CN1316408A - Method for recovering phenylethylene monomer from impact resilience polystyrene - Google Patents

Method for recovering phenylethylene monomer from impact resilience polystyrene Download PDF

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CN1316408A
CN1316408A CN00108078A CN00108078A CN1316408A CN 1316408 A CN1316408 A CN 1316408A CN 00108078 A CN00108078 A CN 00108078A CN 00108078 A CN00108078 A CN 00108078A CN 1316408 A CN1316408 A CN 1316408A
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sulfate
impact
styrene monomer
flask
resistant polystyrene
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佐藤卓巳
增成光夫
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TAIYO DEVELOPMENT Co Ltd
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TAIYO DEVELOPMENT Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/053—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/16—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with inorganic material
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/22—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by depolymerisation to the original monomer, e.g. dicyclopentadiene to cyclopentadiene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/32—Manganese, technetium or rhenium
    • C07C2523/34—Manganese
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
    • C07C2527/053—Sulfates or other compounds comprising the anion (SnO3n+1)2-

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
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  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

To provide a method for recovering styrene monomer from impact- resistant polystyrene, in which the industrially useful styrene monomer can be recovered in a high yield and in a high purity from the impact-resistant polystyrene wastes whose effective recycling method has not been established. SOLUTION: This method for recovering the styrene monomer from the impact-resistant polystyrene is characterized by its thermal decomposition, use of a metal sulfate and/or manganese dioxide as a catalyst.

Description

From impact-resistant polystyrene, reclaim the method for styrene monomer
The present invention relates to a kind of method that from impact-resistant polystyrene, reclaims styrene monomer, this method is by heating and decomposes impact-resistant polystyrene and obtain styrene monomer, and its objective is provides that a kind of to be recovered in industrial with high yield be the method for the high-purity benzene vinyl monomer of useful materials from impact-resistant polystyrene.By convention, also do not set up the effective ways that reclaim these wastes at present.
Impact-resistant polystyrene (HI-PS) is a kind of oyster white resin that is obtained by vinylbenzene and divinyl rubber graft copolymerization, and it has the high impact strength higher 5 to 10 times than polystyrene.
Such impact-resistant polystyrene with excellent shock strength like this has been widely used as different products, as televisor, air conditioning machinery and food container, with our daily life seen in some impact-resistant polystyrene products, for example be used for the packaging vessel of beverage such as Yakult (trade(brand)name).
By convention, among waste, be to be used to make office appliance etc. with one is partially recycled, yet these wastes of the great majority that produced by houseware are as on-fuel waste and buried from this class impact-resistant polystyrene product.
In this case, come into effect, urged specific organization to carry out the recovery operation of PET bottle in the absorption method of on July 1st, 1997 relevant container and packing material (be used to promote that the product classification relevant with container and packing material collected and reclaimed law).In addition, from 2000, the same law about plastic containers except that the PET bottle and packing material came into effect, and therefore, must retrieve the waste from the impact-resistant polystyrene product container of lactic drink (as be used to pack).
Yet at present great majority are as non-burning waste and buried from the wastes of impact-resistant polystyrene product as mentioned above, and do not set up the method for effective recovery impact-resistant polystyrene product.
As the present invention to solve the above problems, thereby the purpose of this invention is to provide a kind of method that from impact-resistant polystyrene, reclaims styrene monomer, styrene monomer wherein is the material in industrial practicality, and it can reclaim by high yield from the impact-resistant polystyrene waste.
The present invention has solved above-mentioned problem, the method that from impact-resistant polystyrene, reclaims styrene monomer of the present invention, it is by heating and decomposes the styrene monomer that impact-resistant polystyrene obtains, it is characterized in that using a kind of vitriol and/or Manganse Dioxide as catalyzer.
The method that reclaims styrene monomer from impact-resistant polystyrene of the present invention is characterized in that described vitriol is metal sulfate.
Of the present inventionly from impact-resistant polystyrene, reclaim cinnamic method, it is characterized in that described vitriol is to be no less than a kind of following material that is selected from least: sal epsom, manganous sulfate, calcium sulfate, antimony trisulfate, sodium sulfate, ferric sulfate (II), zinc sulfate, Tai-Ace S 150 and vitriolate of tartar.
The method that reclaims styrene monomer from impact-resistant polystyrene of the present invention, the Heating temperature that it is characterized in that polystyrene resin is due to being not more than 350 ℃.
The method that reclaims styrene monomer from impact-resistant polystyrene of the present invention is characterized in that when the thermolysis impact-resistant polystyrene, used catalyzer is a kind of vitriol and/or Manganse Dioxide.
These Application of Catalyst make polystyrene carry out thermolysis under low relatively temperature becomes possibility, and has also reduced the content that is included in the lower-molecular-weight component in the thermolysis steam.In addition, can easily obtain these catalyzer, thereby reduce the cost of catalyzer thus with quite low cost.
Below will discuss to the method that from impact-resistant polystyrene, reclaims styrene monomer according to the present invention.
According to the method that reclaims styrene monomer from impact-resistant polystyrene of the present invention, it is that a kind of vitriol and/or Manganse Dioxide are used as catalyzer.
Especially, the example of described vitriol comprises sulphuric anhydride, as zinc sulfate, Tai-Ace S 150, antimonyl sulfate, antimony trisulfate (III), ammonium sulfate, exsiccated ammonium alum, chromium sulphate (III) ammonium, rose vitriol (II) ammonium, ferric sulfate (II) ammonium, ferric sulfate (III) ammonium, manganous sulfate (II) ammonium, sulfuric acid iridium (III), lead sulfate, lead vitriol, Cadmium Sulphate, vitriolate of tartar, gallium sulfate (III), potassium aluminium sulfate, chromium sulphate (III) potassium, calcium sulfate, the standard Sulfuric acid disilver salt, the Tai-Ace S 150 guanidine, chromium sulphate (II), chromium sulphate (III), rose vitriol (II), rose vitriol (III), zirconium sulfate (IV), Mercury bisulfate (I), hydrogen3indryl sulfate, sal enixum, tin sulphate (II), Strontium Sulphate, cerous sulfate (III), cerous sulfate (IV), titanium sulfate (III), titanium sulfate (IV), ferric sulfate (II), ferric sulfate (III), copper sulfate (II), sulfuric acid dodecyl sodium, thorium sulfate (IV), sodium sulfate, aluminium sodium sulfate, lead sulfate (II), lead sulfate (IV), single nickel salt (II), Tai-Ace S 150 nickel (II), nitrosyl sulfate, the sal epsom disodium, Neodymium sulfate (III), sulfuric acid alum (III), barium sulfate, the sulfuric acid hydroxylammonium, praseodymium sulfate (III), sal epsom, sulfuric acid dipotassium magnesium, manganous sulfate (II), manganous sulfate (III), lanthanum sulfat (III), lignosulfates, Lithium Sulphate, rubidiurn sulfate, aluminum rubidium sulfate and cesium sulfate manganese (III), and the hydrate of vitriol, as Zinc sulfate monohydrate, six zinc sulphate hydrates, Zinc vitriol, six hydrazine aluminum sulfates, ten hydrazine aluminum sulfates, 16 hydrazine aluminum sulfates, Patent alum, 27 hydrazine aluminum sulfates, 12 hydration chromium sulphate (III) ammoniums, six hydration rose vitriol (II) ammoniums, six ferric sulfate hydrates (II) ammonium, 12 ferric sulfate hydrates (III) ammonium, six anhydrous manganeses (II) ammonium, the sulfuric acid monohydrate cadmium, 8/3 Cadmium sulfate hydrate, seven Cadmium sulfate hydrates, 24 hydrazine aluminum sulfate potassium, 12 hydrazine aluminum sulfate potassium, 16 hydrazine aluminum sulfate potassium, 12 hydration chromium sulphate (III) potassium, six hydration chromium sulphate (III) potassium, three hydration chromium sulphate (III) potassium, sulfuric acid monohydrate chromium (III) potassium, calcium sulphate dihydrate, seven hydration chromium sulphates (II), 18 water closes chromium sulphate (III), three hydration chromium sulphates (III), six hydration rose vitriols (II), sulfuric acid monohydrate cobalt (II), 18 water closes rose vitriol (III), sulfuric acid monohydrate zirconium (IV), Zirconium disulfate tetrahydrate (IV), eight cerium sulfate hydrates (III), four cerium sulfate hydrates (IV), four hydration titanium sulfates (IV), sulfuric acid monohydrate iron (III), four ferric sulfate hydrates (II), five ferric sulfate hydrates (II), seven ferric sulfate hydrates (II), three ferric sulfate hydrates (III), six ferric sulfate hydrates (III), seven ferric sulfate hydrates (III), 7.5 ferric sulfate hydrate (III), nine ferric sulfate hydrates (III), ten ferric sulfate hydrates (III), 12 ferric sulfate hydrates (III), Salzburg vitriol (II), two hydration thorium sulfates (IV), four hydration thorium sulfates (IV), six hydration thorium sulfates (IV), eight hydration thorium sulfates (IV), nine hydration thorium sulfates (IV), seven hydration sodium sulfate, Disodium sulfate decahydrate, 24 hydrazine aluminum sulfate sodium, sulfuric acid monohydrate nickel (II), two hydration nickel sulfates (II), four hydration nickel sulfates (II), single nickel salts (II), 2.5 Magnesium sulfate heptahydrate disodium, four Magnesium sulfate heptahydrate disodiums, seven hydration Vanadosulfuric acids (II), three hydration Vanadosulfuric acids (III), nine hydration Vanadosulfuric acids (III), monohydrate acid magnesium, 1.5 Magnesium sulfate heptahydrate, two Magnesium sulfate heptahydrates, three Magnesium sulfate heptahydrates, six Magnesium sulfate heptahydrates, bitter salt, four hydration sulfuric acid dipotassium magnesium, six hydration sulfuric acid dipotassium magnesium, Manganous sulfate monohydrate (II), two anhydrous manganeses (II), four anhydrous manganeses (II), five anhydrous manganeses (II), seven anhydrous manganeses (II) and 12 cerium sulfate hydrate manganese (III).
In above-mentioned vitriol, the preferred sulfuric acid metal-salt that uses, and in the sulfuric acid metal-salt, more preferably use the hydrate of sal epsom, calcium sulfate, antimony trisulfate, manganous sulfate, sodium sulfate, ferric sulfate (II), zinc sulfate, Tai-Ace S 150, vitriolate of tartar and these vitriol.
In addition, can use above-mentioned catalyzer or be stated from above-mentioned catalyzer on the carrier.About described carrier, though have no particular limits, carrier preferably uses as diatomite, aluminium, silica gel, gac and zeolite.
Have no particular limits for the method that catalyzer is stated from the carrier, can use the method for known dipping and co-precipitation.
When anti-impact polystyrene (hereinafter referred to as HI-PS) when decomposing, being carried out simple heating to HI-PS and gets final product in the presence of described catalyzer in heat-resisting conversion unit such as pyrolysis device by the above-mentioned catalyzer of use.
The Heating temperature of described polystyrene preferably is not more than 350 ℃, and this temperature is that the type by employed catalyzer decides.
More particularly, for example, as follows to the preferred Heating temperature scope of various catalyzer: if Manganse Dioxide, temperature range is 240-330 ℃; If sal epsom, temperature range is 230-330 ℃; If manganous sulfate, temperature range is 220-320 ℃; If the calcium sulfate temperature range is 220-300 ℃; If antimony trisulfate, temperature range is 210-340 ℃; If sodium sulfate, temperature range are 230-320 ℃; If ferric sulfate (II), temperature range is 250-320 ℃; If zinc sulfate, temperature range is 215-340 ℃; If Tai-Ace S 150, temperature range is 235-320 ℃; If vitriolate of tartar, temperature range is 260-340 ℃.
At this, to the not restriction especially of add-on of every kind of catalyzer, yet its preferred range is the 10-20wt% of HI-PS.
In the presence of catalyzer, HI-PS is heated to above-mentioned predetermined temperature, thereby makes HI-PS be converted to the thermolysis steam of polystyrene.This thermolysis steam includes impurity, for example lower boiling component such as benzene, toluene and high boiling component such as dipolymer and trimer, therefore, be through last process for refining to reclaim highly purified styrene monomer.
Described process for refining is undertaken by known method, for example can use vacuum distilling technology etc.
At this, be grafted on divinyl rubber on the HI-PS and be retained in the reaction unit and can be decomposed.
Below in conjunction with drawings and Examples the present invention is described in detail.
Fig. 1 is the synoptic diagram of an embodiment of thermal decomposer used in the present invention;
The gas chromatographic analysis of Fig. 2 distillage (crude styrene monomer) that to be expression obtained by embodiment 1 is figure as a result;
Fig. 3 is the data by the gas chromatographic analysis result of the distillage (crude styrene monomer) of embodiment 1 acquisition;
The gas chromatographic analysis of Fig. 4 distillage (crude styrene monomer) that to be expression obtained by embodiment 2 is figure as a result;
Fig. 5 represents the data by the gas chromatographic analysis result of the distillage (crude styrene monomer) of embodiment 2 acquisitions;
The gas chromatographic analysis of Fig. 6 distillage (crude styrene monomer) that to be expression obtained by embodiment 3 is figure as a result;
Fig. 7 represents the data by the gas chromatographic analysis result of the distillage (crude styrene monomer) of embodiment 3 acquisitions;
The gas chromatographic analysis of Fig. 8 distillage (crude styrene monomer) that to be expression obtained by embodiment 4 is figure as a result;
Fig. 9 represents the data by the gas chromatographic analysis result of the distillage (crude styrene monomer) of embodiment 4 acquisitions;
The gas chromatographic analysis of Figure 10 distillage (crude styrene monomer) that to be expression obtained by embodiment 5 is figure as a result;
Figure 11 represents the data by the gas chromatographic analysis result of the distillage (crude styrene monomer) of embodiment 5 acquisitions;
The gas chromatographic analysis of Figure 12 distillage (crude styrene monomer) that to be expression obtained by embodiment 6 is figure as a result;
Figure 13 represents the data by the gas chromatographic analysis result of the distillage (crude styrene monomer) of embodiment 6 acquisitions;
The gas chromatographic analysis of Figure 14 distillage (crude styrene monomer) that to be expression obtained by embodiment 7 is figure as a result;
Figure 15 represents the data by the gas chromatographic analysis result of the distillage (crude styrene monomer) of embodiment 7 acquisitions;
The gas chromatographic analysis of Figure 16 distillage (crude styrene monomer) that to be expression obtained by embodiment 8 is figure as a result;
Figure 17 represents the data by the gas chromatographic analysis result of the distillage (crude styrene monomer) of embodiment 8 acquisitions;
The gas chromatographic analysis of Figure 18 distillage (crude styrene monomer) that to be expression obtained by embodiment 9 is figure as a result;
Figure 19 represents the data by the gas chromatographic analysis result of the distillage (crude styrene monomer) of embodiment 9 acquisitions;
The gas chromatographic analysis of Figure 20 distillage (crude styrene monomer) that to be expression obtained by embodiment 10 is figure as a result;
Figure 21 represents the data by the gas chromatographic analysis result of the distillage (crude styrene monomer) of embodiment 10 acquisitions;
Embodiment
Below describe and to discuss to the method for using catalyzer of the present invention to come from impact-resistant polystyrene, to reclaim styrene monomer by embodiment, thereby confirm effect of the present invention.Yet the present invention is limited by these embodiment.
Embodiment 1
Use experimental installation as shown in Figure 1 the anti-impact polystyrene to be carried out thermolysis by following method.
In flask 1, add impact-resistant polystyrene that 60g obtains by crushing container Yakult (trade(brand)name) and 10g through 500 ℃ of incinerating Manganse Dioxide, and web plate 2 is placed on the top in flask 1, places the Raschig tubes of the Ф 5mm that is made by pottery to form filler layer 3 on this web plate 2.
Carry out the heating process process, promptly by heating with bell-type well heater 5 material to flask 1 inside when stirring arm 4 mixes and stirs.
In this outlet of using ribbon well heater (not shown) to heat flask 1, so just improved being distilled the recovering state of liquid in the beginning part.
Thereby receptor 7 linked to each other with the outlet of flask 1 by cooling tube 6 make the be cooled component of water condensation and liquefaction be recycled in the receptor 7.Measure fluid temperature in the flask 1 with thermometer 8, and measure the temperature in of cooling tube 6 with thermometer 9.
At this, the fluid temperature when liquid is distilled is 238.5-333.2 ℃, and the temperature in of cooling tube is 146.5-174.3 ℃.
By gas-chromatography the liquid ingredient that is recovered in the receptor 7 is analyzed, the result shows the content of styrene monomer up to 80.7981%, and the content of toluene and ethylbenzene (it is low-molecular-weight component) is low to moderate 5.855% and 3.7825% respectively.Fig. 2 represents gas chromatographic analysis figure as a result, and Fig. 3 represents gas chromatographic analysis result's data.
Embodiment 2
Use experimental installation as shown in Figure 1 the anti-impact polystyrene to be carried out thermolysis by following method.
In flask 1, add impact-resistant polystyrene that 40g obtains by crushing container Yakult (trade(brand)name) and 16g through 800 ℃ of incinerating sal epsom, and web plate 2 is placed on the top in flask 1, places the Raschig tubes of the Ф 5mm that is made by pottery to form filler layer 3 on this web plate 2.
Carry out the heating process process, promptly by heating with bell-type well heater 5 material to flask 1 inside when stirring arm 4 mixes and stirs.In this outlet of using ribbon well heater (not shown) to heat flask 1, so just improved being distilled the recovering state of liquid in the beginning part.
Thereby receptor 7 linked to each other with the outlet of flask 1 by cooling tube 6 make the be cooled component of water condensation and liquefaction be recycled in the receptor 7.Measure fluid temperature in the flask 1 with thermometer 8, and measure the temperature out of cooling tube 6 with thermometer 9.
At this, the fluid temperature when liquid is distilled is 274-335.5 ℃, and the temperature in of cooling tube is 149.8-171.4 ℃.
By gas-chromatography the liquid ingredient that is recovered in the receptor 7 is analyzed, the result shows the content of styrene monomer up to 87.5956%, and the content of toluene and ethylbenzene (it is low-molecular-weight component) is low to moderate 5.1522% and 1.6041% respectively.Fig. 4 represents gas chromatographic analysis figure as a result, and Fig. 5 represents gas chromatographic analysis result's data.
Embodiment 3
Use experimental installation as shown in Figure 1 the anti-impact polystyrene to be carried out thermolysis by following method.
In flask 1, add impact-resistant polystyrene and the 10g manganous sulfate that 50g obtains by crushing container Yakult (trade(brand)name), and web plate 2 is placed on the top in this flask 1, places the Raschig tubes of the Ф 5mm that is made by pottery to form filler layer 3 on this web plate 2.
Carry out the heating process process, promptly by heating with bell-type well heater 5 material to flask 1 inside when stirring arm 4 mixes and stirs.In this outlet of using ribbon well heater (not shown) to heat flask 1, so just improved being distilled the recovering state of liquid in the beginning part.
Thereby receptor 7 linked to each other with the outlet of flask 1 by cooling tube 6 make the be cooled component of water condensation and liquefaction be recycled in the receptor 7.Measure fluid temperature in the flask 1 with thermometer 8, and measure the temperature in of cooling tube 6 with thermometer 9.
At this, the fluid temperature when liquid is distilled is 228.8-297.3 ℃, and the temperature in of cooling tube is 146.2-168.1 ℃.
By gas-chromatography the liquid ingredient that is recovered in the receptor 7 is analyzed, the result shows the content of styrene monomer up to 87.8054%, and the content of toluene and ethylbenzene (it is low-molecular-weight component) is low to moderate 4.8626% and 1.9443% respectively.Fig. 6 represents gas chromatographic analysis figure as a result, and Fig. 7 represents gas chromatographic analysis result's data.
Embodiment 4
Use experimental installation as shown in Figure 1 the anti-impact polystyrene to be carried out thermolysis by following method.
In flask 1, add impact-resistant polystyrene and the 10g calcium sulfate that 50g obtains by crushing container Yakult (trade(brand)name), and web plate 2 is placed on the top in this flask 1, places the Raschig tubes of the Ф 5mm that is made by pottery to form filler layer 3 on this web plate 2.
Carry out the heating process process, promptly by heating with bell-type well heater 5 material to flask 1 inside when stirring arm 4 mixes and stirs.In this outlet of using ribbon well heater (not shown) to heat flask 1, so just improved being distilled the recovering state of liquid in the beginning part.
Thereby receptor 7 linked to each other with the outlet of flask 1 by cooling tube 6 make the be cooled component of water condensation and liquefaction be recycled in the receptor 7.Measure fluid temperature in the flask 1 with thermometer 8, and measure the temperature in of cooling tube 6 with thermometer 9.
At this, the fluid temperature when liquid is distilled is 200-302.7 ℃, and the temperature in of cooling tube is 153-211 ℃.
By gas-chromatography the liquid ingredient that is recovered in the receptor 7 is analyzed, the result shows the content of styrene monomer up to 86.7463%, and the content of toluene and ethylbenzene (it is low-molecular-weight component) is low to moderate 6.109% and 2.9067% respectively.Fig. 8 represents gas chromatographic analysis figure as a result, and Fig. 9 represents gas chromatographic analysis result's data.
Embodiment 5
Use experimental installation as shown in Figure 1 the anti-impact polystyrene to be carried out thermolysis by following method.
In flask 1, add impact-resistant polystyrene and the 10g antimony trisulfate that 50g obtains by crushing container Yakult (trade(brand)name), and web plate 2 is placed on the top in this flask 1, places the Raschig tubes of the Ф 5mm that is made by pottery to form filler layer 3 on this web plate 2.
Carry out the heating process process, promptly by heating with bell-type well heater 5 material to flask 1 inside when stirring arm 4 mixes and stirs.In this outlet of using ribbon well heater (not shown) to heat flask 1, so just improved being distilled the recovering state of liquid in the beginning part.
Thereby receptor 7 linked to each other with the outlet of flask 1 by cooling tube 6 make the be cooled component of water condensation and liquefaction be recycled in the receptor 7.Measure fluid temperature in the flask 1 with thermometer 8, and measure the temperature in of cooling tube 6 with thermometer 9.
At this, the fluid temperature when liquid is distilled is 202-302.3 ℃, and the temperature in of cooling tube is 163-189.6 ℃.
By gas-chromatography the liquid ingredient that is recovered in the receptor 7 is analyzed, the result shows the content of styrene monomer up to 82.9151%, and the content of toluene and ethylbenzene (it is low-molecular-weight component) is low to moderate 6.1744% and 4.2618% respectively.Figure 10 represents gas chromatographic analysis figure as a result, and Figure 11 represents gas chromatographic analysis result's data.
Embodiment 6
Use experimental installation as shown in Figure 1 the anti-impact polystyrene to be carried out thermolysis by following method.
In flask 1, add impact-resistant polystyrene and the 10g sodium sulfate that 50g obtains by crushing container Yakult (trade(brand)name), and web plate 2 is placed on the top in this flask 1, places the Raschig tubes of the Ф 5mm that is made by pottery to form filler layer 3 on this web plate 2.
Carry out the heating process process, promptly by heating with bell-type well heater 5 material to flask 1 inside when stirring arm 4 mixes and stirs.In this outlet of using ribbon well heater (not shown) to heat flask 1, so just improved being distilled the recovering state of liquid in the beginning part.
Thereby receptor 7 linked to each other with the outlet of flask 1 by cooling tube 6 make the be cooled component of water condensation and liquefaction be recycled in the receptor 7.Measure fluid temperature in the flask 1 with thermometer 8, and measure the temperature in of cooling tube 6 with thermometer 9.
At this, the fluid temperature when liquid is distilled is 245-294.6 ℃, and the temperature in of cooling tube is 153.5-161.9 ℃.
By gas-chromatography the liquid ingredient that is recovered in the receptor 7 is analyzed, the result shows the content of styrene monomer up to 81.5469%, and the content of toluene and ethylbenzene (it is low-molecular-weight component) is low to moderate 6.338% and 3.2322% respectively.Figure 12 represents gas chromatographic analysis figure as a result, and Figure 13 represents gas chromatographic analysis result's data.
Embodiment 7
Use experimental installation as shown in Figure 1 the anti-impact polystyrene to be carried out thermolysis by following method.
In flask 1, add impact-resistant polystyrene and the 15g ferric sulfate that 60g obtains by crushing container Yakult (trade(brand)name), and web plate 2 is placed on the top in this flask 1, places the Raschig tubes of the Ф 5mm that is made by pottery to form filler layer 3 on this web plate 2.
Carry out the heating process process, promptly by heating with bell-type well heater 5 material to flask 1 inside when stirring arm 4 mixes and stirs.In this outlet of using ribbon well heater (not shown) to heat flask 1, so just improved being distilled the recovering state of liquid in the beginning part.
Thereby receptor 7 linked to each other with the outlet of flask 1 by cooling tube 6 make the be cooled component of water condensation and liquefaction be recycled in the receptor 7.Measure fluid temperature in the flask 1 with thermometer 8, and measure the temperature in of cooling tube 6 with thermometer 9.
At this, the fluid temperature when liquid is distilled is 226.3-307.7 ℃, and the temperature in of cooling tube is 158.5-185.1 ℃.
By gas-chromatography the liquid ingredient that is recovered in the receptor 7 is analyzed, the result shows the content of styrene monomer up to 83.8343%, and the content of toluene and ethylbenzene (it is low-molecular-weight component) is low to moderate 5.4205% and 3.4163% respectively.Figure 14 represents gas chromatographic analysis figure as a result, and Figure 15 represents gas chromatographic analysis result's data.
Embodiment 8
Use experimental installation as shown in Figure 1 the anti-impact polystyrene to be carried out thermolysis by following method.
In flask 1, add impact-resistant polystyrene and the 13.5g zinc sulfate that 50g obtains by crushing container Yakult (trade(brand)name), and web plate 2 is placed on the top in this flask 1, places the Raschig tubes of the Ф 5mm that is made by pottery to form filler layer 3 on this web plate 2.
Carry out the heating process process, promptly by heating with bell-type well heater 5 material to flask 1 inside when stirring arm 4 mixes and stirs.In this outlet of using ribbon well heater (not shown) to heat flask 1, so just improved being distilled the recovering state of liquid in the beginning part.
Thereby receptor 7 linked to each other with the outlet of flask 1 by cooling tube 6 make the be cooled component of water condensation and liquefaction be recycled in the receptor 7.Measure fluid temperature in the flask 1 with thermometer 8, and measure the temperature in of cooling tube 6 with thermometer 9.
At this, the fluid temperature when liquid is distilled is 217-345.8 ℃, and the temperature in of cooling tube is 151.3-156.8 ℃.
By gas-chromatography the liquid ingredient that is recovered in the receptor 7 is analyzed, the result shows the content of styrene monomer up to 87.7999%, and the content of toluene and ethylbenzene (it is low-molecular-weight component) is low to moderate 5.0973% and 2.1685% respectively.Figure 16 represents gas chromatographic analysis figure as a result, and Figure 17 represents gas chromatographic analysis result's data.
Embodiment 9
Use experimental installation as shown in Figure 1 the anti-impact polystyrene to be carried out thermolysis by following method.
In flask 1, add impact-resistant polystyrene and the 12.5g Tai-Ace S 150 that 50g obtains by crushing container Yakult (trade(brand)name), and web plate 2 is placed on the top in this flask 1, places the Raschig tubes of the Ф 5mm that is made by pottery to form filler layer 3 on this web plate 2.
Carry out the heating process process, promptly by heating with bell-type well heater 5 material to flask 1 inside when stirring arm 4 mixes and stirs.In this outlet of using ribbon well heater (not shown) to heat flask 1, so just improved being distilled the recovering state of liquid in the beginning part.
Thereby receptor 7 linked to each other with the outlet of flask 1 by cooling tube 6 make the be cooled component of water condensation and liquefaction be recycled in the receptor 7.Measure fluid temperature in the flask 1 with thermometer 8, and measure the temperature in of cooling tube 6 with thermometer 9.
At this, the fluid temperature when liquid is distilled is 206.3-317.8 ℃, and the temperature in of cooling tube is 152.1-176.7 ℃.
By gas-chromatography the liquid ingredient that is recovered in the receptor 7 is analyzed, the result shows the content of styrene monomer up to 84.7884%, and the content of toluene and ethylbenzene (it is low-molecular-weight component) is low to moderate 5.0945% and 3.3919% respectively.Figure 18 represents gas chromatographic analysis figure as a result, and Figure 19 represents gas chromatographic analysis result's data.
Embodiment 10
Use experimental installation as shown in Figure 1 the anti-impact polystyrene to be carried out thermolysis by following method.
In flask 1, add impact-resistant polystyrene and the 12.5g vitriolate of tartar that 50g obtains by crushing container Yakult (trade(brand)name), and web plate 2 is placed on the top in this flask 1, places the Raschig tubes of the Ф 5mm that is made by pottery to form filler layer 3 on this web plate 2.
Carry out the heating process process, promptly by heating with bell-type well heater 5 material to flask 1 inside when stirring arm 4 mixes and stirs.In this outlet of using ribbon well heater (not shown) to heat flask 1, so just improved being distilled the recovering state of liquid in the beginning part.
Thereby receptor 7 linked to each other with the outlet of flask 1 by cooling tube 6 make the be cooled component of water condensation and liquefaction be recycled in the receptor 7.Measure fluid temperature in the flask 1 with thermometer 8, and measure the temperature in of cooling tube 6 with thermometer 9.
At this, the fluid temperature when liquid is distilled is 288.6-329.5 ℃, and the temperature in of cooling tube is 155.5-191.3 ℃.
By gas-chromatography the liquid ingredient that is recovered in the receptor 7 is analyzed, the result shows the content of styrene monomer up to 86.0946%, and the content of toluene and ethylbenzene (it is low-molecular-weight component) is low to moderate 5.5804% and 2.1234% respectively.Figure 20 represents gas chromatographic analysis figure as a result, and Figure 21 represents gas chromatographic analysis result's data.
Be the method by heating and decomposition impact-resistant polystyrene recovery styrene monomer of the present invention as mentioned above, it is a kind of cinnamic method that reclaims from impact-resistant polystyrene, uses vitriol and/or Manganse Dioxide as catalyzer in the method.Therefore, this method makes that having highly purified material styrene monomer in industrial practicality with high yield recovery from the impact-resistant polystyrene waste becomes possibility.Owing to also do not set up the effective ways that reclaim these wastes by convention at present, so present method is effective.

Claims (4)

1, a kind of method that from impact-resistant polystyrene, reclaims styrene monomer, it obtains styrene monomer by heating and decomposition impact-resistant polystyrene, and use therein catalyzer is vitriol and/or Manganse Dioxide.
2, according to the method that reclaims styrene monomer from impact-resistant polystyrene of claim 1, wherein said vitriol is the sulfuric acid metal-salt.
3, according to the method that reclaims styrene monomer from impact-resistant polystyrene of claim 1, wherein said vitriol is to be no less than a kind of following material that is selected from least: sal epsom, manganous sulfate, calcium sulfate, antimony trisulfate, sodium sulfate, ferric sulfate (II), zinc sulfate, Tai-Ace S 150 and vitriolate of tartar.
4, according to the method that reclaims styrene monomer from impact-resistant polystyrene of claim 1, the Heating temperature of wherein said polystyrene resin is not more than 350 ℃.
CN00108078A 2000-04-06 2000-06-12 Method for recovering phenylethylene monomer from impact resilience polystyrene Pending CN1316408A (en)

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KR20020023472A (en) * 2000-09-22 2002-03-29 손재익 Catalyst for recycle of monomer from disused plastic of polyethylene origin
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KR101412409B1 (en) * 2012-07-10 2014-06-27 김윤섭 Polymer adsorbent using by waster source of by-product of polystyrene and the manufacturing method thereof
WO2014040634A1 (en) 2012-09-14 2014-03-20 Outotec Oyj Method and apparatus for recycling plastic wastes
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US5406010A (en) * 1993-01-28 1995-04-11 Ponsford; Thomas E. Method of reclaiming styrene and other products from polystyrene based products
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