JP2009120568A - Method for purifying alkylene glycol - Google Patents
Method for purifying alkylene glycolInfo
- Publication number
- JP2009120568A JP2009120568A JP2007298149A JP2007298149A JP2009120568A JP 2009120568 A JP2009120568 A JP 2009120568A JP 2007298149 A JP2007298149 A JP 2007298149A JP 2007298149 A JP2007298149 A JP 2007298149A JP 2009120568 A JP2009120568 A JP 2009120568A
- Authority
- JP
- Japan
- Prior art keywords
- alkylene glycol
- ethylene glycol
- dye
- ozone
- purifying
- 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
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims abstract description 168
- -1 alkylene glycol Chemical compound 0.000 title claims abstract description 49
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 25
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000004821 distillation Methods 0.000 claims abstract description 24
- 229910017464 nitrogen compound Inorganic materials 0.000 claims abstract description 22
- 150000002830 nitrogen compounds Chemical class 0.000 claims abstract description 22
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 11
- 230000003647 oxidation Effects 0.000 claims abstract description 10
- 239000007800 oxidant agent Substances 0.000 claims abstract description 7
- 229920000728 polyester Polymers 0.000 claims description 16
- 238000012691 depolymerization reaction Methods 0.000 claims description 10
- 239000002699 waste material Substances 0.000 claims description 6
- 229920001283 Polyalkylene terephthalate Polymers 0.000 claims description 3
- 238000004043 dyeing Methods 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 11
- 238000000746 purification Methods 0.000 abstract description 10
- 239000000975 dye Substances 0.000 description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 12
- 238000000605 extraction Methods 0.000 description 11
- 239000004744 fabric Substances 0.000 description 10
- 239000000835 fiber Substances 0.000 description 10
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 229920000139 polyethylene terephthalate Polymers 0.000 description 8
- 239000005020 polyethylene terephthalate Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000005809 transesterification reaction Methods 0.000 description 7
- 230000005587 bubbling Effects 0.000 description 6
- 238000006864 oxidative decomposition reaction Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 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 3
- 238000004042 decolorization Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004737 colorimetric analysis Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- BTVWZWFKMIUSGS-UHFFFAOYSA-N dimethylethyleneglycol Natural products CC(C)(O)CO BTVWZWFKMIUSGS-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000006103 coloring component Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 125000005597 hydrazone group Chemical group 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method 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
- 238000007086 side reaction Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
本発明は、アルキレングリコールの精製方法に関し、更に詳しくは、窒素化合物を不純物として含むアルキレングリコールをオゾン分解による酸化分解と蒸留を組み合わせることにより、高純度のアルキレングリコールを得る方法に関する。 The present invention relates to a method for purifying alkylene glycol, and more particularly, to a method for obtaining high-purity alkylene glycol by combining oxidative decomposition by distillation and distillation of alkylene glycol containing a nitrogen compound as an impurity.
ポリエステル、例えばポリエチレンテレフタレートはその優れた特性により繊維、フィルム、樹脂等として広く用いられている。これらの使用済み後の廃棄されたポリエチレンテレフタレート（以下、ポリエステル廃棄物と略記することがある。）を解重合によりアルキレングリコール、テレフタル酸ジメチル（以下、ＤＭＴと略記することがある。）、テレフタル酸あるいはその誘導体等のモノマーに分解するケミカルリサイクルに関する種々の提案がある。該ケミカルリサイクルには回収したポリエステル廃棄物とメタノール（以下、ＭｅＯＨと略記することがある。）とを反応させ、ＤＭＴとアルキレングリコールを回収する方法が知られている。ペットボトルの回収は広く浸透し、かなりの割合で回収されているが、繊維製品に関してはペットボトルと同じポリエステルを含む素材でありながらリサイクル率は極めて低く、大部分が焼却処理されたり、埋め立て処分されている。繊維製品を回収する場合、染料やその他の添加物がエチレングリコールを汚染し、高品位の製品が回収できない。特に染料や添加物には窒素を含有する化合物が使用されるケースが多く、そのまま回収したエチレングリコールには窒素化合物がコンタミし、この状態のまま重合工程で得られたエチレングリコールを使用するとポリマー品質が低下し、良質のポリエステルを再生することができない。染料等の着色成分を含んだエチレングリコールの精製については吸着処理、イオン交換処理、晶析処理、蒸留処理又はこれらの組み合わせにより精製処理する取り組みがあるが（例えば特許文献１及び特許文献２参照。）、イオン交換処理ではイオン性の物質しか精製処理の対象とできず、また吸着処理ではアルキレングリコールの吸着剤処理は飽和が早いことは公知の事実であり、再生に大きなコストが必要となることから経済的な方法ではなく、染料等の窒素化合物を含むエチレングリコールの精製については効率的且つ、経済的な精製方法が望まれている。回収されたアルキレングリコールを再利用するに際しては、試薬と同程度まで不純物を除去することが好ましいが、不純物の大部分は蒸留により除去可能であるものの、含まれる不純物の極性、分子量、比揮発度が多岐に渡るために、蒸留だけでは分離できない。 Polyesters such as polyethylene terephthalate are widely used as fibers, films, resins and the like due to their excellent properties. These used polyethylene terephthalate (hereinafter sometimes abbreviated as polyester waste) after use is depolymerized to produce alkylene glycol, dimethyl terephthalate (hereinafter abbreviated as DMT), terephthalic acid. There are various proposals regarding chemical recycling that decomposes into monomers such as derivatives thereof. For the chemical recycling, a method of recovering DMT and alkylene glycol by reacting recovered polyester waste with methanol (hereinafter sometimes abbreviated as MeOH) is known. The collection of PET bottles is widely spread and is collected at a considerable rate, but the recycling rate for textile products is extremely low despite being a material containing the same polyester as PET bottles, and most of them are incinerated or landfilled. Has been. When recovering textile products, dyes and other additives contaminate ethylene glycol, and high-quality products cannot be recovered. In particular, nitrogen-containing compounds are often used for dyes and additives. Nitrogen compounds are contaminated with ethylene glycol collected as it is, and polymer quality is obtained when ethylene glycol obtained in the polymerization process is used in this state. Can not be regenerated and good quality polyester cannot be regenerated. As for the purification of ethylene glycol containing coloring components such as dyes, there are efforts to purify by an adsorption treatment, an ion exchange treatment, a crystallization treatment, a distillation treatment, or a combination thereof (for example, see Patent Literature 1 and Patent Literature 2). ) In the ion exchange treatment, only ionic substances can be subjected to purification treatment, and in the adsorption treatment, it is a well-known fact that the adsorbent treatment of alkylene glycol is quickly saturated, which requires a large cost for regeneration. Therefore, an efficient and economical purification method is desired for the purification of ethylene glycol containing nitrogen compounds such as dyes. When the recovered alkylene glycol is reused, it is preferable to remove impurities to the same extent as the reagent, but most of the impurities can be removed by distillation, but the polarity, molecular weight, and relative volatility of the impurities contained. Can not be separated by distillation alone.
本発明の目的は、従来技術が有していた問題点を解決し、染料に含有されている不純物として窒素化合物を含むアルキレングリコールを精製する方法を提供することにある。本発明のさらに他の目的及び利点は、以下の説明から明らかになるであろう。 An object of the present invention is to solve the problems of the prior art and to provide a method for purifying an alkylene glycol containing a nitrogen compound as an impurity contained in a dye. Other objects and advantages of the present invention will become apparent from the following description.
本発明者らは鋭意検討を行った結果、染料に含有されている不純物として窒素化合物を含むアルキレングリコールを蒸留する前にオゾンにより酸化分解を行うことにより、上記従来技術の有していた問題点を解消できることを見出し、本発明を完成するに至った。すなわち、本発明の目的は窒素化合物を含むアルキレングリコールを精製するに際し、該窒素化合物を含むアルキレングリコールに酸化剤を用いた酸化処理操作及び蒸留操作を行うことを特徴とするアルキレングリコールの精製方法を実施することにより達成することができる。 As a result of intensive studies, the present inventors have found that the above-mentioned prior art has a problem by performing oxidative decomposition with ozone before distilling alkylene glycol containing nitrogen compounds as impurities contained in the dye. As a result, the present invention has been completed. That is, an object of the present invention is to provide a method for purifying an alkylene glycol, characterized in that, when purifying an alkylene glycol containing a nitrogen compound, an oxidation treatment operation and a distillation operation using an oxidizing agent for the alkylene glycol containing the nitrogen compound are performed. This can be achieved by implementing.
本発明により、染料由来の窒素化合物を不純物として含むアルキレングリコールを精製するに際し、該アルキレングリコールをオゾンによる酸化分解と蒸留を組み合わせることにより、高純度のアルキレングリコールを得ることが可能となりその工業的価値は大である。 According to the present invention, when purifying alkylene glycol containing a nitrogen compound derived from a dye as an impurity, high-purity alkylene glycol can be obtained by combining the alkylene glycol with oxidative decomposition by ozone and distillation, and its industrial value. Is great.
本発明においては、窒素化合物を不純物として含むアルキレングリコールを精製する際に酸化剤を用いた酸化処理の後、蒸留精製することを特徴とする。酸化剤としてはオゾンを用いる事が好ましい。具体的には、オゾンによる酸化分解を行った後、蒸留を行う方法が挙げられる。また窒素化合物としてはポリエステルの染色用の染料に由来する化合物であることが好ましい。具体的には、アゾベンゼン化合物、又はアミノ基、イミノ基、アミド基、イミド基若しくは尿素基を含むアントラキノン化合物などを挙げる事ができる。 The present invention is characterized in that when an alkylene glycol containing a nitrogen compound as an impurity is purified, it is purified by distillation after an oxidation treatment using an oxidizing agent. It is preferable to use ozone as the oxidizing agent. Specifically, there is a method of performing distillation after oxidative decomposition with ozone. The nitrogen compound is preferably a compound derived from a dye for dyeing polyester. Specific examples include an azobenzene compound or an anthraquinone compound containing an amino group, an imino group, an amide group, an imide group, or a urea group.
オゾンはその強力な酸化作用を利用し、一般的には殺菌、脱臭、脱色、有機物除去、化学物質合成等の用途に使用されている。特に染料を含有する着色排水の脱色方法として以前よりオゾンによる酸化脱色法は一般的に知られている。一例として排水中でのアゾ染料のオゾン酸化機構について説明する。排水中においてヒドラゾン基として存在している染料分子中のアゾ基をオゾンにより酸化処理し、ケトンを経てカルボン酸変換することにより、一方窒素原子は窒素ガスとして分解し、脱色する技術である。一般に染料などで使用される窒素化合物は酸化処理により上記のように化学構造を変化させるものが多いと推定される。本発明の窒素化合物を含むアルキレングリコールを精製するに際し、該窒素化合物を含むアルキレングリコールをオゾンによる酸化分解工程及び蒸留工程を行うことでアルキレングリコールを精製する方法においても、アルキレングリコール中に含まれている窒素化合物がオゾン酸化により上記のような染料の酸化反応が発生し、エチレングリコールを蒸留した際に染料成分が釜残側に濃縮され、市販品と同様に高純度のエチレングリコールが回収されるものと考えられる。 Ozone uses its strong oxidizing action and is generally used for applications such as sterilization, deodorization, decolorization, organic matter removal, and chemical synthesis. In particular, an oxidative decolorization method using ozone has been generally known as a decolorization method for colored wastewater containing a dye. As an example, the mechanism of ozone oxidation of azo dyes in waste water will be described. In this technique, an azo group in a dye molecule existing as a hydrazone group in wastewater is oxidized with ozone and converted into a carboxylic acid through a ketone, whereby nitrogen atoms are decomposed as nitrogen gas and decolorized. In general, it is estimated that many nitrogen compounds used in dyes or the like change the chemical structure as described above by oxidation treatment. When purifying alkylene glycol containing nitrogen compound of the present invention, alkylene glycol containing nitrogen compound is also included in alkylene glycol in the method of purifying alkylene glycol by performing oxidative decomposition step and distillation step with ozone. Oxidation of the nitrogen compound that occurs causes the oxidation reaction of the dye as described above, and when the ethylene glycol is distilled, the dye component is concentrated on the side of the kettle and high-purity ethylene glycol is recovered in the same way as commercially available products. It is considered a thing.
以下に、本発明の実施形態を、実施例等を使用して説明する。なお、これらの実施例等及び説明は本発明を例示するものであり、本発明の範囲を制限するものではない。本発明の趣旨に合致する限り他の実施の形態も本発明の範疇に属し得ることは言うまでもない。 Hereinafter, embodiments of the present invention will be described using examples and the like. In addition, these Examples etc. and description illustrate this invention, and do not restrict | limit the scope of the present invention. It goes without saying that other embodiments may belong to the category of the present invention as long as they match the gist of the present invention.
本発明の精製方法においては、対象とするアルキレングリコールとしては、典型的には、ポリエチレンテレフタレートよりなる繊維や他のポリアルキレンテレフタレートよりなる繊維、それらのポリエチレンテレフタレート、ポリアルキレンテレフタレートの他の成形品、それらの染色された繊維、染色された成形品の廃棄物を解重合反応により得られたアルキレングリコールを例示することができるが、ナイロンや木綿等の他の素材を、混紡等の形で含んでいてもよく、表面改質等の目的のために使用される他のプラスチック成分を含んでいてもよい。 In the purification method of the present invention, as the target alkylene glycol, typically, fibers made of polyethylene terephthalate and fibers made of other polyalkylene terephthalates, their polyethylene terephthalate, other molded products of polyalkylene terephthalate, Alkylene glycols obtained by depolymerization reaction can be exemplified as wastes of those dyed fibers and dyed molded articles, but other materials such as nylon and cotton are included in the form of blended fibers, etc. It may also include other plastic components used for purposes such as surface modification.
本発明の精製方法の説明に先立ち、ケミカルリサイクルによりポリエステル廃棄物からアルキレングリコールを得る方法についてまず説明する。一般的に多量に使用されているポリエチレンテレフタレートの場合について以下詳細に説明する。解重合反応工程においては、まず対象が繊維の場合については染料で着色されている場合が多いので、染着されたポリエステル繊維から染料抽出工程において、染料を抽出・除去する。染料抽出溶剤としては、キシレン抽出溶剤とアルキレングリコール抽出溶剤を組み合わせて使用することができる。抽出溶剤として用いるアルキレングリコールは、回収・蒸留精製の工程を共通化することができること、他の物質とのコンタミネーションを防ぐ観点からポリエステルを構成しているグリコールと同じグリコール化合物を用いる事が好ましい。染料抽出済みポリエステル繊維は、解重合工程において、解重合触媒の存在下、エチレングリコールと一部の解重合反応液を追加投入して解重合反応させて、ビス（ヒドロキシエチル）テレフタレート（ＢＨＥＴ）を含む解重合液とする。次いで、解重合して得られた解重合液から蒸留によりエチレングリコールを留去し回収する。なお、この蒸留は減圧下で実施しても良い。次いで濃縮した解重合液をエステル交換反応槽に供給し、さらにメタノールとエステル交換反応触媒としての炭酸ナトリウムを所定量供給することによって、有用成分としてテレフタル酸ジメチルとエチレングリコールとに転換する。上記の操作によって生成したテレフタル酸ジメチルとエチレングリコールとの混合物は、過剰のメタノールと共に冷却し、ついで固液分離装置を用いて、エチレングリコールとメタノールとの混合液及びテレフタル酸ジメチルのケークに分離し、該混合液からメタノールを留去することによってエチレングリコールを含む釜残を得る。さらに蒸留精製することでエチレングリコールを回収することもできる。本発明の方法においては後述の様に蒸留精製前に酸化処理を行うことができる。以上の操作により、ポリエステル廃棄物からアルキレングリコールを回収することができる。 Prior to the description of the purification method of the present invention, a method for obtaining alkylene glycol from polyester waste by chemical recycling will be described first. The case of polyethylene terephthalate which is generally used in a large amount will be described in detail below. In the depolymerization reaction step, when the target is a fiber, it is often colored with a dye. Therefore, the dye is extracted and removed from the dyed polyester fiber in the dye extraction step. As the dye extraction solvent, a xylene extraction solvent and an alkylene glycol extraction solvent can be used in combination. As the alkylene glycol used as the extraction solvent, it is preferable to use the same glycol compound as the glycol constituting the polyester from the viewpoint that the steps of recovery and distillation purification can be made common and contamination with other substances is prevented. In the depolymerization step, the polyester fiber after dye extraction is subjected to depolymerization reaction by adding ethylene glycol and a part of the depolymerization reaction liquid in the presence of a depolymerization catalyst to obtain bis (hydroxyethyl) terephthalate (BHET). Including depolymerization solution. Next, ethylene glycol is removed by distillation from the depolymerization solution obtained by depolymerization and recovered. This distillation may be carried out under reduced pressure. Next, the concentrated depolymerization liquid is supplied to a transesterification reaction tank, and further, methanol and sodium carbonate as a transesterification reaction catalyst are supplied in a predetermined amount to convert them into dimethyl terephthalate and ethylene glycol as useful components. The mixture of dimethyl terephthalate and ethylene glycol produced by the above operation is cooled together with excess methanol, and then separated into a mixture of ethylene glycol and methanol and a dimethyl terephthalate cake using a solid-liquid separator. Then, methanol is distilled off from the mixed solution to obtain a kettle residue containing ethylene glycol. Further, ethylene glycol can be recovered by distillation purification. In the method of the present invention, an oxidation treatment can be performed before distillation purification as described later. By the above operation, alkylene glycol can be recovered from the polyester waste.
次に酸化剤を用いた酸化処理について説明する。この染料成分由来の窒素成分を含有するエチレングリコールを含む釜残をオゾン発生装置を使用してエチレングリコールを含む釜残量７５重量部に対してオゾンのフィード量はオゾン濃度５ｇ／Ｎｍ３以上のオゾンを１重量部から２重量部の範囲でバブリングすることが好ましい。また、本発明の方法においてオゾンとエチレングリコールを含む釜残とを反応させて酸化分解を行う反応装置の形状に特に制限はなく。オゾンとの接触時間を充分に確保できれば問題ないが、概ね３０分間から６０分間の範囲でオゾンと釜残を接触時間を確保することが好ましい。また、処理温度については特に制限はないが温度が高過ぎるとオゾンの溶解度が下がるため、常温から５０℃の範囲が好ましい。上記条件でオゾン酸化処理した後、１３．３ｋＰａ〜２６．７ｋＰａの減圧下、１４０〜１６０℃、理論段１５段以上の条件で蒸留を行う。あまりに高い温度では該エチレングリコールの脱水反応等の副反応が併発する恐れがあるため、該条件で蒸留を行うことが好ましい。該蒸留操作は回分式、連続式のいずれで行っても良い。回収したエチレングリコールはジエチレングリコール濃度、水分、溶融比色の検査項目において市販品と遜色なく、また、含有する窒素成分も２ｐｐｍ以下と窒素含有量も検出下限以下となっており、高純度の回収エチレングリコールが得ることができる。 Next, the oxidation process using an oxidizing agent will be described. The feed amount of ozone with respect to 75 parts by weight of the remaining amount of the kettle containing ethylene glycol using the ozone generator for the residue of the kettle containing ethylene glycol containing nitrogen component derived from this dye component is an ozone concentration of 5 g / Nm 3 or more. It is preferable to bubble ozone in the range of 1 to 2 parts by weight. Moreover, there is no restriction | limiting in particular in the shape of the reactor which reacts ozone and the kettle residue containing ethylene glycol in the method of this invention, and oxidatively decomposes. There is no problem as long as the contact time with ozone can be sufficiently secured, but it is preferable to secure the contact time between ozone and the residue in the range of approximately 30 minutes to 60 minutes. Further, the treatment temperature is not particularly limited, but if the temperature is too high, the solubility of ozone is lowered. After the ozone oxidation treatment under the above conditions, distillation is performed under a reduced pressure of 13.3 kPa to 26.7 kPa under conditions of 140 to 160 ° C. and 15 or more theoretical plates. If the temperature is too high, side reactions such as dehydration reaction of the ethylene glycol may occur at the same time. Therefore, it is preferable to carry out distillation under such conditions. The distillation operation may be carried out either batchwise or continuously. The collected ethylene glycol is comparable to the commercially available test items for diethylene glycol concentration, moisture, and melt colorimetry, and the nitrogen content is 2 ppm or less, and the nitrogen content is below the lower detection limit. Glycol can be obtained.
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。なお、実施例中の各数値は以下の方法により求めた。
（窒素含有量）
ポリエステル布帛並びにエチレングリコールを含む釜残、回収エチレングリコールに含まれる窒素含有量は微量全窒素分析装置（三菱化成製ＴＮ−１１０）で測定した。
Hereinafter, the contents of the present invention will be described more specifically with reference to examples. In addition, each numerical value in an Example was calculated | required with the following method.
(Nitrogen content)
The nitrogen content contained in the polyester fabric, the residue of the kettle containing ethylene glycol, and the recovered ethylene glycol was measured with a trace total nitrogen analyzer (TN-110 manufactured by Mitsubishi Kasei).
［実施例１］
染着されたポリエステル繊維である、黒色に染色されたポリエチレンテレフタレート布帛（染料抽出前の布帛中の窒素含有量：９００ｐｐｍ）を裁断したもの１００ｇとパラキシレン６００ｇとを２Ｌのセパラブルフラスコに投入して、温度１３０℃にて１０分間加熱・攪拌することによって染料を抽出する工程を実施した。
抽出終了後、固液分離工程として、アスピレーターによる吸引濾過を行い、染料を含むパラキシレンと染料を抽出した布帛（染料抽出済みポリエステル繊維）とを分離した。
[Example 1]
100 g of polyethylene terephthalate fabric dyed in black, which is dyed polyester fiber (nitrogen content in the fabric before dye extraction: 900 ppm), and 600 g of paraxylene are put into a 2 L separable flask. Then, the step of extracting the dye was carried out by heating and stirring at a temperature of 130 ° C. for 10 minutes.
After completion of the extraction, as a solid-liquid separation step, suction filtration with an aspirator was performed to separate the paraxylene containing the dye and the fabric from which the dye was extracted (polyester fiber after dye extraction).
その後、染料を抽出除去した布帛と新たなパラキシレン６００ｇとをセパラブルフラスコに投入して、染料の抽出を同条件で実施した。抽出終了後再度固液分離を行い、染料を含むパラキシレンと染料を抽出除去した布帛とを分離した。 Thereafter, the fabric from which the dye was extracted and removed and 600 g of new para-xylene were put into a separable flask, and the dye was extracted under the same conditions. After completion of the extraction, solid-liquid separation was performed again to separate the paraxylene containing the dye from the fabric from which the dye was extracted and removed.
その後、染料を抽出除去した布帛と新たなエチレングリコール６００ｇとをセパラブルフラスコに投入して、温度１７０℃にて１０分間加熱・攪拌することによって染料を抽出する工程を実施した。この時の加熱により布帛中に含液するパラキシレンの大部分はベント経由で蒸発する。蒸発したパラキシレンは冷却器により回収する。抽出終了後再度固液分離を行い、染料を含むエチレングリコールと染料を抽出除去した布帛とを分離した。 Thereafter, the fabric from which the dye was extracted and removed and 600 g of new ethylene glycol were put into a separable flask, and the dye was extracted by heating and stirring at a temperature of 170 ° C. for 10 minutes. By heating at this time, most of the paraxylene contained in the fabric evaporates via the vent. The evaporated para-xylene is recovered by a cooler. After completion of the extraction, solid-liquid separation was performed again to separate the ethylene glycol containing the dye from the fabric from which the dye was extracted and removed.
その後、解重合反応工程として、この染料抽出済み布帛１００ｇを予め１８５℃まで加熱しておいたエチレングリコール２００ｇ、既に解重合反応を実施した１２０℃〜１８０℃へ加熱した解重合反応液２００ｇ、解重合触媒としての炭酸カリウム３ｇの混合物と一緒に解重合反応器に仕込み、常圧で４時間反応させて、ビス−β−ヒドロキシエチルテレフタレート（ＢＨＥＴ）を含む解重合液を得た。 Thereafter, as a depolymerization reaction step, 100 g of this dye extracted fabric was heated to 185 ° C. in advance, 200 g of ethylene glycol, 200 g of a depolymerization reaction solution heated to 120 ° C. to 180 ° C. that had already been subjected to the depolymerization reaction, A depolymerization reactor was charged together with a mixture of 3 g of potassium carbonate as a polymerization catalyst and reacted at normal pressure for 4 hours to obtain a depolymerization solution containing bis-β-hydroxyethyl terephthalate (BHET).
なお、解重合反応工程の解重合反応後に、目開き３５０μｍ３の金網ストレーナーにより固形物をろ過除去した。この固形物除去工程では、主に、ポリエステル以外のプラスチックを除去することができた。得られたろ過後の解重合液を塔底温度１４０〜１５０℃、圧力１３．３ｋＰａの条件でエチレングリコールを１００ｇ留去して解重合溶液を濃縮する解重合溶液濃縮工程を実施した。次いで、ろ過され、濃縮された解重合溶液２００ｇに、エステル交換触媒としての炭酸カリウム１．７ｇとメタノール２００ｇとを添加して、常圧、７５〜８０℃で１時間、エステル交換反応工程を実施し、エステル交換反応生成混合物を得た。 In addition, after the depolymerization reaction in the depolymerization reaction step, the solid matter was removed by filtration with a wire mesh strainer having an opening of 350 μm 3 . In this solid matter removing step, plastics other than polyester could be mainly removed. The resulting depolymerized solution after filtration was subjected to a depolymerized solution concentration step of concentrating the depolymerized solution by distilling off 100 g of ethylene glycol under the conditions of a tower bottom temperature of 140 to 150 ° C. and a pressure of 13.3 kPa. Next, 1.7 g of potassium carbonate and 200 g of methanol as a transesterification catalyst are added to 200 g of the filtered and concentrated depolymerization solution, and the transesterification reaction step is performed at normal pressure and 75 to 80 ° C. for 1 hour. Thus, a transesterification product mixture was obtained.
反応終了後、エステル交換反応生成混合物を４０℃まで冷却し、遠心分離により粗テレフタル酸ジメチルを主成分とするケークとメタノール、粗エチレングリコールを主成分とするろ液とに固液分離した。次いで粗テレフタル酸ジメチルを圧力６．７ｋＰａ、塔底温度１８０〜２００℃にて蒸留精製して高純度テレフタル酸ジメチルを収率８５％重量で得た。また、ろ液を常圧下、塔頂温度６０〜７０℃の条件で蒸留により精製して、最終的に有用成分としてのテレフタル酸ジメチルを、次いでエチレングリコールとメタノールとの混和液からメタノールを留去することによってエチレングリコールを含む釜残を得た。さらに、該エチレングリコールを含む釜残に含まれる窒素含有量は微量全窒素分析装置(三菱化成製ＴＮ−１１０)で測定した結果、１１ｐｐｍであった。 After completion of the reaction, the transesterification reaction product mixture was cooled to 40 ° C. and subjected to solid-liquid separation by centrifugation into a cake mainly composed of crude dimethyl terephthalate and a filtrate mainly composed of crude ethylene glycol. Subsequently, crude dimethyl terephthalate was purified by distillation at a pressure of 6.7 kPa and a column bottom temperature of 180 to 200 ° C. to obtain high-purity dimethyl terephthalate at a yield of 85% by weight. In addition, the filtrate is purified by distillation under normal pressure and at a tower top temperature of 60 to 70 ° C., and finally dimethyl terephthalate as a useful component is distilled off, and then methanol is distilled off from a mixture of ethylene glycol and methanol. As a result, a residue remaining containing ethylene glycol was obtained. Furthermore, the nitrogen content contained in the kettle residue containing ethylene glycol was 11 ppm as a result of measurement with a trace total nitrogen analyzer (TN-110 manufactured by Mitsubishi Kasei).
この染料成分由来の窒素成分を１１ｐｐｍ含有するエチレングリコールを含む釜残１５０ｇをオゾン発生装置ＰＺ−１Ａ／ＫＯＦＬＯＣ製を使用して常温でオゾン発生濃度８．４ｇ／Ｎｍ３で２．０ｇ／Ｈｒの流量で６０分間バブリングを実施した。バブリング後のエチレングリコールを含む釜残１５０ｇを塔低温度１４０〜１５０℃、圧力１３．３ｋＰａ、理論段数１５段の条件で蒸留し、エチレングリコール１００ｇを留去した。回収したエチレングリコールはジエチレングリコール濃度、水分、溶融比色の検査項目において市販品と遜色なく、また、窒素成分も２ｐｐｍ以下と窒素含有量も検出下限以下となっており、高純度のエチレングリコールが得られた。 Using an ozone generator PZ-1A / KOFLOC, 150 g of the remaining residue of 150 g of ethylene glycol containing 11 ppm of nitrogen component derived from this dye component is 2.0 g / hr at an ozone generation concentration of 8.4 g / Nm 3 at room temperature. Bubbling was performed at a flow rate for 60 minutes. 150 g of the residue in the kettle containing ethylene glycol after bubbling was distilled under the conditions of a tower low temperature of 140 to 150 ° C., a pressure of 13.3 kPa, and a theoretical plate number of 15 to distill off 100 g of ethylene glycol. The collected ethylene glycol is inferior to commercially available products in diethylene glycol concentration, moisture, and melt colorimetric inspection items, and the nitrogen content is 2 ppm or less and the nitrogen content is below the detection limit, resulting in high-purity ethylene glycol. It was.
［実施例２］
実施例１で得たエステル交換反応後の生成混合物から固液分離によりテレフタル酸ジメチルケークを分離し、濾液からメタノールを留去して得たエチレングリコールを含む釜残（窒素含有量１１ｐｐｍ）を用いて実施例２の操作を以下行った。そのエチレングリコールを含む釜残１５０ｇを塔低温度１４０〜１５０℃、圧力１３．３ｋＰａ、理論段数１５段の条件で蒸留し、エチレングリコール１００ｇを留去した。その後、回収したエチレングリコールをオゾン発生装置ＰＺ−１Ａ／ＫＯＦＬＯＣ製を使用して常温でオゾン発生濃度８．４ｇ／Ｎｍ３で２．０ｇ／Ｈｒの流量で６０分間バブリングを実施した。回収したエチレングリコールはジエチレングリコール濃度、水分、溶融比色の検査項目において市販品と遜色はなかったが、５ｐｐｍの窒素を含有しており、若干の品位の低下が認められた。
[Example 2]
The dimethyl terephthalate cake was separated by solid-liquid separation from the product mixture after the transesterification obtained in Example 1, and the residue (nitrogen content 11 ppm) containing ethylene glycol obtained by distilling off methanol from the filtrate was used. Then, the operation of Example 2 was performed as follows. 150 g of the remaining residue containing ethylene glycol was distilled under conditions of a tower low temperature of 140 to 150 ° C., a pressure of 13.3 kPa, and a theoretical plate number of 15 plates, and 100 g of ethylene glycol was distilled off. Thereafter, the collected ethylene glycol was bubbled for 60 minutes at a normal temperature with an ozone generation concentration of 8.4 g / Nm 3 and a flow rate of 2.0 g / Hr using an ozone generator PZ-1A / KOFLOC. The collected ethylene glycol was not inferior to a commercially available product in the inspection items of diethylene glycol concentration, water content, and melt colorimetry, but contained 5 ppm of nitrogen, and a slight deterioration in quality was observed.
[比較例１]
実施例１で得たエチレングリコールを含む釜残１５０ｇをオゾン発生装置ＰＺ−１Ａ／ＫＯＦＬＯＣ製を使用して常温でオゾン発生濃度８．４ｇ／Ｎｍ３で２．０ｇ／Ｈｒの流量で６０分間バブリングを実施し、蒸留は行わなかった。バブリング後の釜残窒素農度は１１ｐｐｍとオゾンバブリング前と変化がなかった。
[Comparative Example 1]
Using the ozone generator PZ-1A / KOFLOC, 150 g of the remaining residue containing ethylene glycol obtained in Example 1 was bubbled at an ozone generation concentration of 8.4 g / Nm 3 at a flow rate of 2.0 g / Hr for 60 minutes. And no distillation was performed. After bubbling, the residue of nitrogen in the kettle was 11 ppm, unchanged from that before ozone bubbling.
[比較例２]
実施例１で得たエチレングリコールを含む釜残１５０ｇをオゾン発生装置ＰＺ−１Ａ／ＫＯＦＬＯＣ製を使用して常温で２．０ｇ／Ｈｒの流量で６０分バブリングを実施し、バブリング後のエチレングリコールを含む釜残を液相用の活性炭にＳＶ＝２（２０ｇ/Ｈｒ）で吸着させたが回収した釜残の窒素濃度は１１ｐｐｍとオゾンバブリングと活性炭による吸着効果は認められなかった。
[Comparative Example 2]
150 g of the residue containing ethylene glycol obtained in Example 1 was bubbled for 60 minutes at a flow rate of 2.0 g / Hr at room temperature using an ozone generator PZ-1A / KOFLOC, and the ethylene glycol after bubbling was The remaining residue was adsorbed on activated carbon for liquid phase at SV = 2 (20 g / Hr), but the nitrogen concentration of the recovered residue was 11 ppm, and no adsorption effect by ozone bubbling and activated carbon was observed.
本発明により、染料由来の窒素化合物を不純物として含むアルキレングリコールを精製するに際し、該アルキレングリコールをオゾンによる酸化分解と蒸留を組み合わせることにより、高純度のアルキレングリコールを得ることが可能となりその工業的価値は大である。 According to the present invention, when purifying alkylene glycol containing a nitrogen compound derived from a dye as an impurity, high-purity alkylene glycol can be obtained by combining the alkylene glycol with oxidative decomposition by ozone and distillation, and its industrial value. Is great.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2013035559A1 (en) * | 2011-09-06 | 2013-03-14 | 東レ株式会社 | Polyester with excellent heat resistance and method for producing same |
| IT201900025039A1 (en) * | 2019-12-20 | 2021-06-20 | Garbo S R L | PROCESS TO PURIFY BIS (2-HYDROXYETHYL) TEREPHTHALATE. |
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| JPH11197679A (en) * | 1998-01-19 | 1999-07-27 | Fuji Photo Film Co Ltd | Method for decoloring yellow dye by azo dye and ozone |
| JP2004144729A (en) * | 2002-08-28 | 2004-05-20 | Nippon Telegr & Teleph Corp <Ntt> | Element, apparatus, and method for detecting gaseous ozone |
| JP2007045874A (en) * | 2005-08-08 | 2007-02-22 | Teijin Fibers Ltd | Method for recovering effective component from dyed polyester fiber |
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| JPH11197679A (en) * | 1998-01-19 | 1999-07-27 | Fuji Photo Film Co Ltd | Method for decoloring yellow dye by azo dye and ozone |
| JP2004144729A (en) * | 2002-08-28 | 2004-05-20 | Nippon Telegr & Teleph Corp <Ntt> | Element, apparatus, and method for detecting gaseous ozone |
| JP2007045874A (en) * | 2005-08-08 | 2007-02-22 | Teijin Fibers Ltd | Method for recovering effective component from dyed polyester fiber |
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| JPN6012038747; 日本化学会誌 Ｎｏ．８, ｐ．１１２４-１１２６ （１９７９）． * |
| JPN6012038748; ＳＥＮ'Ｉ ＧＡＫＫＡＩＳＨＩ（繊維と工業） Ｖｏｌ．６３， Ｎｏ．１０, ｐ．Ｐ-３５０-Ｐ-３５３ （２００７）． * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013035559A1 (en) * | 2011-09-06 | 2013-03-14 | 東レ株式会社 | Polyester with excellent heat resistance and method for producing same |
| JP5316725B1 (en) * | 2011-09-06 | 2013-10-16 | 東レ株式会社 | Polyester having excellent heat resistance and method for producing the same |
| US9175133B2 (en) | 2011-09-06 | 2015-11-03 | Toray Industries, Inc. | Polyester with excellent thermostability and manufacturing method therefor |
| IT201900025039A1 (en) * | 2019-12-20 | 2021-06-20 | Garbo S R L | PROCESS TO PURIFY BIS (2-HYDROXYETHYL) TEREPHTHALATE. |
| WO2021124149A1 (en) * | 2019-12-20 | 2021-06-24 | Garbo S.R.L. | Process for purifying bis(2-hydroxyethyl)terephthalate |
| CN114746391A (en) * | 2019-12-20 | 2022-07-12 | 嘉尔宝有限责任公司 | Process for purifying bis (2-hydroxyethyl) terephthalate |
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| JP5242999B2 (en) | 2013-07-24 |
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