JP2008031399A - Method for reclaiming vinyl chloride material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a widely realizable recycle system for reclaiming processing of wastes of simple PVC substances and (PVC material) laminate composites of paper, aluminum and NWF, comprising a safe aqueous system as a solvent saturation treating method, using little toxic, little inflammable and durable composition, and handling with safety and low pollution, by a simple technique and a general-purpose method. <P>SOLUTION: The reclaiming method established of PVC materials, that is, an ecorecycle system of PVC materials, comprises a system of (1) saturating PVC materials with such a PVC material treating composition consisting of the chief agent of N-methyl-2-pyrrolidone, dimethyl imidazolidinone and morpholine and of the auxiliary material of terpene-based hydrocarbon as is a blend of 50-90% by weight of the chief agent and 10-40% by weight of the auxiliary material to thereby dissolve PVC completely, (2) recovering PVC solid by adding 7-40% by weight of an aqueous medium of water or a lower (1-4C) monohydric alcohol and thereafter by reclaiming PVC solid, and (3) again dehydrating the treating residual liquid and recycling it as PVC material treating composition. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The present invention relates to a regeneration method necessary for safely and reliably recovering vinyl chloride from a single substance or a composite material containing vinyl chloride.
Recycling methods with a view to saving resources and protecting the environment, especially for the recycling of used vinyl chloride waste easily and safely and accurately without the need for special equipment, and collecting and further recycling. Is established.
Vinyl chloride is a film, plate or container containing a plasticizer, and a composite of paper, aluminum, non-woven fabric (NWF), etc. in the living infrastructure, packaging, molding, adhesion, binder, interior / exterior materials, architecture Widely used for materials.
Advantages of processability, good moldability, good internal density, many processing characteristics such as adsorption, gas barrier properties, and colorability, water resistance, weather resistance, chemical resistance, etc. ing.

Under such circumstances, concerns that contribute to so-called environmental hormones, such as dioxin, have emerged as an adverse effect resulting from the fact that vinyl chloride is not properly disposed of, and countermeasures are urgently needed.
("Stolen future" Shia, Colborn et al. 19977.9 Shosuisha, "Dioxin-contaminated archipelago Japan warning" Nagayama Junya 19977.9 Kanki Publishing)
A method of dissolving and recovering by processing with an appropriate solvent is adopted, but the liver and kidney solvent itself becomes a cause of environmental pollution including humans, and VOC measures are also required, and more and more new methods are necessary. It becomes.

Conventional solvents such as aromatics (aromatics) such as toluene, xylene, dichlorobenzene, halogens such as trichloroethylene, perchlorethylene, methylene chloride, trichloroethane, carbon tetrachloride, chlorofluorocarbon solvents, or dimethylformamide Water-soluble solvents such as dimethylacetamide, methylethyleneketone, tetrahydrofuran, acetone, and petitcello, and petroleum-based solvents such as carbon disulfide, kerosene, paraffin, and n-hexane.

However, all of them are harmful and contain information, and various laws and regulations are complicated and cannot be said to be safe and secure in the future.
Not only that, it is volatile and evaporates faster than water at high temperatures. It is also a dangerous material and is difficult to handle. In addition, the irritating odor is large and the influence on the surroundings is not preferable. It still has various problems, such as being insoluble in water and difficult to dissolve (hydrophobic), and expected to cause secondary contamination.
Of course, as alternatives, solvents such as gluconic acid, adipic acid, succinic acid ester, and propylene carbonate disclosed in Japanese Patent Application Laid-Open No. 2000-44724 are also conceivable, but they have poor critical processing power and may not be recyclable Aftercare is a new problem due to water insolubility.

In view of these problems, the present invention is a water-soluble base that is easy to handle, and is a film, plate, packaging material of vinyl chloride alone in consideration of odor and the like in the surrounding environment with low volatility and flammability. Or not only to dissolve and recover only vinyl chloride from laminates such as vinyl chloride and paper, aluminum, NWF, etc., but also to reproduce the vinyl chloride usefully by water treatment again. The processing solution used has also been found to be a system that can be recycled again.

Therefore, the present invention comprises a water-soluble solvent selected from N-methyl-2-pyrrolidone, dimethylimidazolidinone and morpholine as a main component as a water-soluble, low-toxic solvent composition, and a terpene hydrocarbon ( A vinyl chloride product is dissolved by a method such as saturation with a mixed composition containing D-limonene, P-myrcene, α-pinene, turpentine oil, etc. contained in the orange fruit peel component) as an accessory component ( solution) The vinyl chloride resin is separated, and a plasticizer, a laminate material such as paper, NWF, and aluminum is separated to recover the vinyl chloride itself.
Moreover, in the present invention, only vinyl chloride is almost solid by adding water or a mixture of lower monohydric alcohols containing water to regenerate vinyl chloride dissolved in these solvents as a solid content, thereby forming an aqueous mixed solution composition. It is realized to reproduce as a body.
This treatment method is water-based, safe and simple, and also has little secondary contamination and the effectiveness that can be achieved at low cost cannot be overlooked.

Furthermore, in recent years, we have developed a truly rational and economical closed recycling system that can reuse the liquid composition after separating vinyl chloride, plasticizer, paper, aluminum, NWF, etc. from the aqueous mixed solution composition. It will further promote the omission, reduction and regeneration of oil resources, which are regarded as important.

Specifically, the technology of the present invention enables efficient and reliable recovery of vinyl chloride from used vinyl chloride products (single film, plate, packaging material, paper, aluminum, NWF laminate). Because it does not require special equipment and methods, it leads to the spread of the business, and vinyl chloride is treated with water-based treatment without disposal and incineration of precious vinyl chloride. From treatment to solid (solid) This vinyl chloride can be reused as a secondary use (second use) for vinyl chloride products as well as binders, adhesives, masterbatches, and induces potential for resource saving. To do.
Furthermore, the residual liquid of the treated composition can be dehydrated and reused as a treated composition again.
It has literally established an ideal eco-recycling system, which can avoid or reduce the restrictions of VOC, PRTR, and various laws and regulations, and has the potential to help solve the noted vinyl chloride problem.

Specific embodiments of the present invention include 50 to 90 aqueous compositions selected from N-methyl-2-pyrrolidone, dimethylimidazolidinone, and morpholine in immersion tanks (explosion-proof) such as stainless steel and FRP. Terpenic hydrocarbons comprising (C ₅ H ₈ ) n = 1 to 1 (n is a positive integer of 1 or more), for example, D-limonene, α-pinene, P-myrcene, turpentine oil. A composition prepared by mixing 10 to 40 g of non-aqueous citrus oil such as turpentine oil as a secondary material is prepared.
The vinyl chloride material to be treated is immersed in 10 to 40% by weight (more preferably 10 to 25% by weight).
If necessary, the liquid temperature is raised to about 40-50 ° C. Further, a dynamic action may be given by stirring, agitation, shaking, SS (ultrasonic wave), and thus a completely dissolved vinyl chloride material can be obtained after about 1 to 12 hours.
Not soluble paper from this, aluminum, etc. fractionated to recover the NWF, in vinyl chloride lysis composition, an aqueous solution of water or a lower alcohol _{(C 1} ~C 4 1 monohydric alcohol) per 100 weight% (Water-to-alcohol is 200 to 10% by weight of alcohol with respect to water 100) (7 to 40%) (preferably 10 to 15%).
This confirmation (1D) is performed by chromatography, infrared analysis, ion analysis, NMR, or gravimetric analysis before and after treatment.
Solid and vinyl chloride can be converted into binders, adhesive pressure-sensitive adhesives, sealing materials, film materials, and molded product laminates after dehydration, and can also be used as a secondary material for recycling to the original vinyl chloride material.

Also, the residual liquid is dehydrated.
It is possible to heat (60 to 90 ° C.) and use the difference in boiling point (BP) to scatter water with a low Bp, or to absorb water with sulfate, carbonate, or the like.
Then, it is recycled again as the original vinyl chloride (PVC) composition liquid.
Thus, PVC recycling can be realized by establishing a cycle of immersion-dissolution-separation-aggregation (regeneration) -regeneration. (PVC eco recycling system)

Next, specific embodiments and examples of the present invention will be described.

（テスト−１）
各１００ｍｌに市販の塩化ビニールクロス２０ｇを浸漬して常温（２０℃）と５０℃の経時（Ｈ）による外観変化を観察する。

（評価）５−ほぼ完溶し紙の分離した（１００％）
４−約８０％ 完溶
３−６０％位 完溶
２−３０％位 完溶
１−殆んど 残る
本発明の組成物は 温度、経時により 着実に 溶解、分離の効果が認められた。
比較品は揮発性もあり高温に弱いことが判明した。
（テスト−２）
２０℃ １２時間後の 組成物１〜５、ａ−ｉ、を用いてその外観、におい、回収率を調査した。

ａ．４０％位 残る 分離不完全である
ｂ．４０〜５０％ 残る 分離不完全である
ｃ．７０％位 残る 分離不完全である
ｄ．２０〜３０％位 残る 分離不完全である
ｅ．１０％位 残る 分離不完全である
におい：○１、２、４、５、ａ、ｂ、ｃ、ｄ：シトラストーンのかおりあり
○ ３、 ： わずかにアンモニア臭あり
○ｆ、ｇ、ｈ、ｉ ： 強烈な刺激臭あり
○ ｅ ： アルコール臭あり

以上より本発明は 従来の有害な 組成物と同等の回収率を成立させ且つ後述するように再生することができる。The test composition was confirmed by treating with a commercially available vinyl chloride cloth for interior using a composition comprising the following composition.

(Test-1)
20 g of a commercially available vinyl chloride cloth is immersed in each 100 ml, and the appearance change with the passage of time (H) at normal temperature (20 ° C.) and 50 ° C. is observed.

(Evaluation) 5- almost completely dissolved and the paper separated (100%)
4-About 80% complete dissolution 3-60% complete dissolution 2-30% complete dissolution 1-mostly The remaining composition of the present invention was steadily dissolved and separated by temperature and time.
The comparative product was found to be volatile and vulnerable to high temperatures.
(Test-2)
The appearance, odor, and recovery rate of the compositions 1 to 5 and ai after 20 hours at 20 ° C. were examined.

a. About 40% remains incomplete separation b. 40-50% remaining Incomplete separation c. About 70% remaining Incomplete separation d. About 20-30% remaining Incomplete separation e. About 10% remaining Incomplete separation
Odor : ○ 1, 2, 4, 5, a, b, c, d: There is a citrus stone odor ○ 3 ,: Slightly ammonia odor ○ f, g, h, i: Strong irritating odor ○ e: There is alcohol odor

As described above, the present invention can establish a recovery rate equivalent to that of the conventional harmful composition and can be regenerated as described later.

それぞれの処理液濃度１５％のものに対し水及びエチルアルコール混合液を約１０％添加して再生率（ＰＶＣの溶液からＰＶＣが固形にして再生する）割合を調査した。
再生率＝最初の浸漬したＰＶＣの重量（ｇ）を１００としたとき、固形にして再生したＰＶＣの重量（ｇ）で１００に近い程、完全再生が成就していることの１つの目安となる。

以上のように本発明の処理（再生）法はほぼ予想に近いＰＶＣを回収することが出来ることを確認した。
更に組成物に水及びエチルアルコール混合液から脱水−アルコール処理をしてからえた再生組成物を用いて（６、７、８、９）再び市販の塩化ビニールクロス（内装材）を浸漬した。
再生組成物１００に対して重量として１５％の濃度で１２時間浸漬処理したところ次の結果をえた。

即ち本発明組成物はＰＶＣの回収再生ばかりでなく液そのものも再生利用することができる極めて有効なる方法であることが判明した。A composition of the following formulation was immersed in a vinyl chloride plate (PVC) (35 mm × 70 mm × 2 mm thick, with gray coloring material) at 20 ° C. for 12 hours to confirm the following effects.

About 10% of a mixed solution of water and ethyl alcohol was added to each treatment solution having a concentration of 15%, and the regeneration rate (recovered from the PVC solution in which PVC was solidified) was investigated.
Regeneration rate = When the weight (g) of the first immersed PVC is 100, the closer to 100 the weight (g) of the PVC that has been solidified and regenerated is one indication that complete regeneration has been achieved. .

As described above, it was confirmed that the treatment (regeneration) method of the present invention can recover PVC almost as expected.
Furthermore, a commercially available vinyl chloride cloth (interior material) was again immersed in the composition using a regenerated composition obtained after dehydration-alcohol treatment from a mixed solution of water and ethyl alcohol (6, 7, 8, 9).
When the reclaimed composition 100 was immersed for 12 hours at a concentration of 15% by weight, the following results were obtained.

In other words, it has been found that the composition of the present invention is a very effective method that not only collects and recycles PVC but also recycles the liquid itself.

Claims (1)

(1) Aqueous solvent selected from N-methyl-2-pyrrolidone, dimethylimidazolidinone, and morpholine 50 to 90 weights when vinyl chloride is separated and recycled from vinyl chloride alone or laminated products such as paper, aluminum, and NWF. (%) And a terpene hydrocarbon in 10 to 40% by weight (%) of a composition solution to dissolve the vinyl chloride material. (2) Water or water and lower alcohol (C _{1 to} C) in the composition solution ₄ ) is added to 7 to 40% of the mixture, and vinyl chloride is regenerated as a solid, separated and recovered,
(3) A method of regenerating a vinyl chloride material comprising a cycle of (1) to (3), wherein the remaining liquid is dehydrated again and appropriately mixed into the composition liquid of (1) and reused.