JP2007131695A - Method for separating foreign material - Google Patents
Method for separating foreign material Download PDFInfo
- Publication number
- JP2007131695A JP2007131695A JP2005324528A JP2005324528A JP2007131695A JP 2007131695 A JP2007131695 A JP 2007131695A JP 2005324528 A JP2005324528 A JP 2005324528A JP 2005324528 A JP2005324528 A JP 2005324528A JP 2007131695 A JP2007131695 A JP 2007131695A
- Authority
- JP
- Japan
- Prior art keywords
- depolymerization
- liquid
- separating
- polyester
- sedimentation
- 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
- 239000000463 material Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000012691 depolymerization reaction Methods 0.000 claims abstract description 42
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 38
- -1 alkylene glycol Chemical compound 0.000 claims abstract description 35
- 229920000728 polyester Polymers 0.000 claims abstract description 35
- 239000002699 waste material Substances 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 238000000926 separation method Methods 0.000 claims abstract description 20
- 229920001283 Polyalkylene terephthalate Polymers 0.000 claims abstract description 14
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 13
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 238000004062 sedimentation Methods 0.000 claims description 23
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 17
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 17
- 230000001174 ascending effect Effects 0.000 abstract 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 230000005484 gravity Effects 0.000 description 14
- 239000011521 glass Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 239000004576 sand Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000000630 rising effect Effects 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000004698 Polyethylene Substances 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 5
- 239000004480 active ingredient Substances 0.000 description 5
- 239000004567 concrete Substances 0.000 description 5
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 2
- 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
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 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 1
- 235000014171 carbonated beverage Nutrition 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- BTVWZWFKMIUSGS-UHFFFAOYSA-N dimethylethyleneglycol Natural products CC(C)(O)CO BTVWZWFKMIUSGS-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution 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
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000004246 zinc acetate Substances 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 Of Solids By Using Liquids Or Pneumatic Power (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
Description
本発明は、ポリアルキレンテレフタレートを主成分として含有するポリエステル廃棄物から有効成分を回収する方法に関し、さらに詳しくは、ポリエステル廃棄物に含まれる異種素材を沈降分離装置を経由させて分離除去する方法に関する。 The present invention relates to a method for recovering active ingredients from polyester waste containing polyalkylene terephthalate as a main component, and more particularly, to a method for separating and removing different materials contained in polyester waste via a sedimentation separator. .
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。 Since polyethylene terephthalate is excellent in chemical stability, its use in food fields such as life-related materials such as fibers, films and resins, drinking water, bottles for carbonated beverages and the like is rapidly increasing.
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（特に使用済みの飲料用ボトル）、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、ポリエステル廃棄物と略称することがある。）の処理は、大きな社会問題となっている。 However, used polyethylene terephthalate (especially used beverage bottles) generated in large quantities due to the increase in the amount used as described above, or quality ineligible products generated in the polyethylene terephthalate manufacturing stage (hereinafter referred to as polyester waste) Is a big social problem.
上記の問題に対して、ポリエステル廃棄物をモノマーに変換・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 problems, so-called chemical recycling in which polyester waste is converted and recovered into a monomer and polyethylene terephthalate is produced and reused by a polymerization reaction using this monomer as a raw material has been studied. In this method, there is basically no loss, the compound can be reused and the resources can be reused.
これら回収したポリエステル廃棄物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エステル交換反応を行い、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。 These recovered polyester wastes are depolymerized with ethylene glycol, then transesterified with methanol, and further separated and purified to dimethyl terephthalate (hereinafter sometimes abbreviated as DMT) and ethylene glycol. (Hereinafter, it may be abbreviated as EG.), Leading to effective use of resources and a reduction in total cost.
ポリエチレンテレフタレートに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（以下、ＢＨＥＴと略称することがある。）および末端に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（以下、ＭｅＯＨと略称することがある。）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（例えば特許文献１参照。）。 Low polymer containing bis-β-hydroxyethyl terephthalate (hereinafter sometimes abbreviated as BHET) and β-hydroxyethyl ester group at the terminal by depolymerization reaction by adding ethylene glycol in excess to polyethylene terephthalate and heating. Is obtained by adding an excess of methanol (hereinafter sometimes abbreviated as MeOH) to the mixture and subjecting it to a substitution esterification reaction in the presence of a catalyst. (For example, refer to Patent Document 1.)
また、ポリエステル廃棄物からテレフタル酸ジメチル及びエチレングリコールを分離回収する方法において、得られた解重合反応液中に含まれる固形異種素材のうち、反応溶液の表面に浮遊するものは浮遊選別により分離し、反応溶液の表面に浮遊しなかったもの、例えば、金属、土砂、ガラス、無機化合物、ポリ塩化ビニル、ポリ塩化ビニリデン、アクリル、レーヨン、アセテートなどについては、固液分離法により除去する方法が提案されている（例えば特許文献２参照。）。しかしながら、該解重合反応液の固液分離方法に関する具体的な記載はなく、高温溶液中から、効率的に解重合反応液の表面に浮遊しない固形異種素材を分離する方法については、具体的な方法を選択する必要がある。 In the method of separating and recovering dimethyl terephthalate and ethylene glycol from polyester waste, among the solid different materials contained in the obtained depolymerization reaction solution, those floating on the surface of the reaction solution are separated by floating sorting. For those that did not float on the surface of the reaction solution, such as metals, earth and sand, glass, inorganic compounds, polyvinyl chloride, polyvinylidene chloride, acrylic, rayon, acetate, etc., a method of removing by solid-liquid separation was proposed. (For example, refer to Patent Document 2). However, there is no specific description regarding the solid-liquid separation method of the depolymerization reaction solution, and a specific method for separating a solid foreign material that does not float on the surface of the depolymerization reaction solution from a high-temperature solution is described in detail. You need to choose a method.
これら解重合反応液よりも比重の重い固形異種素材が、継続的に解重合槽へ混入すると、塔槽類で堆積して溶液の取り出し不良の発生や、配管、調節弁、流量計などの閉塞が発生し、工程停止を余技なくされる場合がある。更に解重合反応が完全でなく、有効成分である未反応ＰＥＴが解重合液中に存在する場合は、一般的な固液分離法、例えば濾過法、遠心分離法、沈降法などでは、固形異種素材と共に、未反応ＰＥＴが同伴して系外に排出されるので、有効成分ロスによる工程歩留まりの悪化が発生する。 If these different types of solid materials with a higher specific gravity than the depolymerization reaction liquid are continuously mixed in the depolymerization tank, they will accumulate in the tower tanks, causing problems in taking out the solution, and clogging of piping, control valves, flow meters, etc. May occur, and there is a case where the process is stopped without much work. Furthermore, when the depolymerization reaction is not complete and unreacted PET as an active ingredient is present in the depolymerization solution, solid solid-liquid separation methods such as filtration, centrifugation, sedimentation, etc. Since unreacted PET is discharged together with the raw material, the process yield deteriorates due to loss of active ingredients.
本発明の目的は、従来技術が有していた問題点を解決し、ポリエステル廃棄物中に含まれる異物、特に解重合反応液よりも比重が重い異種素材を、有効成分の歩留まりを低下させず、且つ安全に分離除去する方法を確立することにある。 The object of the present invention is to solve the problems of the prior art, and to prevent foreign materials contained in polyester waste, particularly foreign materials having a higher specific gravity than the depolymerization reaction solution, without reducing the yield of active ingredients. And to establish a safe separation and removal method.
本発明者らは上記従来技術に鑑み、鋭意検討を行った結果、本発明を完成するに至った。すなわち、本発明の目的は、沈降分離時の液流れが装置下方から上方へ移動する沈降分離装置が接続された解重合反応槽内に、ポリアルキレンテレフタレートを主成分とし、ポリアルキレンテレフタレート以外の異種素材を含むポリエステル廃棄物を投入し、アルキレングリコールを添加して該ポリエステルの一部または全部を解重合反応させ解重合反応液を得た後、沈降分離装置を解重合反応液の滞留時間が５秒から３００秒、かつ解重合反応液の上昇速度が５０〜３００ｍｍ／秒にて経由させて、異種素材を連続的に分離させながら次工程へ送液することを特徴とするポリエステル廃棄物からの異種素材分離方法によって達成することができる。 As a result of intensive studies in view of the above-described prior art, the present inventors have completed the present invention. That is, an object of the present invention is to provide a polypolymer terephthalate as a main component in a depolymerization reaction tank connected to a sedimentation separator in which the liquid flow during sedimentation separation moves from the lower side to the upper side. The polyester waste containing the raw material is added, and alkylene glycol is added to depolymerize a part or all of the polyester to obtain a depolymerization reaction solution. From the polyester waste, characterized in that the liquid is fed to the next step while continuously separating the different materials through the rising speed of the depolymerization reaction solution from 50 to 300 mm / second from 300 seconds to 300 seconds. This can be achieved by a heterogeneous material separation method.
本発明の分離方法により、回収目的とするポリアルキレンテレフタレートより高比重の異種成分を効果的の取り除くことができ、有効成分の回収と工程ロス防止を図ることができる。 According to the separation method of the present invention, different components having higher specific gravity than the polyalkylene terephthalate to be recovered can be effectively removed, and the recovery of active components and the prevention of process loss can be achieved.
以下に、本発明の実施の形態を実施例などを使用して説明する。尚、これらの実施例など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形態も本発明の範疇に属し得ることは言うまでも無い。 Hereinafter, embodiments of the present invention will be described with reference to examples. 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.
本発明の異種素材分離方法において、ポリアルキレンテレフタレートとはテレフタル酸もしくはその誘導体とアルキレングリコールから当業者が通常の製造方法で得ることができるポリアルキレンテレフタレートを指す。好ましくは後述のポリエステル廃棄物中、８０重量％以上がポリアルキレンテレフタレートであることを示す。またポリエステル廃棄物中のポリエステルとはポリエチレンテレフタレート、ポリトリメチレンテレフタレート、ポリブチレンテレフタレートなどのポリアルキレンテレフタレートが具体的にあげられるが、市場の流通及び経済性の面よりポリエチレンテレフタレートが多く使用されておりかつ好ましく用いられる。また解重合反応にはアルキレングリコールを用いるのが好ましいが、そのアルキレングリコールとは具体的にはエチレングリコール、プロピレングリコール、テトラメチレングリコール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール等が挙げられるが、これらのなかでもエチレングリコールを用いるのが好ましい。この解重合反応に用いるアルキレングリコールとポリアルキレンテレフタレートを構成するアルキレン基は同じ基であることが好ましいが、異なる基であっても本発明の目的を達成することが出来る。また本発明におけるポリエステル廃棄物とはポリエステル以外には、ポリエチレン、ポリプロピレン、ポリスチレン、ポリアクリレート、ポリメタクリレート、ポリ塩化ビニル、ポリ酢酸ビニル、ポリアクリロニトリル等のポリオレフィン、ナイロン、ポリカーボネート等のポリエステル以外の重縮合ポリマー、金属、土砂、ガラス、コンクリート等を含んでいるものを指す。 In the heterogeneous material separation method of the present invention, polyalkylene terephthalate refers to polyalkylene terephthalate that can be obtained from terephthalic acid or a derivative thereof and alkylene glycol by a usual production method. Preferably, 80% by weight or more of the polyester waste described later indicates polyalkylene terephthalate. Polyester in polyester waste specifically includes polyalkylene terephthalates such as polyethylene terephthalate, polytrimethylene terephthalate, and polybutylene terephthalate, but polyethylene terephthalate is often used from the viewpoint of market distribution and economy. And preferably used. In addition, alkylene glycol is preferably used for the depolymerization reaction, and specific examples of the alkylene glycol include ethylene glycol, propylene glycol, tetramethylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol. Of these, ethylene glycol is preferably used. The alkylene glycol and the alkylene group constituting the polyalkylene terephthalate used in this depolymerization reaction are preferably the same group, but the object of the present invention can be achieved even if they are different groups. In addition to polyester, the polyester waste in the present invention is a polycondensation other than polyester, such as polyethylene, polypropylene, polystyrene, polyacrylate, polymethacrylate, polyvinyl chloride, polyvinyl acetate, polyacrylonitrile, and the like, and nylon, polycarbonate, etc. It includes polymers, metals, earth and sand, glass, concrete, etc.
本発明の方法においては、ポリエステル廃棄物は一般に水洗浄及び粗粉砕などの前処理を施し、解重合反応に適した形状にしてから解重合反応槽に投入し、解重合することが好ましい。本発明の方法を回分方式で実施する場合においては、前記ポリエステル廃棄物を、ポリエステル解重合触媒を含みアルキレングリコールが主成分である溶液中に投入して、１５０〜１９０℃の温度、０．１〜０．５ＭＰａの圧力下において解重合反応を行うのが好ましい。また解重合反応槽には沈降分離時の液流れが装置下方から上方へ移動する沈降分離装置が接続されている。後述のように比重の中程度の物質が主成分であり、比重の小さい物質と大きい物質が混合している際に、これらから主成分を分離する際には、比重の小さい物質を取り除き、その後比重の大きい物質と中程度の物質を分離する際には、この構成が好ましい。解重合を行うとアルキレングリコールとポリエステル廃棄物は解重合反応液となる。この解重合反応液となるのはポリエステル廃棄物中のポリエステルが完全に解重合された状態はもちろんのこと、一部のポリエステルのみ解重合され、まだ解重合されていないポリエステルが残っている状態も含むものである。この時使用するアルキレングリコール量は、前記ポリエステル廃棄物の重量の０．５〜２０重量倍とすることが好ましい。またこの際用いるアルキレングリコールとしてエチレングリコールを用いるのが好ましい。またこのときに用いる解重合触媒としては、アルカリ金属の炭酸塩、水酸化物、若しくは酢酸塩、アルカリ土類金属の炭酸塩、水酸化物、若しくは酢酸塩、またはマンガン、若しくは亜鉛の酢酸塩よりなる群から少なくとも１種選ばれる化合物を用いるのが好ましい。該解重合反応槽には、解重合反応を促進させるために撹拌機や解重合反応槽の解重合反応液の自己循環ライン等が設置されていることが好ましい。本発明の除去方法は連続方式又は回分方式のいずれにも採用できる。 In the method of the present invention, it is preferable that the polyester waste is generally subjected to pretreatment such as water washing and coarse pulverization to form a shape suitable for the depolymerization reaction, and then put into a depolymerization reaction tank for depolymerization. In the case where the method of the present invention is carried out in a batch system, the polyester waste is put into a solution containing a polyester depolymerization catalyst and containing alkylene glycol as a main component, at a temperature of 150 to 190 ° C., 0.1 It is preferable to perform the depolymerization reaction under a pressure of ˜0.5 MPa. The depolymerization reaction tank is connected to a sedimentation separation device in which the liquid flow during sedimentation separation moves upward from below the device. As described later, a substance with a medium specific gravity is the main component. When a substance with a low specific gravity is mixed with a substance with a large specific gravity, when the main component is separated from these substances, the substance with a low specific gravity is removed. This configuration is preferable when a substance having a large specific gravity and a medium substance are separated. When depolymerization is performed, the alkylene glycol and the polyester waste become a depolymerization reaction solution. This depolymerization reaction liquid is not only in the state where the polyester in the polyester waste is completely depolymerized, but also in the state where only a part of the polyester is depolymerized and the polyester that has not yet been depolymerized remains. Is included. The amount of alkylene glycol used at this time is preferably 0.5 to 20 times the weight of the polyester waste. Moreover, it is preferable to use ethylene glycol as the alkylene glycol used in this case. The depolymerization catalyst used at this time is an alkali metal carbonate, hydroxide or acetate, an alkaline earth metal carbonate, hydroxide or acetate, or manganese or zinc acetate. It is preferable to use at least one compound selected from the group consisting of In order to promote the depolymerization reaction, the depolymerization reaction tank is preferably provided with a stirrer, a self-circulation line for the depolymerization reaction liquid in the depolymerization reaction tank, and the like. The removal method of the present invention can be employed in either a continuous method or a batch method.
この解重合反応時において、ポリエステル廃棄物に含まれる異種素材としては、解重合反応液に対して比重の小さいポリエチレン、ポリプロピレン、ポリスチレン等のポリオレフィンを主成分とする異種プラスチックや、比重の大きい各種金属、土砂、ガラス、コンクリート粒子等が挙げられる。 In this depolymerization reaction, the dissimilar materials contained in the polyester waste include dissimilar plastics mainly composed of polyolefin such as polyethylene, polypropylene, polystyrene, etc., which have a low specific gravity with respect to the depolymerization reaction solution, and various metals with a high specific gravity. , Earth and sand, glass, concrete particles and the like.
これらの液面近傍に浮遊した異種プラスチックは、解重合反応槽の抜き出し口近くに集めた後、解重合反応槽外に抜き出すことにより除去する。この除去については、解重合反応が完全に終了していない段階でも、異種プラスチックが充分に分離できるほど液面近傍に浮遊している状態、すなわち未反応のポリエステル廃棄物中のポリエステルが残存したスラリー状態であっても実施可能である。このような除去方法を採用することで、比重の小さい異種プラスチックを効率よく、また短時間で除去することが出来、リサイクル工程全体の処理速度の向上が期待できる。 These foreign plastics floating in the vicinity of the liquid level are collected by being collected near the outlet of the depolymerization reaction tank and then removed by removing them from the depolymerization reaction tank. About this removal, even in the stage where the depolymerization reaction is not completely completed, the slurry is floating in the vicinity of the liquid surface so that the different plastics can be sufficiently separated, that is, the slurry in which the polyester in the unreacted polyester waste remains. It can be implemented even in a state. By adopting such a removal method, it is possible to efficiently remove different types of plastics having a small specific gravity in a short time, and an improvement in the processing speed of the entire recycling process can be expected.
一方、解重合反応液に対して比重が重く浮遊しない、金属、土砂、ガラス、コンクリート粒子などの異種素材については、解重合反応終了後に沈降分離槽に送り、通過液（解重合反応液）の滞留時間が５秒から３００秒、かつ解重合反応液の上昇速度が５０〜３００ｍｍ／秒以下、更に好ましくは５０から１００ｍｍ／秒に制御された沈降分離装置（沈降分離槽）を経由させて解重合反応液より比重の大きい連続的に異種素材を分離させながら次工程へ送液しながら分離する必要がある。沈降分離装置内の液流れが装置下方から上方へ移動することがより好ましい。解重合反応液が当該適正な上昇速度に保たれた範囲であれば、液流れが上方へ移動する場合には金属、土砂、ガラス、コンクリート粒子などの異種素材は沈降分離装置の下部へ沈積し、解重合液および未反応ＰＥＴは沈降せずに次工程へと送液される。 On the other hand, for different materials such as metals, earth and sand, glass, and concrete particles that have a heavy specific gravity with respect to the depolymerization reaction liquid and do not float, they are sent to the settling tank after the completion of the depolymerization reaction and passed through (depolymerization reaction liquid). Dissolution is carried out via a sedimentation separation apparatus (sedimentation separation tank) in which the residence time is 5 seconds to 300 seconds and the rising speed of the depolymerization reaction liquid is controlled to 50 to 300 mm / second or less, more preferably 50 to 100 mm / second. It is necessary to separate the different materials with higher specific gravity than the polymerization reaction solution while separating them while feeding them to the next step. It is more preferable that the liquid flow in the sedimentation / separation apparatus moves from the lower side to the upper side. If the depolymerization reaction liquid is in the range where the appropriate rising speed is maintained, dissimilar materials such as metal, earth and sand, glass and concrete particles will be deposited at the bottom of the settling separator when the liquid flow moves upward. The depolymerized solution and unreacted PET are sent to the next step without sedimentation.
沈降分離装置内で上昇する液流れ速度の制御方法は、解重合槽取出し流量、沈降分離装置を経由して解重合槽へ戻る循環流量、次工程送液流量の３点のうち、２点を計測すれば、沈降分離装置内の上昇液速度の制御が可能である。また、解重合取り出し流量が常時一定の場合は、沈降分離装置の内径と容量を適正サイズに設計することで、効果的な上昇液速度を保つことが可能である。 The control method of the liquid flow rate rising in the sedimentation separator is as follows: 2 points out of the 3 points of the depolymerization tank discharge flow rate, the circulation flow rate returning to the depolymerization tank via the sedimentation separation device, and the next process liquid feed flow rate. If measured, the rising liquid speed in the sedimentation separator can be controlled. Further, when the depolymerization take-off flow rate is always constant, it is possible to maintain an effective rising liquid speed by designing the inner diameter and capacity of the sedimentation separator to an appropriate size.
装置内に沈降した金属、土砂、ガラス、コンクリート粒子など異種素材の取り出し操作は、密閉されたスクリューコンベアなどで連続的に取り出しても良いし、沈降分離装置を２系列以上保有させて回分式で切替えながら取り出しても良い。回分式の場合は、沈降した異種素材を取り出す前に、分離装置内にある溶液を抜く必要があり、金網を装置底部に設置すると、圧力輸送などで沈降分離装置内の溶液を解重合槽に戻すことが可能となり、沈降異種素材の捕集と、有効成分の回収を行い、工程ロス防止を図ることができる。 The operation of taking out different materials such as metal, earth and sand, glass and concrete particles that have settled in the apparatus may be taken out continuously with a sealed screw conveyor or the like. You may take out while switching. In the case of a batch type, it is necessary to remove the solution in the separation device before removing the settled foreign material.If a wire mesh is installed at the bottom of the device, the solution in the precipitation separation device is transferred to the depolymerization tank by pressure transportation or the like. It is possible to return the material, and it is possible to collect the sedimented foreign material and collect the active ingredient to prevent the process loss.
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ら限定を受けるものではない。 Hereinafter, the content of the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.
[実施例１]
ポリエチレンテレフタレート廃棄物５０部、ポリスチレン２部、ポリエチレン２部、エチレングリコール２００部と解重合触媒として炭酸ナトリウム１．５部を投入し、１００ｒｐｍ攪拌下、１８０℃で１時間保持した。この時点で、投入したポリエチレンテレフタレートの一部は反応し、未反応分ＰＥＴと、金属、土砂、ガラスなどの固形物は攪拌された液中に浮遊した状態であり、ポリスチレン及びポリエチレンは液面に浮遊した。回転数を５ｒｐｍまで低下させ、浮遊物を一箇所に集積させて、上部の液２０部を分離槽に抜出したところ、ポリスチレン及びポリエチレンは解重合反応槽から完全に抜出した。
[Example 1]
50 parts of polyethylene terephthalate waste, 2 parts of polystyrene, 2 parts of polyethylene, 200 parts of ethylene glycol and 1.5 parts of sodium carbonate as a depolymerization catalyst were added and kept at 180 ° C. for 1 hour with stirring at 100 rpm. At this point, a portion of the polyethylene terephthalate that has been charged has reacted, and the unreacted PET and solids such as metal, earth, and glass are floating in the stirred liquid, and polystyrene and polyethylene are on the liquid surface. Floated. The number of rotations was reduced to 5 rpm, the suspended matter was accumulated in one place, and 20 parts of the upper liquid was extracted into the separation tank. Polystyrene and polyethylene were completely extracted from the depolymerization reaction tank.
次いで、解重合反応液を定量ポンプを用い、通過液の滞留時間１０秒、下方から上方へ移動する液上昇速度を７０ｍｍ／秒に設定した沈降分離装置を経由させて、解重合反応槽から全量抜き出した。沈降分離装置では、金属、土砂、ガラス混合物０．３部が捕集され、未反応ＰＥＴは確認されなかった。また、沈降分離装置を経由させた後の未反応ＰＥＴを含む解重合反応液には、金属、土砂、ガラスなどの固形混合物は全く含まれなかった。 Next, the depolymerization reaction liquid is completely discharged from the depolymerization reaction tank through a sedimentation separator in which the residence time of the passing liquid is set to 10 seconds and the liquid rising speed moving from below to 70 mm / second is set using a metering pump. Extracted. In the sedimentation separator, 0.3 parts of metal, earth and sand, and glass mixture were collected, and unreacted PET was not confirmed. In addition, the depolymerization reaction solution containing unreacted PET after passing through the sedimentation separator did not contain any solid mixture such as metal, earth and sand, and glass.
[比較例１]
実施例１において、下方から上方へ移動する液上昇速度を３５０ｍｍ／秒に設定した沈降分離装置を経由させて、解重合反応槽から全量抜き出したところ、金属、土砂、ガラス混合物は沈降分離槽内で捕集されず、解重合反応液と共に全量同伴した。
[Comparative Example 1]
In Example 1, when the total amount was extracted from the depolymerization reaction tank through a sedimentation separator with the liquid rising speed moving from below to 350 mm / sec, the metal, earth and sand, and the glass mixture were in the sedimentation tank. In this case, the whole amount was accompanied with the depolymerization reaction solution.
［比較例２］
実施例１において、下方から上方へ移動する液上昇速度を４０ｍｍ／秒に設定した沈降分離装置を経由させたところ、未反応ＰＥＴが全量沈降分離装置内で金属、土砂、ガラス混合物と共に沈降し、歩留まりが悪化するのが確認された。
[Comparative Example 2]
In Example 1, when passing through a sedimentation separator whose liquid rising speed moving from the bottom to the top was set to 40 mm / second, unreacted PET settled together with the metal, earth and sand, and glass mixture in the sedimentation separator. It was confirmed that the yield deteriorated.
本発明の分離方法により、回収目的とするポリアルキレンテレフタレートより高比重の異種成分を効果的の取り除くことができ、有効成分の回収と工程ロス防止を図ることができる。その結果一旦石油資源から合成したポリアルキレンテレフタレートを回収・再使用することが出来るので、環境に負荷をかけることを少なくすることにつながり工業的な意義は大きい。 According to the separation method of the present invention, different components having higher specific gravity than the polyalkylene terephthalate to be recovered can be effectively removed, and the recovery of active components and the prevention of process loss can be achieved. As a result, the polyalkylene terephthalate once synthesized from petroleum resources can be recovered and reused, which reduces the burden on the environment and has great industrial significance.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005324528A JP4773799B2 (en) | 2005-11-09 | 2005-11-09 | Method for separating different materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005324528A JP4773799B2 (en) | 2005-11-09 | 2005-11-09 | Method for separating different materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2007131695A true JP2007131695A (en) | 2007-05-31 |
| JP4773799B2 JP4773799B2 (en) | 2011-09-14 |
Family
ID=38153613
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005324528A Expired - Fee Related JP4773799B2 (en) | 2005-11-09 | 2005-11-09 | Method for separating different materials |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4773799B2 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1158382A (en) * | 1997-08-21 | 1999-03-02 | Kawasaki Heavy Ind Ltd | Method and device for separating resin waste |
| JP2000169623A (en) * | 1998-12-10 | 2000-06-20 | Is:Kk | Chemical recycle of polyethylene terephthalate waste |
| WO2001030729A1 (en) * | 1999-10-22 | 2001-05-03 | Teijin Limited | Method for separating and recovering dimethyl terephthalate and ethylene glycol from polyester waste |
| JP2002167357A (en) * | 2000-11-30 | 2002-06-11 | Teijin Ltd | Method for recovering effective component from polyester waste |
| JP2005132901A (en) * | 2003-10-29 | 2005-05-26 | Teijin Fibers Ltd | Method for removing foreign material from aliphatic polyester |
-
2005
- 2005-11-09 JP JP2005324528A patent/JP4773799B2/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1158382A (en) * | 1997-08-21 | 1999-03-02 | Kawasaki Heavy Ind Ltd | Method and device for separating resin waste |
| JP2000169623A (en) * | 1998-12-10 | 2000-06-20 | Is:Kk | Chemical recycle of polyethylene terephthalate waste |
| WO2001030729A1 (en) * | 1999-10-22 | 2001-05-03 | Teijin Limited | Method for separating and recovering dimethyl terephthalate and ethylene glycol from polyester waste |
| JP2002167357A (en) * | 2000-11-30 | 2002-06-11 | Teijin Ltd | Method for recovering effective component from polyester waste |
| JP2005132901A (en) * | 2003-10-29 | 2005-05-26 | Teijin Fibers Ltd | Method for removing foreign material from aliphatic polyester |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4773799B2 (en) | 2011-09-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6706843B1 (en) | Method for separating and recovering dimethyl terephthalate and ethylene glycol from polyester waste | |
| US6410607B1 (en) | Glycolysis process for recycling of post-consumer pet | |
| JP3459919B2 (en) | Method for removing foreign matter from post-consumer polyethylene terephthalate feed streams | |
| KR101561528B1 (en) | Method for chemical recycling of pet wastes | |
| JP2002509962A (en) | An improved method for converting contaminated polyethylene terephthalate to decontaminated polybutylene terephthalate | |
| US20220396680A1 (en) | Method of Separating a First Contaminant from a Feed Stream and Reactor System for Carrying Out the Method | |
| CN114651039B (en) | Method for treating waste material and reactor system therefor | |
| CN103360260A (en) | Preparation technology of ethylene glycol terephthalate and preparation method of polyester | |
| JP4212799B2 (en) | Method for recovering terephthalic acid from polyester fiber waste | |
| JP2015021054A (en) | Method for recovering effective component from mixture of aliphatic polyolefin and polyalkylene aromatic dicarboxylate | |
| JP4773799B2 (en) | Method for separating different materials | |
| JP2009173554A (en) | Method for recovering dimethyl terephthalate having improved hue from pet bottle waste | |
| JP2005002161A (en) | Method for removing different kind of plastic | |
| JP4071655B2 (en) | How to remove different plastics | |
| JP4065659B2 (en) | Method for recovering active ingredients from polyethylene terephthalate waste | |
| JP2005007780A (en) | Method for removing different kind of plastic | |
| CN115335443A (en) | Method for producing regenerated resin | |
| JP2009120766A (en) | Method for recovering dimethyl terephthalate and ethylene glycol | |
| JP2005014279A (en) | Separation method of plastic of different kind | |
| CN100503700C (en) | A method for the decontamination of polyethylene terephthalate | |
| CN210620672U (en) | Refining device of crude polyethylene wax | |
| JP2003300915A (en) | Method for producing monomer from polyalkylene terephthalate | |
| Anwar et al. | Production of Terephthalic Acid from Waste Polyethylene Terephthalate) Materials | |
| WO2010110434A1 (en) | Method for decomposing and recovering thermoset resin | |
| JP2004284022A (en) | Method for crushing polyester waste |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20080827 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20100818 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100824 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20101022 |
|
| A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A712 Effective date: 20110202 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20110315 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20110512 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20110531 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20110624 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140701 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| LAPS | Cancellation because of no payment of annual fees |