JPH10279727A - Method for separating reduced volume liquid from reduced volume expanded polystyrene - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gel, paste or viscous solution containing reduced polystyrene containing d-limonene having high affinity for polystyrene without partial decomposition or coloring of both. Separate and
Collect in a reusable state. SOLUTION: A reduced volume expanded polystyrene mass containing 2 to 60 parts of polystyrene per 100 parts of d-limonene is kept at 50 ° C. to 150 ° C., and can be dissolved with d-limonene but does not dissolve polystyrene. While the solvent is kept at the same temperature, the foamed polystyrene is rinsed in the form of particles having a diameter of 0.6 mm or less, a small piece of a film having a thickness of 0.6 mm or less, or a small piece of a thread having a diameter of 0.6 mm or less. Into a solvent, solid-liquid separation of the mixture to recover powdered polystyrene, and separation of the separated liquid phase to recover d-limonene and the solvent separately. A method for separating a volume-reducing liquid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for separating and recovering a volume-reduced liquid from a polystyrene having a reduced volume using a polystyrene (expanded polystyrene) volume-reducing liquid, and more particularly to a packing material, a beverage container and the like. Bulk foamed polystyrene molded products that are no longer needed after being used as a material are rapidly dissolved, and highly biodegradable polystyrene containing d-limonene as a main component has high biodegradability for handling safety and environmental protection. The present invention relates to a method for collecting a reduced volume solution.

[0002]

2. Description of the Related Art A molded article of expanded polystyrene is made of various instantaneous materials by utilizing its ease of molding, shape retention, lightness, good feel, heat insulation, shock buffering, corrosion resistance, whiteness, and the like. It is produced and consumed in large quantities as containers for storing, transporting, displaying and cooking foods, fresh marine products, vegetables and fruits, and as packing materials for home appliances and the like. These used foamed polystyrene molded articles have been conventionally discarded by various methods as waste.

[0003] These used expanded polystyrene wastes (hereinafter also referred to as wastes) are not thoroughly separated and recovered after use, and even if they are separated and recovered, many techniques for treating them are used. There's a problem. For example, in the case of landfill treatment, the shape retention, light weight, shock buffering property, corrosion resistance, hue, etc. are damaged, they do not corrode naturally, they float up on earth and sand by rainwater and are scattered, and air further Floating inside,
Today it is a social issue. For example, in the case of a so-called toro box used for storing and transporting fresh seafood, the number of empty toro boxes is about 880, although the limit is about 880 even if they are arranged and loaded on a 4-ton truck. Has a total weight of only 1
The weight is only 4.75 kg, which is not much different from the weight of about 12.5 kg of sheets and ropes required for covering and fixing about 880 toro boxes. It is no exaggeration to say that transporting boxes is almost done in the effort of transporting air.
In addition, a method of incineration, a method of thermal decomposition, a method of compressing and crushing by applying high pressure, a method of melting, etc. have been proposed,
Each of these methods has advantages and disadvantages and is not definitive.

Recently, it has been proposed to use d-limonene to reduce the volume of spent expanded polystyrene waste. For example, U.S. Pat. No. 5,223,543 describes the use of activated d-limonene in the form of steam to eliminate problems due to bulkiness of waste. Japanese Patent Application Laid-Open No. Hei 5-2630065 discloses that at least one kind of non-hazardous compound selected from d-limonene, isoamyl acetate, benzyl propionate and ethyl butyrate is contained. It is described that a solvent containing 6% by volume of ethanol is used, and finely crushed polystyrene is stirred well in the solvent to reduce the volume of foamed polystyrene waste. Attention is paid to the use of harmless solvents. However, these techniques are not directed to efficiently recovering d-limonene from reduced volume polystyrene.

[0005] We have already disclosed in Japanese Patent Application No. 7-101654 (Japanese Patent Application Laid-Open No. Hei 8-269226) "a chip obtained by crushing and cutting a used foamed polystyrene molded product is used as a processing container for reducing the volume of foamed polystyrene. Into the container and contacted with an alkaline aqueous solution or aqueous emulsion containing d-limonene and a surfactant in the container to absorb d-limonene in the expanded polystyrene and absorb the d-limonene to form a foam portion. Separating the gelled foamed polystyrene from the aqueous solution or aqueous emulsion by collapsing and reducing the volume, or recovering a naphtha-like oily substance from the gelled foamed polystyrene, the method for reducing the volume of foamed polystyrene And "d- recovered from solidified gel-like foamed polystyrene by solid-liquid separation and distillation." To reuse the monene '', and as an apparatus for carrying out this method, `` an introduction opening for introducing a foamed polystyrene chip into the tank provided at the top, An apron conveyor having a sleeve for forcibly guiding foamed polystyrene into a processing liquid for reducing the volume of foamed polystyrene in a tank and dipping the processing liquid therein, and a heater for heating the processing liquid Provided at the lower portion on the opposite side of the introduction opening, an extraction opening for extracting the processed solid polystyrene foam outside the tank, and a volume disposed near the expansion polystyrene extraction opening. A collecting device for collecting the reduced polystyrene foam from the processing liquid, wherein the collecting device collects the processed polystyrene in the processing liquid in the processing liquid. It is possible to move to a position where the styrofoam is taken up in cooperation with the sleeve of the conveyor located in the collection area of the styrene solids, and to a position that does not hinder the rotation of the sleeve of the apron conveyor when collection is stopped. And an apparatus for reducing the volume of foamed polystyrene, which has a movable polystyrene foam volume reduction treatment tank. This technique is disclosed in Japanese Patent Application Laid-Open No. H5-25-2 in terms of using an aqueous d-limonene reduced solution.
There are considerable advantages over the technique disclosed in JP-A-63065.
According to this method and apparatus, a reduced gel foamed polystyrene can be obtained relatively easily. However, as in the technique described in JP-A-5-263065,
The difficulty of high d-limonene consumption has not been overcome.

Therefore, in order to improve the high consumption of d-limonene, Japanese Patent Application No. 8-39125 discloses that “a foamed polystyrene mass is introduced into a warmed volume reduction treatment apparatus, At the front end of the apparatus, a volume reducing solution comprising an aqueous emulsion containing d-limonene and a surfactant is supplied, and the volume reduction is performed while compressing and transporting the expanded polystyrene through the volume reducing apparatus while keeping the temperature. A torsional force and / or a shearing force is applied to the foamed polystyrene to which the liquid has been supplied to collapse the foamed portion of the foamed polystyrene to reduce the volume of the foamed polystyrene, and the rear end of the volume-reducing apparatus Volume reduction processing of foamed polystyrene, including an operation of discharging a lump of foamed polystyrene having been subjected to volume reduction processing from the rear end of the volume reduction processing apparatus, and an operation of performing compression molding processing. Method And, as an apparatus for smoothly performing this method, `` consisting of a plurality of cylindrical reduced containers having different diameters provided with screw conveyor-shaped transfer volume reducing blades are connected in series, The reduced container has a structure in which the void portion therein is larger than the void portion in the subsequent cylindrical reduced container, and the latter cylindrical reduced container has a greater physical strength than the former cylindrical reduced container, and Heat-retaining means and / or cooling means on the outer surface of the shape-reducing container, and a tip-shaped foamed polystyrene inlet at a front end of a previous stage of the plurality of cylindrical shape-reduced containers; Volume reducing solution spraying means for spraying the heated volume reducing solution in the vicinity on the tip-shaped foamed polystyrene, and volume reduction at the rear end of a cylindrical lower volume container at a later stage of the plurality of cylindrical volume reducing containers Foamed polystyrene And Lumpur outlet,
A volume-reduced foamed polystyrene having a volume-reduced foamed polystyrene and a separating means for separating the volume-reduced liquid from a rear portion of the volume-reduced foamed polystyrene discharge outlet. Device, etc., but this technology is also d-
Although attention is paid to limonene consumption, smooth recovery is not the main focus.

We further disclosed in Japanese Patent Application No. 7-258316, "(A) 50 to 99 parts by weight of a stock solution of d-limonene,
(B) Linear alkylbenzene sulfonate, polyoxyethylene linear or branched alkyl ether, polyoxypropylene linear or branched alkyl ether, linear mixture of a mixed condensate of ethylene oxide and propylene oxide Or branched alkyl ether, polyoxyethylene linear or branched alkyl ether sulfonate, polyoxyethylene linear or branched alkyl ether phosphonate, polyoxyethylene linear or branched alkyl Ether carboxylate, polyoxyethylene linear or branched alkyl ether carboxylic ester, polyoxyethylene sorbitan-fatty acid ester (ethylene oxide condensate of sorbitan fatty acid ester), 4 to 50, preferably 5 to 20 ethylene oxide Units of polio Shi ethylene alkyl phenols,
Surfactants selected from the group consisting of polyoxyethylene alkyl and dialkyl succinic acid compounds, for example, polyoxyethylene dioctyl succinate, having an HLB or an additive HLB of 6.0 to 30.0.
30.0 parts by weight, and (C) emulsion stability and / or
Or 0.0 to 5.0 parts by weight of an auxiliary agent for preventing rough skin, and further contains (D) 30 parts by weight or less of animal and vegetable oils if desired, and a reduced volume solution of expanded polystyrene. However, this technology also pays attention to d-limonene's capacity for reducing volume and other abilities, and does not mainly aim for smooth recovery thereof.

[0008] d-limonene is a kind of terpene contained in living organisms and is generally collected from citrus fruit peel and is a solvent which has no environmental problems and is excellent in detergency. Many applications, for example, as a substitute for CFCs, have been proposed, and while the production volume is limited as a natural product, import costs are increasing as demand is imminent. Therefore, it is desirable to separate and recover d-limonene from gel- or paste-like styrene in which volume has been reduced using d-limonene and reuse it. Also, upon separation and recovery, it is desired that the regenerated polystyrene does not deteriorate or color.

Separating polystyrene material and d-limonene from gel or paste-like polystyrene obtained by reducing the volume of expanded polystyrene with d-limonene;
Several methods are possible for recovery, but no definitive method has been proposed. Since d-limonene is excellent in affinity with the styrene resin, it is excellent as a volume reducing agent for expanded polystyrene and quickly reduces the volume of expanded polystyrene and has affinity with the same, but is difficult to separate.
For example, referring to the solvent separation in the production of polystyrene resin, a gel or paste reduced volume polystyrene containing d-limonene is discharged into a vacuum at a high temperature such as 180 ° C. to 250 ° C. However, in this method, partial decomposition (molecular weight reduction) and coloring of polystyrene are unavoidable, and complete evacuation of d-limonene from polystyrene by vacuum evacuation under relatively mild conditions. We have found that, according to this method, the resulting regenerated polystyrene is difficult to alter, or at least to avoid coloring or incomplete separation.

[0010]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the above-mentioned problems in the prior art and to reduce the volume of a gel, paste or viscous solution containing d-limonene having a high affinity for polystyrene. It is to separate both from the used polystyrene without partial decomposition or coloring, and recover them in a reusable state.

[0011]

Means for Solving the Problems As a result of intensive studies on the above problems, the present invention has been completed. When the gel- or paste-like reduced volume of polystyrene containing d-limonene is subjected to the d-limonene removal operation, d-limonene is more quickly produced on the surface portion of the gel- or paste-like polystyrene mass. The removed portion from which d-limonene has been removed becomes a hard skin, and this hard skin acts as a barrier to prevent the migration of d-limonene remaining in the gel or paste-like polystyrene inside to the surface. To prevent its removal. To avoid this,
In order to allow d-limonene in the gel-like or paste-like polystyrene to be quickly extracted to the surface before the formation of the hard skin, the ratio of the surface area / volume of the gel-like or paste-like polystyrene mass should be as large as possible. What to do, ie
Although it is necessary to make the polystyrene mass as small as possible, there is a risk that the granulation of the polystyrene mass under heating by mechanical shearing force may result in deterioration (molecular weight reduction) of the polystyrene material. In order to extremely reduce the viscosity of the volume-reduced polystyrene without using a high temperature to obtain droplets having a small diameter, a large amount of d-limonene for volume reduction must be used. Not only a large size but also a large amount of thermal energy is required to recover a large amount of d-limonene.

The hardness of the gel or paste reduced volume polystyrene mass containing d-limonene depends, of course, on the d-limonene content and the temperature. For example, 100 parts of d-limonene is mixed with 2 to 70 parts of polysterene (polystyrene in a mixture of d-limonene and polystyrene =
D-limonene-containing polystyrene mass containing 1.96% to 41.18%) has sufficient softness when heated to about 50 ° C. to 150 ° C. irrespective of normal pressure or reduced pressure. It is a plastic chewing gum-like or paste-like and freely deformable, and d-limonene can be removed from the surface of this polystyrene mass.

However, the surface portion from which d-limonene has been removed hardens, forms a hard skin, and contains d-limonene.
It hinders the removal of limonene. Since the d-limonene-containing polystyrene mass has a chewing gum-like shape and is freely deformable, the inner material containing d-limonene can be exposed to the surface by deforming, and d-limonene can be removed from the surface. The removal of d-limonene by such a method, as the hardness increases as the limonene is removed, the internal material containing d-limonene becomes less likely to be exposed on the surface due to deformation and the removal rate of d-limonene decreases; I can't. However, under certain conditions, it was found that the formation of hard epidermis was not exactly at the same time as the removal of d-limonene, but there was a slight time lag, and therefore the rate of removal of d-limonene was less than that of hard epidermis. It has been found that the above problem can be avoided by keeping the value large.

In vacuum evacuation, small gel-like or paste-like polystyrene lumps in a sufficiently heated gas atmosphere evaporate d-limonene from the surface, but take local heat of vaporization at the evaporation site, The lost heat of vaporization cannot be immediately replenished from the surrounding gas. The ambient atmosphere is due to the gas and due to its inherent small heat capacity. That is, it is extremely difficult to keep the removal rate of d-limonene higher than the formation rate of the hard skin. In the vacuum evacuation method, polystyrene is heated and melted at 180 ° C. to 250 ° C. to maintain the molten state so that d-limonene can move from the inside of the polystyrene particles to the surface, and is contained inside the melted polystyrene droplets. The d-limonene is expelled from the inside of the droplet, or the polystyrene droplets or particles are blasted into fine particles by instantaneous expansion to d-limonene.
I have to get rid of Limonene. This is one reason why partial decomposition (molecular weight reduction) and coloring of polystyrene in vacuum evacuation treatment cannot be avoided.

Accordingly, we have proposed a method of avoiding the evaporation and removal of d-limonene in a gas having a small heat capacity, and a method that does not require heat of vaporization so that a local temperature drop on the surface does not occur. By keeping the removal rate high, the d-limonene-containing polystyrene was not colored or deteriorated, and a study was made on a method of removing d-limonene before the formation of the hard and thick epidermis, and reached the present invention.

Therefore, the present invention provides (1) a method in which 2 parts of polystyrene (polystyrene) per 100 parts of d-limonene are used.
The reduced volume foamed polystyrene mass containing d-limonene containing 60 parts is kept at a temperature of 50 ° C. to 150 ° C., and a solvent that can be dissolved or mixed with d-limonene but does not dissolve polystyrene is used. The prepared polystyrene foam mass is prepared in the form of small particles or droplets of a polystyrene, a thin film or a broken piece, or a small piece of a cut fine thread in the solvent heated to 50 ° C. to 150 ° C. In the solvent to remove d-
Limonene is released into the solvent, the mixture is subjected to solid-liquid separation to recover regenerated polystyrene as a powder, and the separated liquid phase is distilled to recover d-limonene and the solvent separately. A method of separating a volume-reducing liquid from a volume-reduced expanded polystyrene ”and (2)“ a method in which the small particles or droplets, thin film pieces, or small pieces obtained by cutting the fine yarn have a diameter or thickness of 0.6 mm or less. A method for separating a volume-reduced liquid from a volume-reduced expanded polystyrene according to any one of the above items (1) and (2).

(3) "The reduced volume expanded polystyrene lump containing d-limonene containing 2 to 60 parts of polystyrene per 100 parts of d-limonene is held at a temperature of 50 ° C. to 150 ° C., Preparing a solvent that can be dissolved or mixed with limonene but does not dissolve polystyrene, and divides the foamed polystyrene mass into small particles of polystyrene by rapidly stirring in the solvent heated to 50 ° C. to 150 ° C. Then, d-limonene in the polystyrene small particles is released into the solvent, the mixture is subjected to solid-liquid separation to recover regenerated polystyrene as a powder, and the separated liquid phase is distilled to obtain d-limonene. A method for separating a reduced volume liquid from a reduced volume expanded polystyrene according to the above (1) or (2), wherein the limonene and the solvent are separately recovered. "
(4) "2-100 polystyrene per 100 parts of d-limonene
A reduced volume polystyrene foam mass containing 60 parts of d-limonene is rolled into a thin film, and a solvent that can be dissolved or mixed with d-limonene but does not dissolve polystyrene is heated to 50 ° C.
１５０150 ° C., the polystyrene thin film is stirred in the warmed solvent and rinsed and / or broken into small pieces, and the d-limonene in the small polystyrene pieces is removed Discharging into a solvent, solid-liquid separation of the mixture to recover the regenerated polystyrene as a powder, and distillation of the separated liquid phase to separately recover d-limonene and the solvent, (5) a method for separating a volume-reduced liquid from a volume-reduced expanded polystyrene according to the above item (1) or (2); and (5) a method containing d-limonene containing 2 to 60 parts of polystyrene per 100 parts of d-limonene. The volume-reduced expanded polystyrene mass is maintained at a temperature of 50 ° C. to 150 ° C., and a solvent that can be dissolved or mixed with d-limonene but does not dissolve polystyrene is prepared. The lump is rinsed and / or broken into small pieces by rolling and / or stirring into a thin film in the presence of the solvent heated to 50 ° C. to 150 ° C., and the thin film is broken into small pieces in the presence of the solvent. The d-limonene in the polystyrene thin film is released into the solvent, the mixture is subjected to solid-liquid separation to recover a regenerated polystyrene as a powder, and the separated liquid phase is distilled to remove d-limonene and the solvent. A method for separating a volume-reduced liquid from a volume-reduced expanded polystyrene according to the above item (1) or (2), wherein the liquid is separately collected.

Further, (6) "a reduced volume of expanded polystyrene mass containing d-limonene containing 2 to 60 parts of polystyrene per 100 parts of d-limonene is formed into a thin thread,
A solvent that can be dissolved or mixed with limonene but does not dissolve polystyrene is kept at a temperature of 50 ° C. to 150 ° C., and the filament of the polystyrene is broken into small pieces in the heated solvent, and After rinsing, d-limonene in the polystyrene small pieces is released into the solvent, the mixture is subjected to solid-liquid separation to recover regenerated polystyrene as a powder, and the separated liquid phase is distilled to obtain d-limonene. And (4) separating the reduced volume liquid from the reduced volume expanded polystyrene according to the above (1) or (2), and (7) “100 parts of d-limonene. The reduced volume of expanded polystyrene containing d-limonene containing 2 to 60 parts of polystyrene per weight is maintained at a temperature of 50 ° C. to 150 ° C. and can be dissolved or mixed with d-limonene, but polystyrene is used. A solvent that does not dissolve the fiber is prepared, and the foamed polystyrene mass is gently extruded with a nozzle into a thin filament in the presence of the solvent heated to 50 to 150 ° C., and the filament is cut into small pieces in the presence of the solvent. Then, d-limonene in the polystyrene small pieces is released into the solvent, the mixture is subjected to solid-liquid separation to recover regenerated polystyrene as a powder, and the separated liquid phase is distilled to obtain d-limonene. A method for separating a reduced volume liquid from a reduced volume expanded polystyrene according to the above item (1) or (2), wherein limonene and a solvent are separately recovered.

Further, (8) "d-limonene containing 2-60 parts of polystyrene per 100 parts of d-limonene is sprayed with a reduced volume of expanded polystyrene mass containing d-limonene to form droplets or spider web-like filaments. None, a solvent that can be dissolved or mixed with d-limonene but does not dissolve polystyrol
Holding at a temperature of 150 ° C. and rinsing and / or breaking into small pieces by stirring the polystyrene droplets or cobweb-like filaments in the heated solvent;
D- in the polystyrene droplets or spider web-like filaments
Limonene is released into the solvent, the mixture is subjected to solid-liquid separation to recover regenerated polystyrene as a powder, and the separated liquid phase is distilled to recover d-limonene and the solvent separately. Method for Separating Reduced Volume Liquid from Reduced Volume Expanded Polystyrene according to Item (1) or (2) ”, (9)“ d containing 100 parts of d-limonene and 2 to 60 parts of polystyrene. -Spraying limonene-containing reduced volume foamed polystyrene mass to form droplets or spider web-like filaments, a solvent that can be dissolved or mixed with d-limonene but does not dissolve polystyrene at 50 ° C Hold at a temperature of 150 ° C. and rinse and / or break into small pieces by stirring the polystyrene droplets or cobweb-like filaments in the heated solvent. The polystyrene small pieces The d-limonene in the spider web-like filament is released into the solvent, the mixture is solid-liquid separated to recover a regenerated polystyrene as a powder, and the separated liquid phase is distilled to obtain d-limonene. -The method for separating a reduced volume liquid from the reduced volume expanded polystyrene according to the above (1) or (2), wherein the limonene and the solvent are separately recovered.
And (10) the step of spraying the volume-reduced expanded polystyrene mass to form droplets having a diameter of 0.6 mm or less or spider web-like filaments simultaneously with the d-limonene; A method for separating a volume-reduced liquid from a volume-reduced expanded polystyrene according to the above item (8) or (9), which comprises spraying a solvent that can be dissolved or mixed but does not dissolve polystyrene. I will provide a.

Furthermore, (11) "as the solvent,
The above items (1) and (2), characterized by using a material which does not azeotrope with d-limonene or has a narrow azeotropic width and does not azeotrope with water or has a narrow azeotropic width. Terms, (3)
Terms, (4), (5), (6), (7), (8)
Method of separating volume-reduced liquid from volume-reduced expanded polystyrene according to any one of paragraphs (9) and (10) ”, (1
2) "characterized by using ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-propanol (isopropanol) and / or 2-butanol as the solvent under normal pressure;
(11) The method for separating a volume-reducing liquid from the volume-reduced expanded polystyrene according to the item (10), and (13), wherein the solvent is 2-propanol (isopropanol). And a method for separating a reduced volume solution from the reduced volume expanded polystyrene described in the section.

Pure d-limonene is one of the terpenes having a boiling point of 177.7 ° C. In the present invention, such pure d-limonene can be used, and commercially available citrus oil can be used. And furthermore, as we proposed in Japanese Patent Application No. 7-258316,
A small amount of a surfactant containing a stock solution of d-limonene as a main component and, if desired, an auxiliary for stabilizing emulsification and / or preventing skin roughness, and optionally a d-limonene solution containing animal and vegetable oils, and a small amount (30% A d-limonene-based water mixture containing water described below can be used.

D-Limonene is generally obtained as a commercially available citrus oil, which contains 80 to 90% of d-limonene, while citrus oil or commercially available d-limonene has a certain boiling point. It is not a single substance but a mixture of many compounds mainly d-limonene. In some cases (when it becomes old), a fraction having a boiling point of 164 ° C. or lower mainly containing organic acids, alcohols and ester components is removed. About 0.15 to 0.2%, a light fraction of 164 ° C to 167 ° C is added to 0.65 to 0.7%.
About 0%, the light fraction at 168 ° C to 170 ° C
About 8.20%, a fraction at 170.5 ° C. is about 10 to 15%, and a fraction at 170.5 ° C. to 172 ° C. is 20 to 26.7%.
About 173 ° C. to 175 ° C.
The fraction at 7 ° C. is about 6 to 8%, and the fraction at 178 ° C. is 3.5 to
About 4.5%, a fraction at 178 ° C to 180 ° C is 7.5 to 9%.
%, The fraction at 180 ° C to 185 ° C is 6.5 to 7.0%
About 185 ° C to 190 ° C for 2.5 to 3.5.
%, A heavy fraction at 190 ° C to 195 ° C is 2.3 to 3%.
About 1% of heavy fraction at 195 ° C to 205 ° C
About 2.8%, colored heavy fraction of 205 ° C. or more 12 to
It contains about 14%, and in some cases (when it is not very old), the initial boiling point also rises to 167 ° C to 170 ° C, while the end point falls to about 210 ° C and the distribution of each fraction The width becomes narrower and, if newer, the boiling point is 174
Most of the fraction at a temperature of from ℃ to 179 ° C (about 95%). The fraction having a boiling point of 114 ° C. to 164 ° C. mainly containing an organic acid component is hardly effective for reducing the volume of foamed polystyrene, and the viscous mixture fraction having a boiling point of 210 ° C. or more is treated with foamed polystyrene. Although it is effective to reduce the volume of polystyrene, it is colored, and it is relatively difficult to remove polystyrene from the reduced volume, and this may cause coloration of regenerated polystyrene. Is preferred. The advantages of the d-limonene-based volume reducing solution containing a small amount of water are as disclosed in the aforementioned Japanese Patent Application No. 7-258316. However, if the water content is too large, the volume reducing efficiency is hindered. -D-limonene liquid used in the present invention is used in the present invention because it reacts with other trace components in the limonene liquid to produce an organic acid component and a coloring component, and also hinders the separation and recovery of d-limonene and the solvent. It is desirable that the water content be 30% or less, preferably 20% or less, more preferably 10% or less.

One of the troublesome points due to the trouble in separating and recovering d-limonene and the solvent by water is that d-limonene and the solvent are emulsified by the presence of water, and the liquid becomes a multiphase. When emulsified, it not only hinders separation and recovery, but also makes it difficult to extract d-limonene to the solvent side by solvent treatment from polystyrene containing d-limonene and reduced in volume. In such a case, the subsequent operation can be performed by breaking the emulsion by adding an emulsion breaking agent. When the solvent is, for example, ethylene glycol monomethyl ether (methyl cellosolve), suitable emulsion breakers include heptanol and hexanol.

The d-limonene used to reduce the volume of the expanded polystyrene is 0.6% of the reduced volume of polystyrene.
In the case of small particles having a diameter of not more than mm, small droplets, small pieces having a thickness of 0.6 mm or less broken, etc., they can be dissolved or mixed with the d-limonene while being heated to 50 ° C to 150 ° C. Solvent treatment (rinsing) with a solvent that does not dissolve the polystyrene quickly and almost completely elutes from the reduced volume polystyrene into the solvent. It has been found that it can be substantially removed before formation.

In the present invention, the used foamed polystyrene is divided into blocks or, if desired, crushed to the size of a thumb head, and then 2 to 70 parts of polystyrene (polystyrene) per 100 parts of d-limonene. Parts, preferably 3 to 50 parts, more preferably 3 to 40 parts, by volume of d-limonene. If the amount of polystyrene to d-limonene is more than 60 parts / 100 parts, the polystyrene cannot be sufficiently gelled into a gel-like mass, and
If the amount is less than 100 parts / part, polystyrene can be converted into a highly viscous liquid, but d required for volume reduction is required.
-Use of a considerable excess of d-limonene relative to the amount of limonene requires extra labor to recover the excess d-limonene.

Solvents which can be dissolved or mixed with d-limonene include aliphatic hydrocarbons such as petroleum ether, ligroin, petroleum benzine, various halogenated hydrocarbons, benzene, toluene, xylene, ethyl acetate, propyl formate and the like. Ester, 1,4-dioxane, ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve), ethylene glycol dimethyl ether, methanol, ethanol, 2-propanol (isopropanol), n-
Most organic solvents such as butanol, 2-butanol, tertiary butanol, n-hexanol, n-heptanol, acetone, methyl ethyl ketone (butanone), dimethylformamide and the like can be mentioned.

Among these solvents, those which do not dissolve polystyrene include aliphatic hydrocarbons such as petroleum ether, ligroin, petroleum benzine, and conversely, ethylene glycol monomethyl ether (methyl cellosolve) and ethylene glycol monoethyl. Examples thereof include ether (ethyl cellosolve), methanol, ethanol, 2-propanol (isopropanol), n-butanol, 2-butanol, tertiary butanol, and n-hexanol. Some of the halogenated hydrocarbons do not dissolve polystyrene, and many others dissolve polystyrene. 1,4-dioxane, acetone, methyl ethyl ketone (butanone), dimethylformamide and the like are polar solvents having strong water solubility or water miscibility, but dissolve polystyrene.

In the case of normal pressure, the solvent used in the present invention preferably has a boiling point of 50 ° C. to 150 ° C.
If a material having a boiling point of less than 50 ° C. is used, it is difficult to heat the volume-reduced expanded polystyrene containing d-limonene to an extremely soft state.
The high temperature causes coloring of the expanded polystyrene which has been reduced in volume, and the operation of separating a high-boiling solvent having a temperature of 150 ° C. or higher from an active ingredient mainly containing d-limonene in the d-limonene liquid becomes difficult.

The solvent used in the present invention is d
-Those which do not azeotrope with limonene or have a narrow azeotropic width, and those which do not azeotrope with water or have a narrow azeotropic width are preferred. Here, “the azeotropic width with d-limonene is narrow” means that the content of d-limonene in the azeotrope is less than 20% (the content of the solvent is 80% or more). And
"Narrow azeotropic width with water" means that the content of water in the azeotrope is less than 20% (the content of the solvent is 80% or more). In the case of a solvent having a wide azeotropic width with d-limonene liquid, and in the case of a solvent having a wide azeotropic width with water, the solvent and d
-The fractionation operation with the limonene liquid becomes inefficient.

As such a solvent, a water-soluble or water-miscible solvent is more preferable. A water-insoluble or water-immiscible aliphatic hydrocarbon is preferably used when the d-limonene solution contains a surfactant and water. Need to be avoided. Of these, it is preferable to mainly use alcohols, particularly ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-propanol (isopropanol) and / or 2-butanol.

The solvent is preferably as high as possible within a range not exceeding a boiling point of 150 ° C., but ethylene glycol monomethyl ether and ethylene glycol monoethyl ether are not preferred because they azeotrope with water and / or d-limonene. Ethanol is water and / or d
-Less azeotropic with limonene and less preferred because it forms a relatively hard skin on polystyrene, whereas 2-butanol azeotropes with water, d-limonene, so isopropanol is most preferred among alcohols, Next, ethylene glycol monomethyl ether is preferred.

A mixed solvent of a plurality of components can be used. In this case, too, a high-temperature treatment at more than 150 ° C. causes coloring of the expanded polystyrene having a reduced volume. It is preferable to avoid it because it becomes difficult to separate it from the active ingredient. In the case of azeotropic distillation with d-limonene liquid at a temperature exceeding 150 ° C., it becomes difficult to separate the same. These solvents are usually d-limonene solution, though depending on the usage of polystyrene in limonene, the number of washings, and the crushing conditions.
60 parts to 3600 per 100 parts of the polystyrene mixture
Parts, preferably 200 to 2000 parts, more preferably 250 to 1000 parts. If the amount is less than 60 parts, d-limonene cannot be sufficiently removed from the mixture,
Even if it is used in an amount of 3600 parts or more, the separation operation of the solvent and d-limonene becomes uneconomical.

[0033]

The present invention will be described in more detail with reference to the following examples. The present invention is not limited to the embodiments. [Example 1] Outer diameter 95 mm, inner diameter 92 mm, width 400 m
A roll roller device that accommodates an electric heat source of 200 W in each of the two rolls of m, the outer surfaces of the rolls are processed with a fluororesin (Tetron, registered trademark), and the temperature can be adjusted by a thermistor element contacting the outer surface ends, The roll surface temperature was set to 80 ° C., and the roll gap was adjusted to 150 μm. 100 g of expanded polystyrene was mixed with polyoxyethylene sorbitan monooleate (Kao Corporation, Rheodol TW-0).
106) 0.9 g, polyoxyethylene lauryl ether (Emulgen 108, Kao Corporation) 0.3 g, water 2.
23 g, d-limonene 211, 175 g (specific gravity 0.84
214.605 g of an aqueous d-limonene solution consisting of 47)
(250 cc), and 334.675 g of the reduced polystyrene content containing d-limonene solution was rolled by the rolling roller device, and the obtained film was immediately heated to 80 ° C.
After being crushed and washed with 3000 cc of isopropanol heated to 80 ° C. for 2 minutes under stirring, 100 g of pure white polystyrene and filtrate 3
210 cc was obtained. The softening point of the dried polystyrene is 1
It was at least 78 ° C. The filtrate was distilled to obtain 2840 cc of isopropanol, 2 cc of water, and d-limonene liquid (citrus oil) 2
44cc (205.3 g) and 1.23 g of a residue mainly composed of a mixture of polyoxyethylene sorbitan monooleate and polyoxyethylene lauryl ether as the balance
was gotten.

Example 2 Using the rolling roller device in Example 1, the roll surface temperature was set to 120 ° C., and the roll gap was adjusted to 60 μm. Expanded polystyrene 100g
Is 0.9 g of polyoxyethylene sorbitan monooleate (Kao Corp., Reodol TW-0106), 0.3 g of polyoxyethylene lauryl ether (Kao Corp., Emulgen 108), 2.23 g of water, d-limonene 2
Aqueous d-consisting of 11,175 g (specific gravity 0.8447)
The volume was reduced with a volume reduction solution of 214.605 g (250 cc) of a limonene solution, and 334.675 g of a reduced volume polystyrene containing d-limonene solution was rolled by the rolling roller device. The mixture was placed in a household mixer set at 0 ° C, crushed and washed with 3000 cc of isopropanol heated to 80 ° C under stirring for 2 minutes, and then filtered to obtain 100 g of pure white polystyrene and 3120 cc of a filtrate. The softening point of the dried polystyrene was 178 ° C or higher. The filtrate was distilled, 2760 cc of isopropanol, 2 cc of water and 227 cc (191.7 g) of d-limonene liquid (citrus oil).
As a result, 1.23 g of a residue mainly containing a mixture of polyoxyethylene sorbitan monooleate and polyoxyethylene lauryl ether was obtained.

Example 3 Using the rolling roller device in Example 1, the roll surface temperature was set to 40 ° C., and the roll gap was adjusted to 60 μm. Expanded polystyrene 100g
Is 0.9 g of polyoxyethylene sorbitan monooleate (Kao Corp., Reodol TW-0106), 0.3 g of polyoxyethylene lauryl ether (Kao Corp., Emulgen 108), 2.23 g of water, d-limonene 2
Aqueous d-consisting of 11,175 g (specific gravity 0.8447)
The volume was reduced with a volume reduction solution of 214.605 g (250 cc) of a limonene solution, and 334.675 g of a reduced volume polystyrene containing d-limonene solution was rolled by the rolling roller device. The mixture was placed in a household mixer set at a temperature of 0 ° C., crushed and washed with 3000 cc of isopropanol heated to 80 ° C. for 2 minutes with stirring, and then filtered to obtain 100 g of pure white polystyrene and 3065 cc of a filtrate. The softening point of the dried polystyrene was 178 ° C or higher. The filtrate was distilled, 2710 cc of isopropanol, 2 cc of water, and 228 cc (192.6 g) of d-limonene liquid (citrus oil).
As a result, 1.23 g of a residue mainly containing a mixture of polyoxyethylene sorbitan monooleate and polyoxyethylene lauryl ether was obtained.

Example 4 Using the rolling roller device in Example 1, the roll surface temperature was set to 50 ° C., and the roll gap was adjusted to 100 μm. Expanded polystyrene 100g
Is 0.9 g of polyoxyethylene sorbitan monooleate (Kao Corp., Reodol TW-0106), 0.3 g of polyoxyethylene lauryl ether (Kao Corp., Emulgen 108), 2.23 g of water, d-limonene 2
Aqueous d-consisting of 11,175 g (specific gravity 0.8447)
The volume of the limonene solution was reduced with a volume reduction solution of 214.605 g (250 cc), and the reduced volume rice cake-like polystyrene gel was passed through the rolling mill, and then placed in a household mixer kept at 80 ° C. After crushing and washing with 2500 cc of isopropanol heated to 80 ° C. for 2 minutes with stirring, the mixture was filtered to obtain 100 g of pure white polystyrene and 2750 cc of a filtrate.
The softening point of the dried polystyrene was 178 ° C or higher. The filtrate was distilled to obtain 2380 cc of isopropanol, 2 cc of water and 194 cc of d-limonene liquid (citrus oil) (16 cc).
3.9 g) and 1.23 g of a residue mainly comprising a mixture of polyoxyethylene sorbitan monooleate and polyoxyethylene lauryl ether were obtained.

Comparative Example 1 The roll surface temperature was set to 40 ° C. and the roll gap was adjusted to 120 μm using the rolling roller device in Example 1. Expanded polystyrene 100g
Is 0.9 g of polyoxyethylene sorbitan monooleate (Kao Corp., Reodol TW-0106), 0.3 g of polyoxyethylene lauryl ether (Kao Corp., Emulgen 108), 2.23 g of water, d-limonene 2
Aqueous d-consisting of 11,175 g (specific gravity 0.8447)
The volume was reduced with a volume reducing solution of 214.605 g (250 cc) of a limonene solution, and 334.675 g of a reduced volume polystyrene containing d-limonene solution was rolled by the rolling roller device. 3,000 cc of isopropanol heated to 40 ° C with stirring.
After crushing and washing for 1 minute, the mixture was filtered to obtain 100 g of polystyrene and 3240 cc of a filtrate. The softening point of the dried polystyrene was 152 ° C. This means that d-limonene in polystyrene has not been removed yet.

Comparative Example 2 Using the rolling roller device in Example 1, the roll gap was adjusted to 150 μm without heating the roll surface. Expanded polystyrene 100g
Is 0.9 g of polyoxyethylene sorbitan monooleate (Kao Corp., Reodol TW-0106), 0.3 g of polyoxyethylene lauryl ether (Kao Corp., Emulgen 108), 2.23 g of water, d-limonene 2
Aqueous d-consisting of 11,175 g (specific gravity 0.8447)
The volume was reduced with a volume reducing solution of 214.605 g (250 cc) of a limonene solution, and 334.675 g of a reduced volume polystyrene containing d-limonene solution was rolled by the rolling roller device. 160 in the mixing mixer
2- (methoxymethoxy) ethanol 25 heated to 25 ° C
After crushing and washing at 00 cc for 2 minutes, filtration was carried out, and this operation was repeated (total of 5000 cc of 2- (methoxymethoxy) ethanol twice), followed by filtration. The resulting polystyrene was colored light brown.

Example 5 100 g of expanded polystyrene
Is 0.9 g of polyoxyethylene sorbitan monooleate (Kao Corp., Reodol TW-0106), 0.3 g of polyoxyethylene lauryl ether (Kao Corp., Emulgen 108), 2.23 g of water, d-limonene 2
Aqueous d-consisting of 11,175 g (specific gravity 0.8447)
The limonene solution was reduced in volume with a 2214.605 g (250 cc) volume reducing solution, and the reduced volume of the rice cake-like polystyrene gel was reduced to 8%.
Place in a household mixer kept at 0 ° C and stir at 80 ° C
After crushing and washing with 3000 cc of isopropanol heated for 2 minutes, the mixture was filtered to obtain 100 g of pure white polystyrene and 3230 cc of a filtrate. The dried polystyrene had an average diameter of 0.585 mm as determined by visual observation under a microscope and a melting point of 1
It was at least 78 ° C. The filtrate was distilled, and 2920 cc of isopropanol, 2 cc of water, and d-limonene liquid (citrus oil) 2
28 cc (192.6 g) and the remainder 1.23 g mainly composed of a mixture of polyoxyethylene sorbitan monooleate and polyoxyethylene lauryl ether.
was gotten.

Example 6 50 g of expanded polystyrene was
0.6 g of polyoxyethylene sorbitan monooleate (Kao Corporation, Leodol TW-0106), 0.5 g of polyoxyethylene lauryl ether (Kao Corporation, Emulgen 108), 2.16 g of water, d-limonene 21
A volume-reduced solution of 217.695 g (250 cc) of an aqueous d-limonene solution consisting of 4,435 g (specific gravity 0.8447) was reduced.
The mixture was crushed and washed with 2500 cc of isopropanol heated to 80 ° C. for 2 minutes under stirring, filtered, and this operation was repeated (total of 5000 cc of isopropanol twice). 50 g of polystyrene and filtrate 5209. cc. The average diameter of the dried polystyrene was 0.58 by visual observation under a microscope.
mm and the melting point was 178 ° C. or higher. The filtrate was distilled and 4865 cc of isopropanol, 1.92 cc of water and d
230 ml (194.3 g) of limonene liquid (citrus oil) and 1.25 g of a residue mainly comprising a mixture of polyoxyethylene sorbitan monooleate and polyoxyethylene lauryl ether were obtained.

Comparative Example 3 100 g of expanded polystyrene
Of polyoxyethylene sorbitan monooleate (Kao Corporation, Reodol TW-0106) (0.5 g), polyoxyethylene lauryl ether (Kao Corporation, Emulgen 108) 3.5 g, water 25 g, d-limonene 21
The volume was reduced with a volume reducing solution of 240.175 g (250 cc) of an aqueous d-limonene solution consisting of 1,175 g (specific gravity 0.8447).
The mixture was placed in a household mixer kept warm, and crushed and washed with 500 cc of isopropanol heated to 80 ° C. for 2 minutes with stirring, followed by filtration. This operation was repeated (1000 cc of isopropanol used twice) to obtain 100% pure white polystyrene.
g and the filtrate 1173 cc were obtained. The dried polystyrene had an average diameter of 1.1 mm and a softening point of about 156 ° C. by visual observation under a microscope. This is the d-
It means that limonene has not been removed yet. The filtrate is distilled and 920 cc of isopropanol, 24 cc of water and d
-229 cc (193.3 g) of limonene liquid (citrus oil) and, as the remainder, 4.37 g of a residue mainly comprising a mixture of polyoxyethylene sorbitan monooleate and polyoxyethylene lauryl ether were obtained.

Example 7 50 g of expanded polystyrene was
0.1 g of polyoxyethylene sorbitan monooleate (Kao Corporation, Leodol TW-0106), 0.6 g of polyoxyethylene lauryl ether (Kao Corporation, Emulgen 108), 22.6 g of water, d-limonene 21
An aqueous d-limonene solution composed of 1,175 g (specific gravity 0.8447) was reduced in volume with a volume reducing solution of 234.475 g (250 cc).
The mixture was placed in a household mixer kept warm, and crushed and washed with 1500 cc of isopropanol heated to 80 ° C. for 2 minutes with stirring, followed by filtration. This operation was repeated, followed by crushing and washing with 3000 cc of heated isopropanol for 2 minutes, followed by filtration. (3 times use of 6000 cc of isopropanol), 50 g of pure white polystyrene and 6105 cc of filtrate were obtained. The average diameter of the dried polystyrene was determined by visual measurement under a microscope.
It was 0.59 mm and the softening point was 176 ° C. or higher. The filtrate was distilled to give 5820 cc of isopropanol and 23 c of water.
195 cc (164.7) of c and d-limonene liquid (citrus oil)
2 g) and, as the remainder, 1.2 g of a residue mainly comprising a mixture of polyoxyethylene sorbitan monooleate and polyoxyethylene lauryl ether were obtained.

Example 8 50 g of expanded polystyrene was
0.5 g of polyoxyethylene sorbitan monooleate (Kao Corporation, Leodol TW-0106), 3.0 g of polyoxyethylene lauryl ether (Kao Corporation, Emulgen 108), 113.0 g of water, d-limonene 1
A volume-reduced solution of 1172.375 g (1250 cc) of an aqueous d-limonene solution composed of 056 g (specific gravity 0.8447) was used to reduce the volume of the reduced polystyrene gel, and a commercially available water jet nozzle (Ikeuchi Co., Ltd.) Made, AKI J
et; registered trademark) as a nozzle adapter,
Water is compressed from each central hole provided concentrically inside each of the annular outlet holes for compressed air arranged so that the internal piston is actuated by the compressed air and bifurcated to collide with the compressed air flow. SOA type A that is ejected in a mist along with the flow
Aerial spraying treatment is performed using KI075PPSS303 (produced by Ikeuchi Co., Ltd.) with the gas-liquid mixing inner cap removed and attached, and the obtained mist droplets or spider web-like thread-like adhesive substance are treated at 80 ° C. Isopropanol heated to 6000
The mixture was gently received along the rotation direction of the vortex due to the stirring of cc, and after stirring for 5 minutes after spraying, the mixture was filtered to obtain 50 g of pure white polystyrene and 7150 cc of filtrate. The average diameter of the dried polystyrene was 0.31 as determined by visual observation under a microscope.
mm and the softening point was 185 ° C or higher.

Comparative Example 4 In the same manner as in Example 5, 100 g of expanded polystyrene was charged with polyoxyethylene sorbitan monooleate (Kao Corporation, Rheodol TW-01).
06) 0.9 g, 0.3 g of polyoxyethylene lauryl ether (Emulgen 108, Kao Corporation), 2.2 water
3 g, d-limonene 211, 175 g (specific gravity 0.844
214.605 g of an aqueous d-limonene solution consisting of 7) (2
50 cc) of the volume-reduced solution, put the reduced volume of the dough-like polystyrene gel into a household mixer kept at 80 ° C., and 3,000 cc of isopropanol which is not heated under stirring.
Crushed and washed for 1 minute, filtered and 108 g of polystyrene
3236 cc of a filtrate was obtained. The dried polystyrene had an average diameter of 1.16 mm and a softening point of 149.5 ° C. by visual measurement under a microscope. This is the d in polystyrene
It means that limonene has not yet been removed.

Comparative Example 5 In the same manner as in Example 5, foamed polystyrene (50 g) was mixed with polyoxyethylene sorbitan monooleate (Kao Corporation, Rheodol TW-010).
6) 0.6 g, polyoxyethylene lauryl ether (Kao Corporation, Emulgen 108) 0.5 g, water 2.1
6 g, d-limonene 214, 435 g (specific gravity 0.844
217.695 g of an aqueous d-limonene solution consisting of 7) (2
53.85 cc) was reduced in volume, and the reduced volume rice cake-like polystyrene gel was placed in a household mixer kept at 160 ° C. and heated to 160 ° C. with stirring. After crushing and washing with 2500 cc of ethanol for 2 minutes, filtration was performed, and this operation was repeated (total of 2 times, 2 times).
-(Methoxymethoxy) ethanol 5000 cc) and filtered. The resulting polystyrene was colored light brown.

Comparative Example 6 In the same manner as in Example 6, foamed polystyrene (50 g) was mixed with polyoxyethylene sorbitan monooleate (Kao Corporation, Rheodol TW-010).
6) 0.6 g, 2.8 g of polyoxyethylene lauryl ether (Emulgen 108, Kao Corporation), 100 parts of water
g, d-limonene 114.435 g (specific gravity 0.844
21.835 g of an aqueous d-limonene solution consisting of 7) (2
Although the volume was reduced with a volume reducing solution of 53.85 cc), the volume could not be completely reduced. This incompletely volume-reduced polystyrene gel is placed in a household mixer kept at 80 ° C., crushed and washed with 2500 cc of isopropanol heated to 80 ° C. for 2 minutes under stirring, filtered, and this operation is repeated ( Two times, 5000 cc of isopropanol) and filtration to obtain 86 g of an incompletely reduced volume polystyrene gel and a cloudy filtrate. The polystyrene had an odor peculiar to d-limonene and was still soft, and the fingertip was wet when strongly compressed with the fingertip. This means that d-limonene in polystyrene has not been removed yet. The effect of the difference in water content was as shown in Table 1 below.

[0047]

[Table 1]

Comparative Example 7 In the same manner as in Example 5, 100 g of expanded polystyrene was added to polyoxyethylene sorbitan monooleate (Kao Corporation, Rheodol TW-01).
06) 0.9 g, 0.3 g of polyoxyethylene lauryl ether (Emulgen 108, Kao Corporation), 2.2 water
3 g, d-limonene 211, 175 g (specific gravity 0.844
23.675 g of an aqueous d-limonene solution consisting of 7) (2
The volume reduced with a 50 cc) volume reducing solution, the reduced volume of the dough-shaped polystyrene gel was placed in a household mixer kept at 35 ° C., and isopropanol 300 heated to 35 ° C. with stirring.
After crushing and washing with 0 cc for 1 minute, filtration and polystyrene 1
14 g and 3240 cc of filtrate were obtained. The dried polystyrene had an average diameter of 0.98 mm and a softening point of 142.6 ° C. by visual observation under a microscope. This means that d-limonene in polystyrene has not been removed yet.

[Comparative Example 8] In the same manner as in Example 5, 10 g of expanded polystyrene was added to polyoxyethylene sorbitan monooleate (Kao Corporation, Rheodol TW-010).
6) 0.09 g, polyoxyethylene lauryl ether (Emulgen 108, Kao Corporation) 0.03 g, water 0.1%.
223 g, d-limonene 21, 1175 g (specific gravity 0.8
23.4675 g of an aqueous d-limonene solution consisting of 447)
(25 cc), and the reduced volume rice cake-shaped polystyrene gel was placed in a mortar kept at 60 ° C.
After crushing and washing with 120 cc of isopropanol heated to 10 ° C. for 10 minutes, the mixture was filtered and 12 g of polystyrene and filtrate 112 were added.
cc. The dried polystyrene has an average diameter of at least 2.45 mm as determined by visual observation under a microscope, and has a standard deviation (σ).
Was 15, and the softening point was 137.2 ° C. This means that d-limonene in polystyrene has not been removed yet.

[Comparative Example 9] In the same manner as in Example 6, 50 g of expanded polystyrene was mixed with polyoxyethylene sorbitan monooleate (Raodol TW-010, manufactured by Kao Corporation).
6) 0.6 g, polyoxyethylene lauryl ether (Kao Corporation, Emulgen 108) 0.5 g, water 2.1
6 g, d-limonene 214, 435 g (specific gravity 0.844
217.695 g of an aqueous d-limonene solution consisting of 7) (2
A volume-reduced solution of 50 cc) is used to reduce the volume. The reduced volume of the dough-shaped polystyrene gel is placed in a ball mill previously kept at 40 ° C., and 800 cc of isopropanol heated to 40 ° C.
After crushing under natural cooling for 0 minutes, the mixture was filtered and polystyrene 1
2 g and a filtrate of 112 cc were obtained. The dried polystyrene had an average diameter of 1.37 mm or more, a standard deviation (σ) of 8.7, and a softening point of 143.9 ° C. as determined by visual observation under a microscope. This means that d-limonene in polystyrene has not been removed yet.

Comparative Example 10 In the same manner as in Comparative Example 3, 10 g of expanded polystyrene was added to polyoxyethylene sorbitan monooleate (Kao Corporation, Rheodol TW-01).
06) 0.05 g, polyoxyethylene lauryl ether (Kao Co., Ltd., Emulgen 108) 0.35 g, water 2.5 g, d-limonene 21.1175 g (specific gravity 0.8)
24.0175 g of an aqueous d-limonene solution consisting of 447)
(25 cc) The volume-reduced solution was reduced in volume, and the reduced volume rice cake-shaped polystyrene gel was placed in a household mixer kept at 80 ° C. and stirred with 50 cc of acetone heated to 50 ° C. for 3 minutes. Became homogeneous with acetone. This means that polystyrene and d-limonene cannot be solid-liquid separated.

[Comparative Example 11] In the same manner as in Example 7, 5 g of expanded polystyrene was added to polyoxyethylene sorbitan monooleate (Kao Corporation, Rheodol TW-010).
6) 0.01 g, polyoxyethylene lauryl ether (Kao Corporation, Emulgen 108) 0.06 g, water 2.
26 g, d-limonene 21, 1175 g (specific gravity 0.84
23.4475 g of an aqueous d-limonene solution consisting of 47)
(25 cc) was reduced in volume with a volume reducing solution, and the reduced volume rice cake-shaped polystyrene gel was placed in a household mixer kept at 80 ° C. and stirred with 150 cc of dioxane heated to 80 ° C. for 3 minutes. Became homogeneous with dioxane. This means that polystyrene and d-limonene cannot be solid-liquid separated.

[Comparative Example 12] In the same manner as in Example 5, 100 g of expanded polystyrene was charged with polyoxyethylene sorbitan monooleate (Kao Corporation, Rheodol TW-0).
Aqueous d-limonene liquid comprising 0.09 g, 0.03 g of polyoxyethylene lauryl ether (Emulgen 108, Kao Corporation), 0.223 g of water, 21,1175 g of d-limonene (specific gravity: 0.8447) 23. 46
An attempt was made to reduce the volume with a 75 g (25 cc) volume reducing solution. The polystyrene became hard and could not be completely reduced in volume. The effect of the difference in volume reduction solution was as shown in Table 2 below.

[0054]

[Table 2]

In the case of the sample c, the first crushing and washing with 85 cc of isopropanol resulted in a slightly hard rice cake and could not be crushed. The second crushing and washing produced coarse particles mixed with fine particles.

Example 9 One end of a steel pipe was sealed with a steel plug having an outer diameter of 30 mm, and a cylinder provided with 24 holes of 150 μm in diameter on the surface of the plug was formed. An extruder comprising a rod was prepared. 10 g of expanded polystyrene was mixed with polyoxyethylene sorbitan monooleate (Kao Corporation, Rheodol TW-010).
6) 0.9 g, polyoxyethylene lauryl ether (Kao Co., Ltd., Emulgen 108) 0.3 g, water 2.2
3 g, d-limonene 211, 175 g (specific gravity 0.844
221.675 g of an aqueous d-limonene solution consisting of 7) (2
231.675 g of the reduced polystyrene containing d-limonene solution was placed in the extruder, and isopropanol 2000 heated to 80 ° C.
The powder was rapidly extruded from the hydraulic device at an air pressure of 7 kg into the cc, but the isopropanol liquid served as a barrier, and the filament changed from a filament to a lump in the isopropanol liquid, and was not sufficiently contacted with isopropanol. Then, slowly extrude by hand with an extruding rod, set the polystyrene-containing d-limonene solution to 80 ° C., receive isopropanol, and receive it in a very mildly agitated household mixer. Isopropanol heated to 80 ° C (20 in total)
(00 cc) for 2 minutes, followed by filtration to obtain 100 g of pure white polystyrene and 2210 cc of a filtrate. The softening point of the dried polystyrene was 178 ° C or higher. The filtrate is distilled and 1840 cc of isopropanol, 2 cc of water and d
-228 cc (192.6 g) of limonene liquid (citrus oil) and as residue 1.23 g of a residue mainly comprising a mixture of polyoxyethylene sorbitan monooleate and polyoxyethylene lauryl ether.

[Examples 10] to [Example 16] and [Comparative Examples 13] to [Comparative Example 14] The same tests as in Examples 1 to 9 were performed for the following Examples and Comparative Examples. The results are shown in Table 3.

[Examples 17] to [Example 22] and [Comparative Examples 15] to [Comparative Example 22] Further, ethylene glycol monomethyl ether (methyl cellosolve) was used in place of isopropanol. Each test of Example and Comparative Example was further performed in the same manner as described above. The results are shown in Table 4.

[0059]

[Table 3]

[0060]

[Table 4]

[0061]

As is clear from the above detailed and specific description, according to the present invention, both gel and paste-containing reduced polystyrene containing d-limonene having high affinity for polystyrene are used. An excellent effect is obtained in that they can be almost completely separated without partial decomposition or coloring, and both can be recovered in a reusable state.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Seiji Tsumagori 6-11-3 Nishi-Shinjuku, Shinjuku-ku, Tokyo Nishi-Shinjuku KB Building Shinko Refine Co., Ltd. (72) Inventor Yutaka Saito 6, Nishi-Shinjuku, Shinjuku-ku, Tokyo 11-11-3 Nishishinjuku KB Building Shinko Refine Co., Ltd.

Claims (13)

[Claims] 1. A reduced volume polystyrene foam lump containing d-limonene containing 2 to 60 parts of polystyrene (polystyrene) per 100 parts of d-limonene is treated at 50 ° C. to 150 ° C.
C., kept in a state of being warmed to C, preparing a solvent that can be dissolved or mixed with d-limonene but does not dissolve polystyrene, and the foamed polystyrene mass is heated to 50C to 150C.
Rinsing in the solvent in the state of small particles or droplets of polystyrene, small pieces in which a thin film or a film is broken, or small pieces in which fine threads are cut in the solvent warmed in the solvent, and removing the polystyrene particles or small pieces in the small pieces. releasing d-limonene into the solvent, solid-liquid separation of the mixture to recover regenerated polystyrene as a powder, and distillation of the separated liquid phase to separately recover d-limonene and the solvent. A method for separating a reduced volume solution from a reduced volume expanded polystyrene. 2. The reduced polystyrene foam according to claim 1, wherein said small particles or droplets, thin film pieces, or small pieces obtained by cutting fine threads have a diameter or thickness of 0.6 mm or less. To separate the volume-reduced solution from water. 3. A volume-reduced expanded polystyrene mass containing d-limonene containing 2 to 60 parts of polystyrene per 100 parts of d-limonene is kept at a temperature of 50 ° C. to 150 ° C. and dissolved with d-limonene. Alternatively, a solvent that can be mixed but does not dissolve polystyrene is prepared, and the foamed polystyrene mass is divided into small particles of polystyrene by rapidly stirring in the solvent heated to 50 ° C. to 150 ° C. The d-limonene in the polystyrene small particles is released into the solvent, the mixture is subjected to solid-liquid separation to recover a regenerated polystyrene as a powder, and the separated liquid phase is distilled to remove d-limonene and the solvent. The method for separating a volume-reduced liquid from a volume-reduced expanded polystyrene according to claim 1, wherein the volume-reduced liquid is collected separately. 4. A reduced volume polystyrene foam containing d-limonene containing 2 to 60 parts of polystyrene per 100 parts of d-limonene is rolled into a thin film, which can be dissolved or mixed with d-limonene, but is polystyrene. Is kept in a heated state at 50 ° C. to 150 ° C., and the thin film of polystyrene is agitated in the heated solvent to be rinsed and / or broken into small pieces, and the polystyrene small pieces are broken. The d-limonene in the solvent is released into the solvent, the mixture is solid-liquid separated to recover a regenerated polystyrene as a powder, and the separated liquid phase is distilled to collect the d-limonene and the solvent separately. A method for separating a volume-reduced liquid from a volume-reduced expanded polystyrene according to any one of claims 1 and 2, characterized in that: 5. A volume-reduced expanded polystyrene block containing d-limonene containing 2 to 60 parts of polystyrene per 100 parts of d-limonene is kept at a temperature of 50 to 150 ° C., and d-limonene is heated. A solvent which can be dissolved or mixed with but does not dissolve polystyrene, is prepared by rolling and / or stirring the foamed polystyrene mass into a thin film in the presence of the solvent heated to 50 ° C. to 150 ° C. And / or breaks into small pieces, breaks the thin film into small pieces in the presence of the solvent, releases d-limonene in the polystyrene thin film into the solvent, and separates the mixture into solid and liquid to form a powder. The volume-reduced expanded polystyrene according to claim 1 or 2, wherein the recovered polystyrene is recovered, and the separated liquid phase is distilled to recover d-limonene and a solvent separately. To separate the volume-reducing liquid from the solution. 6. A volume-reduced expanded polystyrene block containing d-limonene containing 2 to 60 parts of polystyrene per 100 parts of d-limonene is formed into a thin thread, which can be dissolved or mixed with d-limonene but is polystyrene. Is kept at 50 ° C. to 150 ° C. in a heated state, the filaments of the polystyrene are broken into small pieces in the heated solvent, and the d-limonene in the small pieces of polystyrene is rinsed by rinsing. Into the solvent, solid-liquid separation of the mixture to recover the regenerated polystyrene as a powder, and distillation of the separated liquid phase to separately recover d-limonene and the solvent. A method for separating a reduced volume solution from the reduced volume expanded polystyrene according to claim 1. 7. A volume-reduced expanded polystyrene block containing d-limonene containing 2 to 60 parts of polystyrene per 100 parts of d-limonene is kept at a temperature of 50 ° C. to 150 ° C., and d-limonene is heated. A solvent that can be dissolved or mixed with but does not dissolve polystyrene is prepared, and the foamed polystyrene mass is gently nozzle-extruded into a thin filament in the presence of the solvent heated to 50 ° C. to 150 ° C. The filamentous body is cut into small pieces below, d-limonene in the small pieces of polystyrene is released into the solvent, and the mixture is subjected to solid-liquid separation to recover the regenerated polystyrene as a powder. The method for separating a reduced volume liquid from a reduced volume expanded polystyrene according to any one of claims 1 and 2, wherein the liquid phase is distilled to recover d-limonene and a solvent separately. 8. A volume-reduced expanded polystyrene block containing d-limonene containing 2 to 60 parts of polystyrene per 100 parts of d-limonene is sprayed to form droplets or spider web-like filaments. A solvent that can be dissolved or mixed with limonene but does not dissolve polystyrene is kept at a temperature of 50 ° C. to 150 ° C., and the polystyrene droplets or spider webs are formed in the heated solvent. The body is rinsed and / or broken into small pieces by stirring to release the polystyrene droplets or d-limonene in the spider web into the solvent and solid-liquid separation of the mixture. 3. The volume reduction according to claim 1, wherein recovered polystyrene as a powder is recovered, and the separated liquid phase is distilled to recover d-limonene and a solvent separately. From pre-expanded polystyrene A method for separating a volume-reducing liquid. 9. A volume-reduced expanded polystyrene mass containing d-limonene containing 2 to 60 parts of polystyrene per 100 parts of d-limonene is sprayed to form droplets or spider web-like filaments. A solvent that can be dissolved or mixed with limonene but does not dissolve polystyrene is kept at a temperature of 50 ° C. to 150 ° C., and the droplets of the polystyrol or spider webs are formed in the heated solvent. The filaments are rinsed and / or broken into pieces by stirring, and the polystyrene flakes or d-limonene in the web-like filaments are released into the solvent by rinsing, and the mixture is subjected to solid-liquid separation. 3. The method according to claim 1, wherein the recovered polystyrene as a powder is recovered, and the separated liquid phase is distilled to recover d-limonene and the solvent separately. Containerized foaming police A method for separating the volume-reducing liquid from styrene. 10. The step of spraying the volume-reduced expanded polystyrene mass to form droplets or spider webs having a diameter of 0.6 mm or less simultaneously with the d-limonene and The method for separating a reduced volume liquid from a reduced volume expanded polystyrene according to claim 8, wherein the method comprises spraying a solvent which can be dissolved or mixed but does not dissolve polystyrene. . 11. A solvent which does not azeotrope with d-limonene or has a narrow azeotropic width and does not azeotrope with water or has a narrow azeotropic width as water,
A method for separating a reduced volume liquid from a reduced volume expanded polystyrene according to any one of claims 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10. 12. The method according to claim 10, wherein the solvent is mainly ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-propanol (isopropanol) and / or 2-butanol under normal pressure. A method for separating a reduced volume solution from a reduced volume expanded polystyrene. 13. The method for separating a reduced volume liquid from a reduced volume expanded polystyrene according to claim 12, wherein 2-propanol (isopropanol) is used as the solvent.