 polymer Polymers 0.000 abstract description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 abstract 2
- 239000000376 reactant Substances 0.000 abstract 1
- 238000002156 mixing Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000004817 gas chromatography Methods 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- WJJGAKCAAJOICV-UHFFFAOYSA-N N-dimethyltyrosine Natural products CN(C)C(C(O)=O)CC1=CC=C(O)C=C1 WJJGAKCAAJOICV-UHFFFAOYSA-N 0.000 description 2
- ZVOOGERIHVAODX-UHFFFAOYSA-N O-demycinosyltylosin Natural products O=CCC1CC(C)C(=O)C=CC(C)=CC(CO)C(CC)OC(=O)CC(O)C(C)C1OC1C(O)C(N(C)C)C(OC2OC(C)C(O)C(C)(O)C2)C(C)O1 ZVOOGERIHVAODX-UHFFFAOYSA-N 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 102100032566 Carbonic anhydrase-related protein 10 Human genes 0.000 description 1
- 101000867836 Homo sapiens Carbonic anhydrase-related protein 10 Proteins 0.000 description 1
- DMULVCHRPCFFGV-UHFFFAOYSA-N N,N-dimethyltryptamine Chemical compound C1=CC=C2C(CCN(C)C)=CNC2=C1 DMULVCHRPCFFGV-UHFFFAOYSA-N 0.000 description 1
- 239000008118 PEG 6000 Substances 0.000 description 1
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 1
- 229920002584 Polyethylene Glycol 6000 Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 235000014171 carbonated beverage Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011979 disease modifying therapy Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ポリブチレンテレ
フタレートを少なくとも含むポリエステル混合物からな
るポリエステル廃棄物からテレフタル酸ジメチルとエチ
レングリコールとを回収する方法に関し、更に詳しく
は、該混合物をエチレングリコールで解重合反応させな
がら１，４−ブチレングリコール骨格が変換し生じるテ
トラヒドロフランと水を除去した後、テレフタル酸ジメ
チルとエチレングリコールとを回収する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for recovering dimethyl terephthalate and ethylene glycol from a polyester waste comprising a polyester mixture containing at least polybutylene terephthalate, and more particularly, to depolymerizing the mixture with ethylene glycol. The present invention relates to a method for recovering dimethyl terephthalate and ethylene glycol after removing tetrahydrofuran and water generated by conversion of 1,4-butylene glycol skeleton during the reaction.
【０００２】[0002]
【従来の技術】ポリエチレンテレフタレートは、その化
学的安定性が優れていることから、繊維、フイルム、樹
脂などの生活関連資材、飲料水、炭酸飲料用ボトル等の
食品分野などでの使用が急速に増大している。2. Description of the Related Art Polyethylene terephthalate is rapidly used in daily life-related materials such as fibers, films and resins, and in the food field such as drinking water and carbonated beverage bottles because of its excellent chemical stability. Is growing.
【０００３】しかしながら、上記のような使用量の増大
に伴って大量に発生する、使用済みポリエチレンテレフ
タレート、あるいはポリエチレンテレフタレート製造段
階で発生する品質不適格品（以下、廃ポリエチレンテレ
フタレートと称することもある。）の処理は、大きな社
会問題となっている。However, used polyethylene terephthalate, which is generated in large quantities with the increase in the amount of use as described above, or an unqualified product generated in the stage of producing polyethylene terephthalate (hereinafter sometimes referred to as waste polyethylene terephthalate). The treatment of ()) is a major social problem.
【０００４】上記の問題に対して、廃ポリエチレンテレ
フタレートをモノマーに変換・回収し、このモノマーを
原料にして再度重合反応によってポリエチレンテレフタ
レートを製造し再利用する、いわゆるケミカルリサイク
ルが検討されている。この方法は基本的にロスの無い、
化合物の循環再使用が可能であり、資源の再利用が可能
となる。In order to solve the above-mentioned problem, so-called chemical recycling in which waste polyethylene terephthalate is converted and recovered into a monomer, and this monomer is used as a raw material to produce and reuse polyethylene terephthalate by a polymerization reaction has been studied. This method is basically lossless,
The compound can be recycled and the resources can be reused.
【０００５】これら回収した廃ポリエチレンテレフタレ
ートはエチレングリコールで解重合反応し、次いでメタ
ノールを用いて置換エステル化反応を行い、更に分離精
製することでテレフタル酸ジメチル（以下、ＤＭＴと略
称することがある。）およびエチレングリコール（以
下、ＥＧと略称することがある。）として回収され、資
源の有効利用、トータルコストの低下につながる。The recovered waste polyethylene terephthalate is subjected to a depolymerization reaction with ethylene glycol, followed by a substitution esterification reaction using methanol, and further separation and purification to obtain dimethyl terephthalate (hereinafter abbreviated as DMT). ) And ethylene glycol (hereinafter sometimes abbreviated as EG), leading to effective use of resources and a reduction in total cost.
【０００６】特公昭４３−２０８８号公報には、ポリエ
チレンテレフタレートをエチレングリコールを過剰に加
えて加熱し、解重合反応によりビス（β−ヒドロキシエ
チル）テレフタレート及び末端にβ−ヒドロキシエチル
エステル基を含む低重合体の混合物を得、該混合物に対
し過剰のメタノールを加え触媒の存在下、置換エステル
化反応することによりテレフタル酸ジメチルを回収する
方法が記載されている。JP-B-43-2088 discloses that polyethylene terephthalate is added with an excess of ethylene glycol, heated, and depolymerized to form a bis (β-hydroxyethyl) terephthalate and a low-molecular-weight compound containing a terminal β-hydroxyethyl ester group. A method is described in which a mixture of polymers is obtained, an excess of methanol is added to the mixture, and a substitution esterification reaction is performed in the presence of a catalyst to recover dimethyl terephthalate.
【０００７】しかしながら、廃ポリエチレンテレフタレ
ートはポリエチレンテレフタレート以外の異物を含有す
る場合が多く、特に異物としてポリブチレンテレフタレ
ートを含有する場合には、１，４−ブチレングリコール
（以下、ＢＧと略称することがある。）や該化合物が環
化反応する結果副生するテトラヒドロフラン（以下、Ｔ
ＨＦと略称することがある。）が生成し、回収するテレ
フタル酸ジメチル、エチレングリコール更には置換エス
テル化反応に過剰に用いたメタノール内に分散してしま
い品質的に大きな問題が生じる。However, waste polyethylene terephthalate often contains foreign substances other than polyethylene terephthalate, and particularly when polybutylene terephthalate is contained as a foreign substance, 1,4-butylene glycol (hereinafter sometimes abbreviated as BG). .) Or tetrahydrofuran (hereinafter referred to as T) which is a by-product of the cyclization reaction of the compound.
It may be abbreviated as HF. ) Is generated and dispersed in the recovered dimethyl terephthalate, ethylene glycol and further in methanol used excessively in the substitution esterification reaction, causing a serious problem in quality.
【０００８】[0008]
【発明が解決しようとする課題】本発明の目的は、ポリ
ブチレンテレフタレートを少なくとも含むポリエステル
混合物からなるポリエステル廃棄物から、従来技術にな
かった繊維等のポリマー原料として使用できる品質のＤ
ＭＴとＥＧとを回収する方法を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a polyester waste containing a polyester mixture containing at least polybutylene terephthalate from a polyester waste having a quality which can be used as a raw material for a polymer such as fiber which has not been available in the prior art.
An object of the present invention is to provide a method for recovering MT and EG.
【０００９】[0009]
【課題を解決するための手段】本発明者らは、このよう
な困難な課題を解決するために、ポリブチレンテレフタ
レートを少なくとも含むポリエステル混合物からなるポ
リエステル廃棄物から、テレフタル酸ジメチルとエチレ
ングリコールとを回収する方法について鋭意研究を重ね
てきた。その結果、これらの混合物を、特定の温度条件
下で、エチレングリコールで解重合反応させた時、１，
４−ブチレングリコール骨格を脱水反応によりテトラヒ
ドロフランへ変換する。該テトラヒドロフランは反応系
内から容易に除去でき、更には除去したテトラヒドロフ
ランはメタノールと混合することがないため容易に分離
できテトラヒドロフランのみを系外へパージできること
を見出し、本発明を完成するに至った。Means for Solving the Problems In order to solve such a difficult problem, the present inventors have prepared dimethyl terephthalate and ethylene glycol from a polyester waste comprising a polyester mixture containing at least polybutylene terephthalate. We have been conducting intensive research on the method of collection. As a result, when these mixtures were depolymerized with ethylene glycol under specific temperature conditions,
The 4-butylene glycol skeleton is converted to tetrahydrofuran by a dehydration reaction. The inventors have found that the tetrahydrofuran can be easily removed from the reaction system, and furthermore, the removed tetrahydrofuran does not mix with methanol, so that it can be easily separated and only tetrahydrofuran can be purged out of the system, thereby completing the present invention.
【００１０】即ち、本発明の目的は、ポリブチレンテレ
フタレートを少なくとも含むポリエステル混合物からな
るポリエステル廃棄物を解重合触媒存在下で解重合し、
次いで置換エステル化触媒存在下でメタノールを用いて
置換エステル化反応を行ったのち、さらに分離精製する
ことでテレフタル酸ジメチルとエチレングリコールとを
回収する方法において、該混合物を、エチレングリコー
ルを用いて１８０℃以上３００℃以下の温度範囲で、解
重合反応させながら１，４−ブチレングリコール骨格が
変換し生じるテトラヒドロフランと水を除去し、次いで
置換エステル化反応させることを特徴とする、ポリエス
テル廃棄物からの有価成分回収方法によって達成するこ
とができる。That is, an object of the present invention is to depolymerize a polyester waste comprising a polyester mixture containing at least polybutylene terephthalate in the presence of a depolymerization catalyst,
Next, in a method of performing a substituted esterification reaction using methanol in the presence of a substituted esterification catalyst, and further separating and purifying dimethyl terephthalate and ethylene glycol, the mixture is mixed with ethylene glycol by 180%. In a temperature range of not less than 300 ° C and not more than 300 ° C, tetrahydrofuran and water generated by conversion of 1,4-butylene glycol skeleton are removed during depolymerization reaction, followed by substitution esterification reaction, from polyester waste, This can be achieved by a valuable component recovery method.
【００１１】[0011]
【発明の実施の形態】本発明の回収方法においては、あ
らかじめポリブチレンテレフタレートを少なくとも含む
ポリエステル混合物からなるポリエステル廃棄物をエチ
レングリコールで解重合する際、ポリブチレンテレフタ
レートから生じるテトラヒドロフランと水を系内から除
去・分離する必要がある。BEST MODE FOR CARRYING OUT THE INVENTION In the recovery method of the present invention, when a polyester waste consisting of a polyester mixture containing at least polybutylene terephthalate is depolymerized with ethylene glycol, tetrahydrofuran and water generated from polybutylene terephthalate and water are removed from the system. It needs to be removed and separated.
【００１２】該除去・分離方法としては、先ず、ポリブ
チレンテレフタレートを少なくとも含むポリエステル混
合物からなるポリエステル廃棄物を解重合触媒存在下、
１８０〜３００℃の温度、０〜１．４７ＭＰａＧにて解
重合させる必要がある。The removal / separation method is as follows: first, a polyester waste comprising a polyester mixture containing at least polybutylene terephthalate is removed in the presence of a depolymerization catalyst.
It is necessary to depolymerize at a temperature of 180 to 300 ° C. and 0 to 1.47 MPaG.
【００１３】該温度は低すぎると、解重合反応と１，４
−ブチレングリコール骨格の環化反応が充分行われず、
混合物からの１，４−ブチレングリコール骨格除去効果
が少ない。一方、該温度が高すぎると、使用するエネル
ギーが多くなり、コスト的に好ましくない。該温度は、
１８５〜２８０℃であることが好ましい。If the temperature is too low, the depolymerization reaction and 1,4
-The cyclization reaction of the butylene glycol skeleton is not sufficiently performed,
The effect of removing the 1,4-butylene glycol skeleton from the mixture is small. On the other hand, if the temperature is too high, more energy is used, which is not preferable in terms of cost. The temperature is
The temperature is preferably from 185 to 280 ° C.
【００１４】圧力が低すぎると、解重合で用いるエチレ
ングリコールが蒸発し解重合が十分行われず、一方、該
圧力が高すぎると、テトラヒドロフランの除去率が低く
なる。該圧力は、各解重合温度におけるエチレングリコ
ールの蒸気圧であることが好ましい。If the pressure is too low, the ethylene glycol used in the depolymerization will evaporate and the depolymerization will not be carried out sufficiently. On the other hand, if the pressure is too high, the removal rate of tetrahydrofuran will be low. The pressure is preferably the vapor pressure of ethylene glycol at each depolymerization temperature.
【００１５】ここで、解重合触媒及び置換エステル化触
媒として既知の解重合触媒及び置換エステル化触媒のい
ずれも用いることができるが、アルカリ金属及びアルカ
リ土類金属の、炭酸塩、炭酸水素塩、及びカルボン酸塩
からなる群から選ばれた少なくとも１種以上の化合物を
用いることが触媒能の高さの面から好ましい。更には、
いずれも炭酸ナトリウムを用いることが特に好ましい。Here, any of the known depolymerization catalysts and substituted esterification catalysts can be used as the depolymerization catalyst and the substituted esterification catalyst, but carbonates, bicarbonates, alkali metal and alkaline earth metals can be used. It is preferable to use at least one compound selected from the group consisting of carboxylate and carboxylate from the viewpoint of high catalytic ability. Furthermore,
In any case, it is particularly preferable to use sodium carbonate.
【００１６】上記の操作によってポリエチレンテレフタ
レートとポリブチレンテレフタレートが解重合し、更に
ポリブチレンテレフタレートの１，４−ブチレングリコ
ール骨格からテトラヒドロフランと水が発生し、該化合
物は気相状態であるので、容易に系外へ除去することが
可能となり、また、テトラヒドロフランは共沸化合物を
形成するメタノールと混ざることもない。By the above operation, polyethylene terephthalate and polybutylene terephthalate are depolymerized, and tetrahydrofuran and water are generated from the 1,4-butylene glycol skeleton of polybutylene terephthalate. It can be removed outside the system, and tetrahydrofuran does not mix with methanol which forms an azeotropic compound.
【００１７】また、ポリエステル廃棄物に含まれている
その他の混合物であるポリエチレン、ポリプロピレン及
び無機化合物は、濾過や浮遊分離などの単位操作にて除
去する。Further, polyethylene, polypropylene and inorganic compounds, which are other mixtures contained in the polyester waste, are removed by a unit operation such as filtration or floating separation.
【００１８】次いで、系内に残留した混合物はメタノー
ルとともに反応器内へ導入し、ポリエチレンテレフタレ
ートモノマーと置換エステル化させて、生成したＤＭＴ
及びＥＧと未反応のメタノールとを各々分別回収するこ
とによって、各々の成分として再利用することができ
る。Next, the mixture remaining in the system is introduced into a reactor together with methanol, and is substituted and esterified with a polyethylene terephthalate monomer.
And EG and unreacted methanol are separated and recovered, respectively, so that they can be reused as respective components.
【００１９】尚、分別回収方法としては公知の方法をい
ずれも採用することができ、例えば、ＤＭＴの場合に
は、蒸留、遠心分離及び濾過操作を行えばよく、未反応
のメタノール、ＥＧの場合には蒸留操作を行えばよい。Any known method can be used for the separation and recovery. For example, in the case of DMT, distillation, centrifugation and filtration may be performed, and in the case of unreacted methanol and EG, , A distillation operation may be performed.
【００２０】本発明の回収方法において、混合物を解重
合反応させる際の方式は、回分式と連続式でも、どちら
でも問題なく採用することができ、混合物の解重合反応
系内での滞留時間または平均滞留時間は、ポリブチレン
テレフタレートの混入割合にも影響を受けるが、該滞留
時間が長いほどテトラヒドロフランの除去効果は上がる
が、一方、エネルギー損失の増大及び設備効率の低下と
もなるので、０．１〜１５時間程度であればよく、１〜
１０時間であることが好ましい。In the recovery method of the present invention, either a batch system or a continuous system may be employed without any problem when the mixture is subjected to the depolymerization reaction, and the residence time of the mixture in the depolymerization reaction system or Although the average residence time is also affected by the mixing ratio of polybutylene terephthalate, the longer the residence time, the higher the effect of removing tetrahydrofuran, but on the other hand, it also increases energy loss and decreases equipment efficiency. It only needs to be about 15 hours,
Preferably, it is 10 hours.
【００２１】また、テトラヒドロフランを除去した後の
解重合物をメタノールを用いて置換エステル化反応する
際の反応条件としては、公知の反応条件をいずれも採用
することができ、例えばメタノールの使用量は、ポリエ
チレンテレフタレートとポリブチレンテレフタレートを
基準として１〜５重量倍程度であればよく、特に１．５
〜３倍程度であることが好ましい。As the reaction conditions for subjecting the depolymerized product after the removal of tetrahydrofuran to a substitution esterification reaction using methanol, any known reaction conditions can be adopted. For example, the amount of methanol used is It may be about 1 to 5 times by weight based on polyethylene terephthalate and polybutylene terephthalate, especially 1.5
It is preferably about 3 times.
【００２２】また、置換エステル化反応を行う際の反応
温度としては、５０〜１２０℃の範囲、反応圧力として
は、０〜０．５９ＭＰａＧの範囲とすることが好まし
く、この範囲にある際には、置換エステル化反応が十分
に行われる。なお、置換エステル化反応時間は３０分〜
４時間とすることが好ましい。置換エステル化反応生成
物は、従来公知の方法、例えば、再結晶、固液分離及び
蒸留により、メタノール、ＤＭＴ及びＥＧに分離回収す
ることができる。The reaction temperature for performing the substitution esterification reaction is preferably in the range of 50 to 120 ° C., and the reaction pressure is preferably in the range of 0 to 0.59 MPaG. The substitution esterification reaction is sufficiently performed. In addition, the substitution esterification reaction time is 30 minutes or more.
Preferably, it is 4 hours. The substituted esterification reaction product can be separated and recovered into methanol, DMT and EG by a conventionally known method, for example, recrystallization, solid-liquid separation and distillation.
【００２３】[0023]
【実施例】以下実施例により本発明の内容を更に具体的
に説明するが本発明はこれにより何等限定を受けるもの
ではない。EXAMPLES The contents of the present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
【００２４】（１）ＤＭＴ回収率（％）：解重合を行う
前のポリエチレンテレフタレートとポリブチレンテレフ
タレートを構成するＤＭＴ成分量を基準として、実際に
解重合反応及び置換エステル化反応を行った後の反応系
内に含まれるＤＭＴをガスクロマトグラフィー（装置：
ヒューレット パッカード社製ＨＰ５８９０、キャピラ
リーカラム：ジーエルサイエンス社製ＴＣ−１７０１）
によって定量し、その回収率を求めた。(1) DMT recovery rate (%): based on the amount of the DMT component constituting polyethylene terephthalate and polybutylene terephthalate before depolymerization, and after the actual depolymerization reaction and substitution esterification reaction are performed. DMT contained in the reaction system was subjected to gas chromatography (apparatus:
Hewlett-Packard HP5890, Capillary column: GL Sciences TC-1701)
And the recovery was determined.
【００２５】（２）ＤＭＴ純度 置換エステル化反応を実施した後の反応生成物を、固液
分離し得られたケーク分を更に蒸留して精製したＤＭＴ
を得た。このＤＭＴをガスクロマトグラフィー（装置：
ヒューレット パッカード社製ＨＰ５８９０、キャピラ
リーカラム：ジーエルサイエンス社製ＴＣ−１７０１）
によって分析し、ＤＭＴの純度を求めた。(2) DMT Purity DMT purified by subjecting the reaction product after the substitution esterification reaction to solid-liquid separation and further distilling the cake obtained.
I got This DMT was subjected to gas chromatography (apparatus:
Hewlett-Packard HP5890, Capillary column: GL Sciences TC-1701)
And the purity of DMT was determined.
【００２６】（３）ＥＧ回収率（％）：解重合を行う前
のポリエチレンテレフタレートを構成するＥＧ成分量を
基準として、実際に解重合反応及び置換エステル化反応
を行った後の反応系内に含まれるＥＧをガスクロマトグ
ラフィー（装置：島津製作所社製ＧＣ−７Ａ、充填式カ
ラム 充填材：ジーエルサイエンス社製ＰＥＧ−６００
０）によって定量し、解重合反応で用いたＥＧ量を差し
引いた上で、ＥＧの回収率を求めた。(3) EG recovery (%): based on the amount of the EG component constituting the polyethylene terephthalate before depolymerization, the reaction system after the depolymerization reaction and the substitution esterification reaction are actually performed The contained EG was subjected to gas chromatography (apparatus: GC-7A, manufactured by Shimadzu Corporation, packed column). Filler: PEG-600, manufactured by GL Sciences Inc.
0), the amount of EG used in the depolymerization reaction was subtracted, and the EG recovery was determined.
【００２７】（４）ＥＧ純度 置換エステル化反応を実施した後の反応生成物を、固液
分離し得られた濾液分を更に蒸留し精製したＥＧを得
た。このＥＧをガスクロマトグラフィー（装置：島津製
作所社製ＧＣ−７Ａ、充填式カラム 充填材：ジーエル
サイエンス社製ＰＥＧ−６０００）によって分析し、そ
のＥＧの純度を求めた。(4) EG Purity The reaction product after the substitution esterification reaction was subjected to solid-liquid separation, and the filtrate obtained was further distilled to obtain purified EG. The EG was analyzed by gas chromatography (apparatus: GC-7A manufactured by Shimadzu Corporation, packed column filler: PEG-6000 manufactured by GL Sciences) to determine the purity of the EG.
【００２８】［実施例１］ポリエチレンテレフタレート
９５ｇ、ポリブチレンテレフタレート５ｇ、解重合触媒
として炭酸ナトリウム１．５ｇ及びエチレングリコール
１００ｇを冷却管、撹拌機、温度計の三者を備えた５０
０ｍｌの三つ口フラスコ中にて１９８〜２１０℃で十分
撹拌混合しながら１０時間解重合反応させつつ、生成す
るテトラヒドロフランと水を系外へ抜出した。EXAMPLE 1 95 g of polyethylene terephthalate, 5 g of polybutylene terephthalate, 1.5 g of sodium carbonate and 100 g of ethylene glycol as a depolymerization catalyst were equipped with a cooling tube, a stirrer, and a thermometer.
The resulting tetrahydrofuran and water were discharged out of the system while performing a depolymerization reaction for 10 hours in a 0 ml three-necked flask at 198 to 210 ° C. with sufficient stirring and mixing.
【００２９】解重合反応終了後、解重合物全量、メタノ
ール２００ｇ及び置換エステル化触媒として炭酸ナトリ
ウム０．５ｇを冷却管、撹拌機、温度計の三者を備えた
５００ｍｌの三つ口フラスコ中にて６５℃で十分撹拌混
合しながら、１時間反応させ粗生成物を得た。After the completion of the depolymerization reaction, the total amount of the depolymerized product, 200 g of methanol and 0.5 g of sodium carbonate as a substituted esterification catalyst were placed in a 500 ml three-necked flask equipped with a condenser, a stirrer and a thermometer. The mixture was reacted for 1 hour while stirring and mixing at 65 ° C to obtain a crude product.
【００３０】ＤＭＴとＥＧへの解重合はほぼ定量的に進
行し、これら得られたＤＭＴ回収率とＥＧ回収率をはそ
れぞれ８２％と７２％であった。更に、生成物を蒸留分
離・精製して、ＤＭＴ純度とＥＧ純度とをガスクロマト
グラフィーで分析したところ、それぞれ９９％以上であ
った。The depolymerization into DMT and EG proceeded almost quantitatively, and the obtained DMT recovery and EG recovery were 82% and 72%, respectively. Further, the product was separated and purified by distillation, and the purity of DMT and the purity of EG were analyzed by gas chromatography.
【００３１】［実施例２］ポリエチレンテレフタレート
９５ｇ、ポリブチレンテレフタレート５ｇ、ポリエチレ
ン１０ｇ、解重合触媒として炭酸ナトリウム１．５ｇ及
びエチレングリコール１００ｇを冷却管、撹拌機、温度
計及び圧力計の四者を備えた５００ｍｌの三つ口フラス
コ中にて１９８〜２１０℃で十分撹拌混合しながら１０
時間解重合反応させつつ、生成するテトラヒドロフラン
と水を系外へ抜出した。Example 2 95 g of polyethylene terephthalate, 5 g of polybutylene terephthalate, 10 g of polyethylene, 1.5 g of sodium carbonate and 100 g of ethylene glycol as a depolymerization catalyst were equipped with a cooling tube, stirrer, thermometer and pressure gauge. In a 500 ml three-necked flask with sufficient stirring and mixing at 198 to 210 ° C.
The resulting tetrahydrofuran and water were drawn out of the system during the time of the depolymerization reaction.
【００３２】解重合反応終了後、未反応のポリエチレン
を分離除去し、残りの解重合物全量、メタノール２００
ｇ及び置換エステル化触媒として炭酸ナトリウム０．５
ｇを冷却管、撹拌機、温度計の三者を備えた５００ｍｌ
の三つ口フラスコ中にて６５℃で十分撹拌混合しなが
ら、１時間反応させ粗生成物を得た。After the completion of the depolymerization reaction, unreacted polyethylene was separated and removed, and the remaining depolymerized product was completely dissolved in methanol 200
g and sodium carbonate 0.5 as a substituted esterification catalyst.
500 ml equipped with a cooling tube, a stirrer, and a thermometer
The reaction was carried out for 1 hour while sufficiently stirring and mixing at 65 ° C. in a three-necked flask to obtain a crude product.
【００３３】ＤＭＴとＥＧへの解重合はほぼ定量的に進
行し、これら得られたＤＭＴ回収率とＥＧ回収率とはそ
れぞれ８２％と７２％であった。更に、生成物を蒸留分
離し、精製したＤＭＴ純度とＥＧ純度とをガスクロマト
グラフィーで分析したところ、それぞれ９９％以上であ
った。The depolymerization into DMT and EG proceeded almost quantitatively, and the obtained DMT recovery and EG recovery were 82% and 72%, respectively. Further, the product was distilled and separated, and the purity of purified DMT and the purity of EG were analyzed by gas chromatography.
【００３４】［実施例３］ポリエチレンテレフタレート
９５ｇ、ポリブチレンテレフタレート５ｇ、ポリエチレ
ン１０ｇを解重合触媒として炭酸ナトリウム１．５ｇ及
びエチレングリコール１００ｇを冷却管、撹拌機、温度
計及び圧力計の四者を備えた５００ｍｌのオートクレー
ブ中にて２６０℃、０．４９ＭＰａＧで十分撹拌混合し
ながら１．５時間解重合反応させつつ、生成するテトラ
ヒドロフランと水を系外へ抜出した。[Example 3] 95 g of polyethylene terephthalate, 5 g of polybutylene terephthalate and 10 g of polyethylene were used as depolymerization catalysts. 1.5 g of sodium carbonate and 100 g of ethylene glycol were equipped with a cooling tube, a stirrer, a thermometer and a pressure gauge. The resulting tetrahydrofuran and water were drained out of the system while performing a depolymerization reaction for 1.5 hours in a 500 ml autoclave at 260 ° C. and 0.49 MPaG with sufficient stirring and mixing.
【００３５】解重合反応終了後、解重合物全量、メタノ
ール２００ｇ及び置換エステル化触媒として炭酸ナトリ
ウム０．５ｇを冷却管、撹拌機、温度計の三者を備えた
５００ｍｌの三つ口フラスコ中にて６５℃で十分撹拌混
合しながら、１時間反応させ粗生成物を得た。After the completion of the depolymerization reaction, the total amount of the depolymerized product, 200 g of methanol and 0.5 g of sodium carbonate as a substituted esterification catalyst were placed in a 500 ml three-necked flask equipped with a condenser, a stirrer and a thermometer. The mixture was reacted for 1 hour while stirring and mixing at 65 ° C to obtain a crude product.
【００３６】ＤＭＴとＥＧへの解重合はほぼ定量的に進
行し、これら得られたＤＭＴ回収率とＥＧ回収率はそれ
ぞれ８１％と７０％であった。更に、生成物を蒸留分離
・精製して、ＤＭＴ純度とＥＧ純度とをガスクロマトグ
ラフィーで分析したところ、それぞれ９９％以上であっ
た。The depolymerization into DMT and EG proceeded almost quantitatively, and the obtained DMT recovery and EG recovery were 81% and 70%, respectively. Further, the product was separated and purified by distillation, and the purity of DMT and the purity of EG were analyzed by gas chromatography.
【００３７】［比較例１］ポリエチレンテレフタレート
９５ｇ、ポリブチレンテレフタレート５ｇ、解重合触媒
として炭酸ナトリウム１．５ｇ及びエチレングリコール
１００ｇを冷却管、撹拌機、温度計の三者を備えた５０
０ｍｌの三つ口フラスコ中にて１７０℃で十分撹拌混合
しながら１０時間解重合反応させたが、解重合反応はほ
とんど進行せず、また１，４−ブチレングリコール由来
のテトラヒドロフランと水の生成が全く見られなかっ
た。Comparative Example 1 95 g of polyethylene terephthalate, 5 g of polybutylene terephthalate, 1.5 g of sodium carbonate and 100 g of ethylene glycol as a depolymerization catalyst were equipped with a cooling tube, a stirrer, and a thermometer.
The depolymerization reaction was carried out for 10 hours in a 0 ml three-necked flask with sufficient stirring and mixing at 170 ° C., but the depolymerization reaction hardly proceeded, and the formation of tetrahydrofuran and water derived from 1,4-butylene glycol was not observed. I didn't see it at all.
【００３８】[0038]
【発明の効果】本発明の回収方法によれば、ポリブチレ
ンテレフタレートを少なくとも含むポリエステル混合物
からなるポリエステル廃棄物をケミカルリサイクルする
に際し、ポリブチレンテレフタレートから生成する１，
４−ブチレングリコールやテトラヒドロフラン影響を受
けることなく、従来技術になかった繊維等のポリマー原
料として使用できる品質のＤＭＴとＥＧとを容易に回収
することができ、回収したＤＭＴはテレフタル酸、ビス
（β−ヒドロキシエチル）テレフタレート及びポリエス
テルの製造における原料として用いることができる。According to the recovery method of the present invention, when a polyester waste comprising a polyester mixture containing at least polybutylene terephthalate is subjected to chemical recycling, 1,1 produced from polybutylene terephthalate is produced.
Without being affected by 4-butylene glycol or tetrahydrofuran, DMT and EG having a quality that can be used as a polymer raw material such as fibers, which were not available in the prior art, can be easily recovered. The recovered DMT is terephthalic acid, bis (β -Hydroxyethyl) terephthalate and polyesters.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 長谷川 英雄 愛媛県松山市北吉田町77番地 帝人株式会 社松山事業所内 (72)発明者 佐藤 和広 愛媛県松山市北吉田町77番地 帝人株式会 社松山事業所内 Ｆターム(参考） 4F301 AA13 AA14 AA25 AB02 AB03 CA23 CA26 CA41 CA71 CA72 CA73 4G069 AA02 AA09 BA21A BB16A BB16B BC01A BC02A BC02B BC08A BE08A CA10 CB01 CB75 DA05 EA01Y FC04 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hideo Hasegawa 77, Kitayoshida-cho, Matsuyama-shi, Ehime Teijin Co., Ltd.Matsuyama Office (72) Inventor Kazuhiro Sato 77, Kitayoshida-cho, Matsuyama-shi, Ehime Teijin Co., Ltd. Matsuyama Office F-term (reference) 4F301 AA13 AA14 AA25 AB02 AB03 CA23 CA26 CA41 CA71 CA72 CA73 4G069 AA02 AA09 BA21A BB16A BB16B BC01A BC02A BC02B BC08A BE08A CA10 CB01 CB75 DA05 EA01Y FC04
Claims (9)
も含むポリエステル混合物からなるポリエステル廃棄物
を解重合触媒存在下で解重合し、次いで置換エステル化
触媒存在下でメタノールを用いて置換エステル化反応を
行ったのち、さらに分離精製することでテレフタル酸ジ
メチルとエチレングリコールとを回収する方法におい
て、 該混合物を、エチレングリコールを用いて１８０℃以上
３００℃以下の温度範囲で、解重合反応させながら１，
４−ブチレングリコール骨格が変換し生じるテトラヒド
ロフランと水を除去し、次いで置換エステル化反応させ
ることを特徴とする、ポリエステル廃棄物からの有価成
分回収方法。1. A polyester waste comprising a polyester mixture containing at least polybutylene terephthalate is depolymerized in the presence of a depolymerization catalyst, and then subjected to a substituted esterification reaction using methanol in the presence of a substituted esterification catalyst. In a method of recovering dimethyl terephthalate and ethylene glycol by further separating and purifying, the mixture is subjected to a depolymerization reaction using ethylene glycol in a temperature range of 180 ° C. or more and 300 ° C. or less,
A method for recovering valuable components from polyester waste, comprising removing tetrahydrofuran and water generated by conversion of a 4-butylene glycol skeleton, followed by a substitution esterification reaction.
土類金属の、炭酸塩、炭酸水素塩、及びカルボン酸塩か
らなる群から選ばれた少なくとも１種以上の化合物とす
る、請求項１記載の回収方法。2. The method according to claim 1, wherein the depolymerization catalyst is at least one compound selected from the group consisting of carbonates, bicarbonates, and carboxylate salts of alkali metals and alkaline earth metals. Collection method.
求項２記載の回収方法。3. The method according to claim 2, wherein the depolymerization catalyst is sodium carbonate.
アルカリ土類金属の、炭酸塩、炭酸水素塩、及びカルボ
ン酸塩からなる群から選ばれた少なくとも１種以上の化
合物とする、請求項１記載の回収方法。4. The method according to claim 1, wherein the substituted esterification catalyst is at least one compound selected from the group consisting of carbonates, bicarbonates, and carboxylate salts of alkali metals and alkaline earth metals. Collection method.
する、請求項４記載の回収方法。5. The recovery method according to claim 4, wherein the substituted esterification catalyst is sodium carbonate.
レフタレート以外に、ポリエチレンテレフタレート、ポ
リエチレン、ポリプロピレン、金属及び無機化合物から
なる群から選ばれた少なくとも１種を含む、請求項１記
載の回収方法。6. The recovery method according to claim 1, wherein the polyester waste contains at least one selected from the group consisting of polyethylene terephthalate, polyethylene, polypropylene, metals and inorganic compounds, in addition to polybutylene terephthalate.
酸ジメチルを、テレフタル酸製造の原料として用いる、
回収有価成分の利用方法。7. The purified and recovered dimethyl terephthalate according to claim 1 is used as a raw material for producing terephthalic acid.
How to use recovered valuable components.
酸ジメチルを、ビス（β−ヒドロキシエチル）テレフタ
レート製造の原料として用いる、回収有価成分の利用方
法。8. A method for using a recovered valuable component, wherein the purified and recovered dimethyl terephthalate according to claim 1 is used as a raw material for producing bis (β-hydroxyethyl) terephthalate.
酸ジメチルを、ポリエステル製造の原料として用いる、
回収有価成分の利用方法。9. The purified and recovered dimethyl terephthalate according to claim 1 is used as a raw material for producing a polyester.
How to use recovered valuable components.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010215676A (en) * | 2009-03-12 | 2010-09-30 | National Institute Of Advanced Industrial Science & Technology | Decomposition method by high-temperature water for polybutylene terephthalate |
| CN112341315A (en) * | 2020-11-05 | 2021-02-09 | 艾凡佳德(上海)环保科技有限公司 | Dehydration method of gas-phase substance obtained after continuous alcoholysis of waste polyester |
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2000
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010215676A (en) * | 2009-03-12 | 2010-09-30 | National Institute Of Advanced Industrial Science & Technology | Decomposition method by high-temperature water for polybutylene terephthalate |
| CN112341315A (en) * | 2020-11-05 | 2021-02-09 | 艾凡佳德(上海)环保科技有限公司 | Dehydration method of gas-phase substance obtained after continuous alcoholysis of waste polyester |
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| Publication number | Publication date |
|---|---|
| JP4444443B2 (en) | 2010-03-31 |
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