JPS5813089B2 - Recovery method for plasticizer in soft vinyl chloride - Google Patents
Recovery method for plasticizer in soft vinyl chlorideInfo
- Publication number
- JPS5813089B2 JPS5813089B2 JP10787380A JP10787380A JPS5813089B2 JP S5813089 B2 JPS5813089 B2 JP S5813089B2 JP 10787380 A JP10787380 A JP 10787380A JP 10787380 A JP10787380 A JP 10787380A JP S5813089 B2 JPS5813089 B2 JP S5813089B2
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- plasticizer
- soft vinyl
- extraction
- solvent
- 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.)
- Expired
Links
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Description
【発明の詳細な説明】
本発明は軟質塩化ビニル中に含有される可塑剤の回収方
法に関し、詳しくは抽出溶媒の種類を調節することによ
り軟質塩化ビニル中の可塑剤の抽出率を高めると共に、
その抽出率を調節する、軟質塩化ビニル中の可塑剤の回
収方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for recovering plasticizers contained in soft vinyl chloride, and more specifically, by adjusting the type of extraction solvent, the extraction rate of plasticizers in soft vinyl chloride is increased, and
The present invention relates to a method for recovering a plasticizer in soft vinyl chloride, which adjusts its extraction rate.
その目的は軟質塩化ビニル廃棄物の処理、再資源化の方
法として廃棄軟質塩化ビニル中の可塑剤を抽出、再利用
すると共に、抽出する可塑剤の抽出比率を調節すること
によって、残塩化ビニル中の可塑剤の量を、その利用の
目的に合せて加減する方法を提供することにある。The purpose is to extract and reuse the plasticizer in the waste soft vinyl chloride as a method for processing and recycling soft vinyl chloride waste, and by adjusting the extraction ratio of the plasticizer to be extracted, The object of the present invention is to provide a method for adjusting the amount of plasticizer in accordance with the purpose of its use.
廃プラスチック類は自然条件下での分解が困難であるた
め、その適正処理、再資源化法の研究は重要な課題であ
る。Since waste plastics are difficult to decompose under natural conditions, research into proper treatment and recycling methods is an important issue.
特に、施設園芸の拡大により飛躍的に増加した農業用塩
化ビニル廃棄物は加熱焼却すれば有害な塩化水素ガスを
発生するので決定的な処理法がない。In particular, agricultural vinyl chloride waste, which has increased dramatically due to the expansion of greenhouse horticulture, generates harmful hydrogen chloride gas when heated and incinerated, so there is no definitive treatment method.
従来、重油回収法などが試みられたが、いずれも経済的
に成立するに至らず、現在、有価物回収という観点から
、溶媒による可塑剤抽出法が最も有望視される方法であ
る。Conventionally, heavy oil recovery methods have been tried, but none of them have been economically viable, and currently, from the perspective of recovering valuables, the plasticizer extraction method using a solvent is considered the most promising method.
実験室的には従来から、塩化ビニル分析に際しての可塑
剤抽出溶媒として、エチルエーテル、アセトンなどが使
用されていたが、抽出に長時間を要し、また経済的に成
り立つものではない。In the laboratory, ethyl ether, acetone, etc. have traditionally been used as plasticizer extraction solvents for vinyl chloride analysis, but extraction takes a long time and is not economically viable.
工業的には、ヘキサン、メタノールなどが抽出溶媒とし
て研究されているが、沸点下、あるいは加圧下でないと
充分な抽出能力が期待できない上、メタノールなどの水
溶性溶媒は溶媒損失が大きいという欠点がある。Industrially, hexane, methanol, etc. are being researched as extraction solvents, but sufficient extraction ability cannot be expected unless they are at the boiling point or under pressure, and water-soluble solvents such as methanol have the disadvantage of large solvent loss. be.
例えば、その中、現在用いられている方法は、８０％メ
タノール水溶液を用い、９０〜１００℃の高温、加圧下
で抽出する方法であるが、高温、圧力を用いるため、操
作が複雑な上溶剤のロスも多く、かつそれに対応した設
備を要する不便さがある。For example, the currently used method is to extract at a high temperature of 90 to 100°C and under pressure using an 80% aqueous methanol solution. There is also a lot of loss, and it is inconvenient that equipment corresponding to this loss is required.
本発明者は、この欠点を改良するため種々研究の結果、
炭化水素系溶媒とハロゲン化炭化水素系溶媒との所要比
率の混合溶媒をもって抽出すれば常温において従来より
はるかに優れた収率をもって軟質塩化ビニル中から可塑
剤を抽出し、かつその混合溶媒中の炭化水素系溶媒とハ
ロゲン化炭化水素系溶媒の比率を調節することにより、
その残留可塑剤の量をも調節して、残留塩化ビニルの再
利用をその目的に合せて効果的に行い得ることを知り、
本発明を完成するにいたった。As a result of various studies to improve this drawback, the inventor of the present invention found that
If the plasticizer is extracted with a mixed solvent of a hydrocarbon solvent and a halogenated hydrocarbon solvent in the required ratio, the plasticizer can be extracted from soft vinyl chloride at room temperature with a much better yield than conventional methods, and the plasticizer in the mixed solvent can be By adjusting the ratio of hydrocarbon solvent and halogenated hydrocarbon solvent,
I learned that it is possible to effectively reuse residual vinyl chloride according to the purpose by adjusting the amount of residual plasticizer,
This led to the completion of the present invention.
すなわち、本発明は、軟質塩化ビニル製品、その細断物
、またはその再製粒状製品を、炭化水素系溶媒とハロゲ
ン化炭化水素系溶媒との所要比率の混合溶媒をもって抽
出することを特徴とする軟質塩化ビニル中の可塑剤の回
収法を要旨とする発明である。That is, the present invention provides a soft vinyl chloride product, which is characterized by extracting a soft vinyl chloride product, its shredded product, or its remanufactured granular product using a mixed solvent of a hydrocarbon solvent and a halogenated hydrocarbon solvent in a desired ratio. The gist of this invention is a method for recovering plasticizers in vinyl chloride.
以下、本発明を説明する。The present invention will be explained below.
本発明の廃棄軟質塩化ビニルはフイルム、パイプ（チュ
ーブ）等の種々の形態の軟質塩化ビニルがその素材とし
て使用できるが、特に園芸用の塩化ビニルフイルムの量
が最も多く、その可塑剤もＤＯＰ（ジ−２−エチルへキ
シルフタレート）が最も多く、次にＤＢＰ（ジブチルフ
タレート）、ＤＨＰ（ジヘキシルフタレート）、ＴＣＰ
（トリクレジルホスフエー
等の一種又は二種以上が用いられており、その配合量も
１０〜８０％にいたる種々の量、普通は２０〜４５％の
量が配合されており、その何れも本発明の回収の対象と
なる。The waste soft vinyl chloride of the present invention can be made of various forms of soft vinyl chloride such as films and pipes (tubes), but horticultural vinyl chloride film has the largest amount, and its plasticizer is also DOP ( Di-2-ethylhexyl phthalate) is the most common, followed by DBP (dibutyl phthalate), DHP (dihexyl phthalate), and TCP.
(One or more types of tricresyl phosphate etc. are used, and the blended amount varies from 10 to 80%, usually 20 to 45%. It is subject to collection according to the present invention.
これらの被抽出の廃棄物は、そのままでも抽出の対象と
なるが、工業的にはこれを水洗、細断し、又は最近行わ
れているペレット化したペレット又は粉末として抽出す
るのが、抽出効率はよい。These extracted wastes can be extracted as they are, but industrially, extraction efficiency is improved by washing them with water, shredding them, or extracting them as pellets or powder, which has been done recently. Yes.
本発明に用いる石油系炭化水素としては、Ｃ５〜Ｃ１０
のノルマルのペンタン、ヘキサン、ヘプタン、オクタン
、ノナン、デカン等、又はその異性化合物及びそれらの
混合物である石油エーテル、ベンジン等が何れも用いら
れ、ヘキサン（Ｂ．Ｐ．６８．７℃）、ヘプタン（Ｂ．
Ｐ．９８．４℃）等が好ましく用いられる。The petroleum hydrocarbons used in the present invention include C5 to C10
Normal pentane, hexane, heptane, octane, nonane, decane, etc., or their isomer compounds, petroleum ether, benzine, etc. are used, and hexane (B.P. 68.7°C), heptane (B.
P. 98.4°C) etc. are preferably used.
使用するハロゲン化炭化水素としても、トリクロルエタ
ン（αはＢ．Ｐ．７４℃、βはＢ．Ｐ．１１３．７℃）
、トリクロルエチレン（Ｂ．Ｐ．８８〜９０℃）、塩化
メチレン（Ｂ．Ｐ．３９．９℃）等が用いられ、混合溶
媒等の回収蒸溜分溜の必要性，共沸混合物の有無、逆浸
透等による分離硅を考慮に入れて、所要のハロゲン化炭
化水素を選択して用いる。The halogenated hydrocarbon used is trichloroethane (α is B.P. 74°C, β is B.P. 113.7°C).
, trichlorethylene (B.P. 88-90°C), methylene chloride (B.P. 39.9°C), etc., and the necessity of recovery distillation/fractionation of mixed solvents, the presence or absence of azeotropic mixtures, and the reverse The required halogenated hydrocarbon is selected and used, taking into account separation by osmosis, etc.
次に、先ず石油系炭化水素としてヘキサンを選び、ハロ
ゲン化炭化水素の例として、トリクロルエタンを用いて
、可塑剤として、ＤＯＰ３０％を含有する農業用軟質塩
化ビニルフイルムのペレツト（径１〜２ｍｍ）の１０ｇ
ｒをソックスレー抽出器中に入れ、ヘキサン６０：１・
１・１・トリクロルエタン４０の割合の混合溶媒１００
ｍｌにより１時間還流させ、可塑剤を抽出した。Next, first, hexane was selected as a petroleum hydrocarbon, trichloroethane was used as an example of a halogenated hydrocarbon, and agricultural soft vinyl chloride film pellets (1 to 2 mm in diameter) containing 30% DOP were used as a plasticizer. 10g of
Place r in a Soxhlet extractor and add hexane 60:1.
1.1-trichloroethane 40 parts mixed solvent 100 parts
ml for 1 hour to extract the plasticizer.
抽出残渣の分析の結果、塩化ビニル中の可塑剤は約３０
％存在したものが約３％に減少した事が判明した。As a result of analysis of the extraction residue, the plasticizer content in vinyl chloride was approximately 30%.
It was found that the percentage present had decreased to about 3%.
ヘキサンあるいはメタノール単一溶媒による同条件での
抽出の場合、１０〜１５％の可塑剤が塩ビ中に残留する
のに対し、１２〜７％多く可塑剤を抽出することができ
る。In the case of extraction under the same conditions using a single solvent of hexane or methanol, 10 to 15% of the plasticizer remains in the PVC, whereas 12 to 7% more plasticizer can be extracted.
なお、この抽出によって可塑剤のみならず、安定剤とし
て用いられるエボキシ化大豆油、有機酸のＣａ又はＺｎ
の石鹸類、キレート化合物等の一部が抽出されるが、抽
出された可塑剤は再び軟質の塩化ビニルの製造に使用さ
れるので、何等支障なく、むしろその場合改めて添加さ
れる安定剤の量を強化して通常の軟質塩化ビニルより優
れた性質の軟質塩化ビニルが得られる。Note that this extraction extracts not only the plasticizer but also the epoxidized soybean oil used as a stabilizer, the organic acid Ca or Zn.
Some of the soaps, chelate compounds, etc. are extracted, but since the extracted plasticizer is used again for the production of soft vinyl chloride, there is no problem; rather, the amount of stabilizer added in that case is can be strengthened to obtain soft vinyl chloride with better properties than ordinary soft vinyl chloride.
なお、上記の実験はソックスレー装置を用いて溶剤の沸
点下で実施したが、この方法の特徴として室温（２０〜
３０℃）において実施しても、ソックスレーの場合の９
０〜８０％程度の抽出が可能である。The above experiment was carried out using a Soxhlet apparatus at the boiling point of the solvent, but the characteristic of this method is that it can be carried out at room temperature (20 to
9 in the case of Soxhlet even when carried out at 30℃)
Extraction of about 0 to 80% is possible.
次の例は径３ｃｍ、高さ３０ｃｍの硝子製の筒に上下に
目皿を入れて上記の軟質塩化ビニルを充填して下記の溶
剤１ｌで１時間連続に抽出した結果を示す。The following example shows the results of a glass cylinder with a diameter of 3 cm and a height of 30 cm, with perforated plates on the top and bottom, filled with the above-mentioned soft vinyl chloride, and extracted continuously for 1 hour with 1 liter of the following solvent.
以上の実験によって、本発明の方法により従来の６０〜
７０％に比較して、沸点下では９０％以上、常温でも８
０〜９０％の好収率をもって抽出ができることが確かめ
られる。Through the above experiments, it was found that the method of the present invention can
Compared to 70%, it is more than 90% below the boiling point and 8 at room temperature.
It is confirmed that extraction can be performed with a good yield of 0 to 90%.
これらの抽出された抽出物から可塑剤を分離するには、
蒸溜によって溶剤を溜出することにより簡単に行うこと
ができる。To separate the plasticizer from these extracted extracts,
This can be easily done by distilling off the solvent.
さらに、粉末塩化ビニルを原料として、回収可塑剤３０
％を混入して、所要の安定剤を用い混練して、ロールを
用いて１５０℃、１０分間混練した後、カレンダーロー
ルによりフイルムを作製しこのフィルムについての熱安
定性の試験結果は次のとおりである。Furthermore, using powdered vinyl chloride as a raw material, 30% of recovered plasticizer
%, kneaded with the required stabilizer, kneaded using a roll at 150°C for 10 minutes, and then produced a film using a calendar roll. The thermal stability test results for this film are as follows. It is.
すなわち、新しいＤＯＰを用いたものより、寧ろ良好な
熱安定性を示した。That is, it showed better thermal stability than that using new DOP.
これは先にも述べたように一つは抽出されたＤＯＰには
製品中の安定剤がそれだけ多く含まれ良好な結果を示し
ているものとも考えられる。As mentioned above, one reason for this may be that the extracted DOP contains more of the stabilizer in the product, resulting in better results.
なお、この方法によって可塑剤を抽出した、残塩化ビニ
ルは、その可塑剤の含量を３〜５％にまで低下できるの
で、硬質塩化ビニルとして再生可能で再使用ができる。Note that the residual vinyl chloride from which the plasticizer has been extracted by this method can be recycled and reused as hard vinyl chloride because the plasticizer content can be reduced to 3 to 5%.
従来法ではその抽出によっても１０％以下とすることが
困難であり、１０％以上であると、耐衝撃性が悪く硬質
塩化ビニルとしては不適であったが、本発明の方法で３
〜５％に低下できるので硬質塩化ビニルとして適合した
再生品として再利用が実用化され、一石二鳥の効果をも
たらすことができる。In the conventional method, it is difficult to reduce the amount to 10% or less even by extraction, and if it is more than 10%, the impact resistance is poor and it is unsuitable as hard vinyl chloride.
Since it can be reduced to ~5%, reuse as a recycled product suitable as hard vinyl chloride can be put into practical use, and it can bring about the effect of killing two birds with one stone.
再生可塑剤の利用化試験
塩化ビニールの用途として需要の多い電線被覆材料への
利用化を図るため、回収可塑剤、塩ビポリマー、安定剤
等を配合して、厚さ１ｍｍのフイルムを作製し、６００
ボルトビニール電線（１種１号）、器具コード（１種２
号）、ケーブルシース（２種）用として、ＪＩＳ Ｋ
６７２３により試験を行った。Utilization test of recycled plasticizer In order to utilize vinyl chloride as a material for covering electric wires, which is in high demand, a film with a thickness of 1 mm was prepared by blending recycled plasticizer, PVC polymer, stabilizer, etc. 600
Bolt vinyl electric wire (Class 1, No. 1), appliance cord (Class 1, No. 2)
JIS K for cable sheaths (class 2)
6723 was used for testing.
これらの試験の結果から再生可塑剤は標準品とほぼ同等
の品質を保持していることが確認され、またＪＩＳ規格
にも適合するため、電線の外部被覆用として充分使用で
きる。The results of these tests confirm that the recycled plasticizer maintains almost the same quality as the standard product, and also complies with JIS standards, so it can be used satisfactorily for the outer coating of electric wires.
可塑剤抽出残渣（半硬質頃ビ）を用いた成型品の品質試
験
可塑剤抽出後の半硬質塩ビを成型品とした場合、その品
質についての強度が問題となる。Quality test of molded products using plasticizer extraction residue (semi-rigid vinyl chloride) When molded products are made from semi-rigid vinyl chloride after plasticizer extraction, the strength of the quality becomes an issue.
今回は曲げ強度及び圧縮強度について試験を行った。This time, we conducted tests on bending strength and compressive strength.
この試験において可塑剤抽出残清の成型品はバージンレ
ジン成型品より強度が低下しているが、残渣中には可塑
剤が約１０％残留しており、これが強度に影響している
ものと考えられる。In this test, the strength of molded products made from plasticizer extraction residue was lower than that of virgin resin molded products, but approximately 10% plasticizer remained in the residue, and this is thought to have an effect on the strength. It will be done.
今後は混合溶剤等により抽出率を高め、残留可塑剤量を
低下させる研究を続ける。In the future, we will continue research to increase the extraction rate using mixed solvents and reduce the amount of residual plasticizer.
Claims (1)
粒状製品を、炭化水素系溶媒とハロゲン化炭化水素系溶
媒との所要比率の混合溶媒をもって抽出することを特徴
とする軟質塩化ビニル中の可塑剤の回収法。 ２ 炭化水素系溶媒とハロゲン化炭化水素系溶媒の比率
を調節することによって軟質塩化ビニル中の可塑剤の抽
出率を調節する、特許請求範囲第１項の軟質塩化ビニル
中の可塑剤の回収法。[Claims] 1. A soft vinyl chloride product, its shredded product, or its reprocessed granular product is extracted with a mixed solvent of a hydrocarbon solvent and a halogenated hydrocarbon solvent in a desired ratio. Recovery method for plasticizers in soft vinyl chloride. 2. A method for recovering a plasticizer in soft vinyl chloride according to claim 1, which adjusts the extraction rate of the plasticizer in soft vinyl chloride by adjusting the ratio of a hydrocarbon solvent and a halogenated hydrocarbon solvent. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10787380A JPS5813089B2 (en) | 1980-08-06 | 1980-08-06 | Recovery method for plasticizer in soft vinyl chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10787380A JPS5813089B2 (en) | 1980-08-06 | 1980-08-06 | Recovery method for plasticizer in soft vinyl chloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5731941A JPS5731941A (en) | 1982-02-20 |
| JPS5813089B2 true JPS5813089B2 (en) | 1983-03-11 |
Family
ID=14470246
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10787380A Expired JPS5813089B2 (en) | 1980-08-06 | 1980-08-06 | Recovery method for plasticizer in soft vinyl chloride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5813089B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021211647A1 (en) * | 2020-04-15 | 2021-10-21 | The Procter & Gamble Company | Reducing surface and bulk contamination in plastic |
-
1980
- 1980-08-06 JP JP10787380A patent/JPS5813089B2/en not_active Expired
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021211647A1 (en) * | 2020-04-15 | 2021-10-21 | The Procter & Gamble Company | Reducing surface and bulk contamination in plastic |
| US11628379B2 (en) | 2020-04-15 | 2023-04-18 | The Procter & Gamble Company | Reducing surface and bulk contamination in plastic |
| US11794128B2 (en) | 2020-04-15 | 2023-10-24 | The Procter & Gamble Company | Reducing surface and bulk contamination in plastic |
| US11986750B2 (en) | 2020-04-15 | 2024-05-21 | The Procter & Gamble Company | Reducing surface and bulk contamination in plastic |
| US11992787B2 (en) | 2020-04-15 | 2024-05-28 | The Procter & Gamble Company | Reducing surface and bulk contamination in plastic |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5731941A (en) | 1982-02-20 |
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