JP2000212126A - Purification of bishydroxyalkyl terephthalate - Google Patents
Purification of bishydroxyalkyl terephthalateInfo
- Publication number
- JP2000212126A JP2000212126A JP11013294A JP1329499A JP2000212126A JP 2000212126 A JP2000212126 A JP 2000212126A JP 11013294 A JP11013294 A JP 11013294A JP 1329499 A JP1329499 A JP 1329499A JP 2000212126 A JP2000212126 A JP 2000212126A
- Authority
- JP
- Japan
- Prior art keywords
- exchange resin
- terephthalate
- crude
- passing
- acidic cation
- 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.)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ビスヒドロキシア
ルキルテレフタレートの精製方法およびその装置に関す
るものである。さらに詳しくは、本発明は再生ポリエチ
レンテレフタレートの原料として使用可能な粗ビスヒド
ロキシアルキルテレフタレートの精製方法およびその装
置に関するものである。[0001] The present invention relates to a method for purifying bishydroxyalkyl terephthalate and an apparatus therefor. More specifically, the present invention relates to a method for purifying crude bishydroxyalkyl terephthalate that can be used as a raw material for recycled polyethylene terephthalate and an apparatus therefor.
【０００２】[0002]
【従来の技術】従来、ポリエチレンテレフタレートやポ
リブチレンテレフタレート（以下、「ＰＥＴ等」と略称
する）は、テレフタル酸ジメチルまたはテレフタル酸と
エチレングリコールまたは１，４−ブタンジオールを反
応させて、ビスヒドロキシエチルテレフタレートまたは
ビスヒドロキシブチルテレフタレート（以下、「ＢＨＥ
Ｔ等」と略称する）を製造し、次いでＢＨＥＴ等を縮合
させて製造されている。2. Description of the Related Art Conventionally, polyethylene terephthalate and polybutylene terephthalate (hereinafter abbreviated as "PET") have been prepared by reacting dimethyl terephthalate or terephthalic acid with ethylene glycol or 1,4-butanediol to form bishydroxyethyl. Terephthalate or bishydroxybutyl terephthalate (hereinafter referred to as “BHE
T, etc.) and then condensation with BHET, etc.
【０００３】テレフタル酸ジメチルまたはテレフタル酸
から得られた粗ＢＨＥＴ等は、副生物のメタノールや水
が含まれているため、縮合させる前に、蒸留によりメタ
ノールや水を留去して精製していた。[0003] Since crude BHET obtained from dimethyl terephthalate or terephthalic acid contains by-products such as methanol and water, it was purified by distilling off methanol and water by distillation before condensation. .
【０００４】一方、容器包装リサイクル法が１９９７年
４月に施行されてから、ＰＥＴ等のリサイクル需要が高
まっている。ＰＥＴ等をリサイクルする方法としては、
回収したＰＥＴ等を細断して溶融し、繊維状のＰＥＴ等
に加工して、生地に再生する方法と、回収ＰＥＴ等を原
料のモノマー（ＢＨＥＴ等）に分解して回収し、回収モ
ノマーから再度ＰＥＴ等を合成するケミカルリサイクル
法がある。On the other hand, since the Containers and Packaging Recycling Law was enforced in April 1997, the demand for recycling PET and the like has been increasing. As a method of recycling PET etc.,
A method of chopping and melting the collected PET, etc., processing it into fibrous PET, etc., and regenerating it into dough, and decomposing the collected PET, etc. into raw material monomers (BHET, etc.) There is a chemical recycling method for synthesizing PET or the like again.
【０００５】ＰＥＴ等のケミカルリサイクル法として
は、触媒の存在下にアルコールやグリコール類等の溶媒
を用いて加溶媒分解反応によりＰＥＴ等を分解し、モノ
マー（ＢＨＥＴ等）を回収する方法等が知られている。As a chemical recycling method for PET or the like, a method of decomposing PET or the like by a solvolysis reaction using a solvent such as alcohol or glycol in the presence of a catalyst to recover a monomer (BHET or the like) is known. Have been.
【０００６】[0006]
【発明が解決しようとする課題】しかし、ケミカルリサ
イクル法で回収されたモノマー（ＢＨＥＴ等）には、様
々な副分解生成物、着色剤、付着物やリサイクル工程中
に用いる水に含まれるイオン等の不純物が含まれてい
る。ＰＥＴ等を合成するためには、高純度のモノマーを
用いる必要があり、ケミカルリサイクル法で回収された
モノマーは不純物が多く、そのままではＰＥＴ等の合成
に用いることができない。However, monomers (BHET, etc.) recovered by the chemical recycling method include various by-products, coloring agents, deposits, ions contained in water used in the recycling process, and the like. Impurities. In order to synthesize PET or the like, it is necessary to use a high-purity monomer. The monomer recovered by the chemical recycling method has many impurities and cannot be used for synthesis of PET or the like as it is.
【０００７】本発明者等は粗ＢＨＥＴ等を含む溶液中か
ら不純物のイオンを除去するためには、イオン交換樹脂
を使用すればよいことを見出し、特許出願（特願平１０
−３３３１７９号）をした。特願平１０−３３３１７９
号において使用されるイオン交換樹脂は強酸性カチオン
交換樹脂と弱塩基性アニオン交換樹脂である。脱塩性能
を重視する場合、アニオン交換樹脂として強塩基性アニ
オン交換樹脂を用いることが好ましいが、粗ＢＨＥＴ等
の濃度によっては通液温度を６０℃以上にする必要があ
り、このような高温下での通液処理を行うためにはアニ
オン交換樹脂として弱塩基性アニオン交換樹脂を用いざ
るを得ない。The present inventors have found that an ion-exchange resin can be used to remove impurity ions from a solution containing crude BHET or the like.
-333179). Japanese Patent Application No. 10-333179
The ion exchange resins used in No. 1 are strongly acidic cation exchange resins and weakly basic anion exchange resins. When desalination performance is important, it is preferable to use a strongly basic anion exchange resin as the anion exchange resin. However, depending on the concentration of crude BHET or the like, it is necessary to set the liquid passing temperature to 60 ° C. or higher. In order to carry out the liquid-passing treatment, the weakly basic anion exchange resin must be used as the anion exchange resin.
【０００８】ところが、弱塩基性アニオン交換樹脂を用
いる場合、処理を繰り返すにつれて塩類のリーク量が増
え、高純度のモノマーを回収できないことが判明した。However, it has been found that when a weakly basic anion exchange resin is used, the amount of salt leakage increases as the treatment is repeated, and it is impossible to recover a high-purity monomer.
【０００９】本発明が解決しようとする課題は、ＰＥＴ
等の合成に使用しうる高純度のモノマーとすることが可
能な、粗ビスヒドロキシアルキルテレフタレートの精製
方法を提供することである。[0009] The problem to be solved by the present invention is PET.
An object of the present invention is to provide a method for purifying crude bishydroxyalkyl terephthalate, which can be used as a high-purity monomer that can be used for the synthesis of the above.
【００１０】[0010]
【課題を解決するための手段】本発明者らは上記課題を
解決するため、鋭意研究を重ねた結果、本発明を完成す
るに至った。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention.
【００１１】すなわち、本発明は、粗ビスヒドロキシア
ルキルテレフタレートを活性炭とイオン交換樹脂を組み
合わせて通液処理して精製するビスヒドロキシアルキル
テレフタレートの精製方法において、イオン交換樹脂に
よる処理を、単層の強酸性カチオン交換樹脂に通液した
後、強酸性カチオン交換樹脂と弱塩基性アニオン交換樹
脂の混層に通液することを特徴とするビスヒドロキシア
ルキルテレフタレートの精製方法に関するものである。That is, the present invention relates to a method for purifying bishydroxyalkyl terephthalate in which crude bishydroxyalkyl terephthalate is subjected to a liquid passing treatment using a combination of activated carbon and an ion exchange resin to purify the bishydroxyalkyl terephthalate with a single layer of strong acid. The present invention relates to a method for purifying bishydroxyalkyl terephthalate, wherein the solution is passed through an acidic cation exchange resin and then passed through a mixed layer of a strongly acidic cation exchange resin and a weakly basic anion exchange resin.
【００１２】[0012]
【発明の実施の形態】本発明の処理対象となる粗ビスヒ
ドロキシアルキルテレフタレートとは、不純物を含むビ
スヒドロキシアルキルテレフタレートであり、ポリオキ
シエチレンテレフタレートを加水分解もしくは加溶媒分
解して得られるビスヒドロキシエチルテレフタレート
や、ポリオキシブチレンテレフタレートを加水分解もし
くは加溶媒分解して得られるビスヒドロキシブチルテレ
フタレートである。BEST MODE FOR CARRYING OUT THE INVENTION The crude bishydroxyalkyl terephthalate to be treated in the present invention is bishydroxyalkyl terephthalate containing impurities, and is obtained by hydrolyzing or solvolyzing polyoxyethylene terephthalate. Terephthalate and bishydroxybutyl terephthalate obtained by hydrolysis or solvolysis of polyoxybutylene terephthalate.
【００１３】本発明の処理対象となる粗ＢＨＥＴ等は、
廃ＰＥＴ等のケミカルリサイクル工程で得られる粗ＢＨ
ＥＴ以外にも、通常のＰＥＴ等の合成の高純度原料であ
るテレフタル酸ジメチルやテレフタル酸から得られる粗
ＢＨＥＴ等であってもよい。The crude BHET or the like to be processed by the present invention is as follows:
Crude BH obtained in the chemical recycling process of waste PET etc.
In addition to ET, dimethyl terephthalate or crude BHET obtained from terephthalic acid which is a high-purity raw material for synthesis of ordinary PET or the like may be used.
【００１４】なお、ＰＥＴ等のケミカルリサイクル工程
としては、ＰＥＴ等を粗ＢＨＥＴ等に分解処理できる方
法であればよく、例えば溶媒を用いたＰＥＴ等の加溶媒
分解法や、超臨界溶液を用いた分解法等を挙げることが
できる。The chemical recycling step for PET or the like may be any method capable of decomposing PET or the like into crude BHET or the like. For example, a solvolysis method for PET or the like using a solvent or a supercritical solution may be used. A decomposition method can be used.
【００１５】ケミカルリサイクル工程で分解した粗ＢＨ
ＥＴ等には、ＰＥＴの重合触媒や無機顔料が不溶性無機
不純物として含まれているので、本発明の精製処理を行
う前に、セラミックフィルター等により不溶性無機不純
物を除去する必要がある。Crude BH decomposed in the chemical recycling process
Since ET and the like contain a PET polymerization catalyst and an inorganic pigment as insoluble inorganic impurities, it is necessary to remove the insoluble inorganic impurities using a ceramic filter or the like before performing the purification treatment of the present invention.
【００１６】回収ＰＥＴボトルから得られる粗ＢＨＥＴ
中のイオン種は詳しく判明していないが、強酸性カチオ
ン交換樹脂と弱塩基性アニオン交換樹脂の混層に通液す
ることにより塩類のリークが少なくなることが判った。Crude BHET obtained from recovered PET bottle
Although the ionic species therein are not known in detail, it has been found that leaking salts is reduced by passing the mixture through a mixed layer of a strongly acidic cation exchange resin and a weakly basic anion exchange resin.
【００１７】また、回収ＰＥＴボトルから得られる粗Ｂ
ＨＥＴのイオン濃度は詳しくは判明していないが、アニ
オン成分に比べカチオン成分が多く溶解していることが
判り、その分カチオン成分を除去するために強酸性カチ
オン交換樹脂と弱塩基性アニオン交換樹脂との混層に通
液する前に、単層の強酸性カチオン交換樹脂に通液する
ことで、処理液品質を落とすことなく、処理量を増やす
ことができる。The crude B obtained from the recovered PET bottle
Although the ion concentration of HET is not known in detail, it has been found that the cation component is dissolved more than the anion component, and in order to remove the cation component, a strongly acidic cation exchange resin and a weakly basic anion exchange resin are used. By passing the solution through a single layer of strongly acidic cation exchange resin before passing through the mixed layer with the above, the throughput can be increased without lowering the quality of the processing solution.
【００１８】強酸性カチオン交換樹脂と弱塩基性アニオ
ン交換樹脂の混層における、両樹脂の混合割合は、容量
で強酸性カチオン交換樹脂：弱塩基性アニオン交換樹脂
＝２：１〜１：４、好ましくは１：１〜１：２である。In the mixed layer of the strongly acidic cation exchange resin and the weakly basic anion exchange resin, the mixing ratio of the two resins is preferably 2: 1 to 1: 4 in terms of volume: strongly acidic cation exchange resin: weakly basic anion exchange resin. Is 1: 1 to 1: 2.
【００１９】本発明において粗ＢＨＥＴ等が精製される
詳しい除去機構は判明していないが、粗ＢＨＥＴ等に含
まれる着色剤はイオン交換樹脂では吸着されにくく、活
性炭で吸着されることが分かった。Although a detailed removal mechanism for purifying crude BHET and the like in the present invention has not been clarified, it has been found that the coloring agent contained in the crude BHET and the like is hardly adsorbed by the ion exchange resin and adsorbed by the activated carbon.
【００２０】粗ＢＨＥＴ等は、溶媒に加熱溶解して処理
することが好ましく、用いる溶媒としては、メタノール
やＰＥＴ等の加溶媒分解に用いられるエチレングリコー
ル等を挙げることができる。The crude BHET or the like is preferably treated by dissolving it in a solvent by heating. Examples of the solvent to be used include ethylene glycol used for solvolysis of methanol and PET.
【００２１】活性炭とイオン交換樹脂による処理は、ど
ちらが先でも問題はないが、活性炭の精製度によっては
通液により酸化物の溶出があるので、好ましくは活性炭
処理を行った後に、イオン交換樹脂による処理を行うこ
とが好ましい。Either of the treatment with activated carbon and the ion exchange resin does not matter, but the oxide is eluted by passing the activated carbon depending on the degree of purification of the activated carbon. Therefore, the treatment with the ion exchange resin is preferably performed after the activated carbon treatment. Preferably, a treatment is performed.
【００２２】[0022]
【実施例】実施例および比較例で用いた粗ＢＨＥＴ溶液
は、ＰＥＴボトルをケミカルリサイクルする工程で得ら
れる濾過処理後の溶液であり、組成は、ＰＥＴ１８重量
％、エチレングリコール８１重量％、水１重量％であ
る。The crude BHET solution used in Examples and Comparative Examples is a solution after a filtration treatment obtained in a step of chemically recycling a PET bottle, and has a composition of 18% by weight of PET, 81% by weight of ethylene glycol, and 1% of water. % By weight.
【００２３】実施例１ 粗ＢＨＥＴ溶液を温度６０℃で、通液速度２５０ｍｌ／
ｈｒで木質活性炭（二村化学（株）製、「太閤ＳＧ
Ａ」）１００ｍｌを充填した活性炭層に通液後、単床式
の強酸性カチオン交換樹脂（ローム・アンド・ハース社
製「アンバーライトＩＲ−１２０Ｂ」２４ｍｌ）層に通
液した後、混床式のイオン交換樹脂（ローム・アンド・
ハース社製「アンバーライト ＩＲＡ９６ＳＢ」１２ｍ
ｌ＋「アンバーライト ＩＲ−１２０Ｂ」１２ｍｌ）層
に通液した。粗ＢＨＥＴ溶液を１０００ｍｌ、２０００
ｍｌ、３０００ｍｌ通液したときの電気伝導率を表１に
示す。Example 1 A crude BHET solution was heated at a temperature of 60 ° C. at a flow rate of 250 ml /
hr wood-based activated carbon (manufactured by Nimura Chemical Co., Ltd., Taiko SG
A ") After passing through an activated carbon layer filled with 100 ml, the mixture was passed through a single-bed type strongly acidic cation exchange resin (" Amberlite IR-120B "manufactured by Rohm and Haas Company, 24 ml) layer, and then mixed bed type. Ion exchange resin (ROHM &
Haas "Amberlight IRA96SB" 12m
1+ "Amberlite IR-120B" 12 ml) layer. 1000 ml of the crude BHET solution, 2000
Table 1 shows the electrical conductivity when 3000 ml of the solution was passed.
【００２４】比較例１ 粗ＢＨＥＴ溶液を温度６０℃、通液速度２５０ｍｌ／ｈ
ｒで木質活性炭（二村化学（株）製、「太閤ＳＧＡ」）
１００ｍｌを充填した活性炭層に通液した後、単床式の
強酸性カチオン交換樹脂（「アンバーライト ＩＲ−１
２０Ｂ」３６ｍｌ）層に通液した後、単床式の弱塩基性
アニオン交換樹脂（「アンバーライトＩＲＡ９６ＳＢ」
１２ｍｌ）層に通液した。Comparative Example 1 A crude BHET solution was heated at a temperature of 60 ° C. and a flow rate of 250 ml / h.
r for wood activated carbon (Taiko SGA, manufactured by Nimura Chemical Co., Ltd.)
After passing through an activated carbon layer filled with 100 ml, a single-bed strongly acidic cation exchange resin (“Amberlite IR-1
After passing through a layer of “20B” (36 ml), a single-bed weakly basic anion exchange resin (“Amberlite IRA96SB”)
12 ml).
【００２５】粗ＢＨＥＴ溶液を１０００ｍｌ、２０００
ｍｌ、３０００ｍｌ通液したときの電気伝導率を表１に
示す。1000 ml of the crude BHET solution, 2000
Table 1 shows the electrical conductivity when 3000 ml of the solution was passed.
【００２６】比較例２ 粗ＢＨＥＴ溶液を温度６０℃、通液速度２５０ｍｌ／ｈ
ｒで木質活性炭（二村化学（株）製、「太閤ＳＧＡ」）
１００ｍｌを充填した活性炭層に通液した後、混床式の
イオン交換樹脂（ローム・アンド・ハース社製「アンバ
ーライト ＩＲＡ９６ＳＢ」１２ｍｌ＋「アンバーライ
ト ＩＲ−１２０Ｂ」３６ｍｌ）層に通液した。粗ＢＨ
ＥＴ溶液を１０００ｍｌ、２０００ｍｌ、３０００ｍｌ
通液したときの電気伝導率を表１に示す。Comparative Example 2 A crude BHET solution was heated at a temperature of 60 ° C. and a flow rate of 250 ml / h.
r for wood activated carbon (Taiko SGA, manufactured by Nimura Chemical Co., Ltd.)
After passing through an activated carbon layer filled with 100 ml, the solution was passed through a mixed bed type ion exchange resin (12 ml of “Amberlite IRA96SB” manufactured by Rohm and Haas Co., Ltd. + 36 ml of “Amberlite IR-120B”). Crude BH
1000ml, 2000ml, 3000ml of ET solution
Table 1 shows the electric conductivity when the liquid was passed.
【００２７】[0027]
【表１】 [Table 1]
【００２８】表１に示した結果から明らかなように、単
床式の強酸性カチオン交換樹脂層と単床式の弱塩基性ア
ニオン交換樹脂層に通液した比較例１の精製法では２０
００ｍｌを通液した時点で塩類がリークし始めており、
強酸性カチオン交換樹脂と弱塩基性アニオン交換樹脂と
の混床式のイオン交換樹脂層に通液した比較例２の精製
法では、１０００ｍｌ通液した時点で塩類がリークして
くるのに対し、単床式の強酸性カチオン交換樹脂層を通
液した後に混床式のイオン交換樹脂層に通液した実施例
１の精製方法は、３０００ｍｌの通液処理をしても塩類
のリークが少ないことが判る。As is clear from the results shown in Table 1, the purification method of Comparative Example 1 in which the solution was passed through a single-bed strongly acidic cation-exchange resin layer and a single-bed weakly basic anion-exchange resin layer was used.
At the time of passing through 00 ml, salts have started to leak,
In the purification method of Comparative Example 2 in which the solution was passed through a mixed-bed type ion exchange resin layer of a strongly acidic cation exchange resin and a weakly basic anion exchange resin, salts leaked at the time of passing 1,000 ml, The purification method of Example 1 in which the solution was passed through a single-bed strongly acidic cation-exchange resin layer and then passed through a mixed-bed ion-exchange resin layer had a small amount of salt leakage even when the solution was passed through 3000 ml. I understand.
【００２９】[0029]
【発明の効果】粗ＢＨＥＴ等を活性炭とイオン交換樹脂
を組み合わせて精製処理する方法において、単床式の強
酸性カチオン交換樹脂に通液した後、強酸性カチオン交
換樹脂と弱塩基性アニオン交換樹脂の混床式のイオン交
換樹脂層に通液することにより、塩類のリークの少ない
粗ＢＨＥＴ等の精製処理を行うことができる。According to the method for purifying crude BHET or the like by combining activated carbon and an ion exchange resin, the crude BHET is passed through a single-bed strongly acidic cation exchange resin, and then the strongly acidic cation exchange resin and the weakly basic anion exchange resin. By passing the solution through a mixed bed type ion exchange resin layer, a purification treatment such as crude BHET with less salt leakage can be performed.
Claims (2)
トを活性炭とイオン交換樹脂を組み合わせて通液処理し
て精製するビスヒドロキシアルキルテレフタレートの精
製方法において、イオン交換樹脂による処理を、単層の
強酸性カチオン交換樹脂に通液した後、強酸性カチオン
交換樹脂と弱塩基性アニオン交換樹脂の混層に通液する
ことを特徴とするビスヒドロキシアルキルテレフタレー
トの精製方法。1. A bishydroxyalkyl terephthalate purification method for purifying crude bishydroxyalkyl terephthalate by passing a mixture of activated carbon and an ion-exchange resin through a liquid treatment, wherein the treatment with the ion-exchange resin is a single-layer strongly acidic cation-exchange resin. And then passing the mixture through a mixed layer of a strongly acidic cation exchange resin and a weakly basic anion exchange resin.
がビスヒドロキシエチルテレフタレートまたはビスヒド
ロキシブチルテレフタレートであることを特徴とする請
求項１に記載の精製方法。2. The method according to claim 1, wherein the bishydroxyalkyl terephthalate is bishydroxyethyl terephthalate or bishydroxybutyl terephthalate.
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| Application Number | Priority Date | Filing Date | Title |
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| JP01329499A JP3784561B2 (en) | 1999-01-21 | 1999-01-21 | Method for purifying bishydroxyalkyl terephthalate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01329499A JP3784561B2 (en) | 1999-01-21 | 1999-01-21 | Method for purifying bishydroxyalkyl terephthalate |
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| Publication Number | Publication Date |
|---|---|
| JP2000212126A true JP2000212126A (en) | 2000-08-02 |
| JP2000212126A5 JP2000212126A5 (en) | 2004-11-25 |
| JP3784561B2 JP3784561B2 (en) | 2006-06-14 |
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| JP01329499A Expired - Lifetime JP3784561B2 (en) | 1999-01-21 | 1999-01-21 | Method for purifying bishydroxyalkyl terephthalate |
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| Country | Link |
|---|---|
| JP (1) | JP3784561B2 (en) |
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|---|---|
| JP3784561B2 (en) | 2006-06-14 |
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