JP5155087B2 - Method for treating synthetic resin foam containing fluorocarbon or fluorocarbon-like substance - Google Patents

Description

  The present invention relates to a method for treating a synthetic resin foam containing chlorofluorocarbon or a chlorofluorocarbon-like substance. The present invention relates to a method for treating synthetic resin foams such as urethane foam and styrene foam.

  Conventionally, synthetic resin foams such as urethane foam and styrene foam have been mainly used as heat insulating materials for home appliances such as refrigerators or heat insulating materials for building materials. In particular, urethane resins have been widely used because they can be foamed in situ. Many of these constitute closed cells, and as a foaming agent for forming bubbles, Freon having good foamability and low thermal conductivity has been used, and excellent heat insulating foams have been constructed.

  However, since the production of fluorocarbons was completely abolished in 1996 due to global environmental problems such as ozone depletion and global warming, alternative fluorocarbon foaming agents are being studied. Fluorocarbon-like substances such as HCFC and HFC are used as alternative chlorofluorocarbon blowing agents. However, there is still a possibility of ozone layer destruction, etc., and 2020 production will be abolished in principle by 2020. In addition, although HFC has no danger of destruction of the ozone layer, the global warming potential is as large as 140 to 11700 (carbon dioxide = 1), and its emission suppression is an important issue.

  Here, in order to prevent ozone layer destruction and global warming, it is not enough to stop the production of chlorofluorocarbon or chlorofluorocarbon-like substances, and it contains a large amount of chlorofluorocarbon or chlorofluorocarbon-like substances that have been produced and used so far. The treatment for detoxifying the synthetic resin foam is essential. In other words, when a synthetic resin foam containing fluorocarbons or fluorocarbon-like substances as a foaming agent is disposed of in landfills, fluorocarbons or fluorocarbon-like substances are released into the atmosphere over time, leading to ozone layer destruction and global warming. It becomes. Therefore, techniques and institutionalization for completely decomposing waste of synthetic resin foams containing chlorofluorocarbon or chlorofluorocarbon-like substances as foaming agents are being studied.

Several methods have been proposed for treating chlorofluorocarbons contained in these synthetic resin foams.
For example, Patent Document 1 discloses a technique for condensing and recovering a foaming agent from a synthetic resin foam. Patent Document 2 discloses a method of separating a foamed urethane resin from urethane by dry distillation as a method for recovering chlorofluorocarbons contained in the foamed urethane resin. However, these techniques are only related to a method for recovering chlorofluorocarbons and do not indicate any method for decomposing the recovered chlorofluorocarbons. In addition, it takes considerable time and energy to completely separate and recover chlorofluorocarbon from the synthetic resin foam, and there is a problem that the efficiency is poor.

  As for the decomposition treatment method for chlorofluorocarbon, for example, Patent Document 3 discloses a technique for decomposition by plasma discharge, and Patent Document 4 discloses a technique for decomposition by a catalytic method. However, these techniques are only related to a method for decomposing chlorofluorocarbons after they are collected, and no treatment method including separation of chlorofluorocarbons from solid waste, that is, synthetic resin foam has been shown. Therefore, when the chlorofluorocarbon contained in the waste is decomposed by a simple combination of these prior arts, there is a problem that the energy required for recovery of the chlorofluorocarbon is required and the processing cost increases.

  On the other hand, Patent Document 5 discloses a system for recovering chlorofluorocarbons from urethane foam and destroying the recovered chlorofluorocarbons. In such a chlorofluorocarbon destruction treatment system, a heat insulating material containing urethane foam is crushed in a crusher, and chlorofluorocarbon gas and / or flammable gas generated at that time is sucked together with air, and the chlorofluorocarbon gas and / or flammable gas is collected. And the air are sent to an incinerator containing at least 10% by weight of a hydrocarbon compound and the temperature of the exhaust gas is 850 ° C. to 1000 ° C., thereby destroying and burning the Freon gas and the combustible gas.

Japanese Patent Laid-Open No. 3-500857 JP-A-8-229539 JP-A-4-279179 JP-A-4-313344 JP 2003-302031 A

  However, in the system disclosed in Patent Document 5, since the fluorocarbon is separated by crushing, the urethane foam must be crushed to a considerable particle size, and the crushing cost increases. In addition, the finely pulverized urethane powder has a high risk of dust explosion, and when a flammable gas is used for urethane foam, the risk of explosion is further increased. In addition, some chlorofluorocarbons or chlorofluorocarbon-like substances have a boiling point lower than room temperature, and it is impossible to separate the entire amount of chlorofluorocarbon present in the foamed urethane simply by crushing. The treatment of foamed urethane in which chlorofluorocarbon remains is not disclosed in Patent Document 5, and the treatment of foamed urethane after being crushed becomes a problem.

  On the other hand, since oil sludge such as oil sludge and waste oil regeneration residue has high energy, it is expected to be effectively used as fuel without being incinerated or landfilled as industrial waste. Because there are things that have viscosity, those that do not flow at room temperature, and those that solid matter settles and settles, etc., handling is bad during transportation through pipes, etc. It had a problem that it was difficult to handle.

  The present invention has been made in view of the various problems of the background art described above, and its purpose is to use a synthetic resin foam containing chlorofluorocarbon or chlorofluorocarbon-like substance, and chlorofluorocarbon or chlorofluorocarbon-like substance in the atmosphere. It is possible to promote the effective use of oil mud by effectively using the thermal energy of the synthetic resin foam as a resource and improving the handling property of the oil mud, as well as reliably decomposing without letting it be released. The object is to propose a method for treating a synthetic resin foam containing a fluorocarbon or fluorocarbon-like substance.

In order to achieve the above-described object, the present invention provides a method for treating a synthetic resin foam containing the following [1] to [5] chlorofluorocarbon or chlorofluorocarbon-like substances.
[1] Synthetic foams containing chlorofluorocarbon or chlorofluorocarbon-like substances are crushed, the crushed synthetic resin foam and oil mud are mixed to produce solid fuel, and chlorofluorocarbons generated during production and supply of the solid fuel Alternatively, a fluorocarbon-like substance is sucked and the suction gas is introduced into a firing furnace as combustion air for cement firing, and the manufactured solid fuel is introduced into the firing furnace as an auxiliary fuel for cement firing. Or the processing method of the synthetic resin foam containing a CFC-like substance.
[2] The Freon or Freon-like substance as described in [1] above, wherein the synthetic resin foam containing the Freon or Freon-like substance is crushed with an average particle size of 0.1 mm to 40 mm. Of a synthetic resin foam containing selenium.
[3] The above [1] or [2], wherein the crushed synthetic resin foam and the oil mud are mixed in 50 to 400 parts by weight of the oil mud with respect to 100 parts by weight of the synthetic resin foam. A method for treating a synthetic resin foam containing the fluorocarbon or fluorocarbon-like substance described in 1.
[4] The Freon or Freon-like substance according to any one of [1] to [3], wherein the synthetic resin foam containing the Freon or Freon-like substance is a heat insulating material for building materials. A method for treating a synthetic resin foam.
[5] The Freon or Freon-like substance according to any one of [1] to [4] above, wherein the oil mud mixed with the crushed synthetic resin foam is oil sludge or waste oil regeneration residue. A method for treating a synthetic resin foam.

  According to the present invention described above, the synthetic resin foam containing chlorofluorocarbon or chlorofluorocarbon-like substance is crushed and mixed with oil mud to obtain a solid fuel, and the solid fuel is fed into a calcination furnace as an auxiliary fuel for cement calcination. Therefore, chlorofluorocarbon or chlorofluorocarbon-like substances present in the synthetic resin foam are exposed to high temperatures of 1500 ° C. or higher to be surely decomposed, and the synthetic resin foam and oil mud are combusted, and the thermal energy is converted to cement. Used for firing. Therefore, according to the present invention, a synthetic resin foam containing chlorofluorocarbon or chlorofluorocarbon-like material, which has been disposed of in landfill as it is or reduced in volume in the past, can be used as a resource using existing equipment. It can be used effectively and in large quantities, and it can effectively prevent the destruction of the ozone layer and global warming due to the release of chlorofluorocarbons and chlorofluorocarbon-like substances into the atmosphere. Mixing with foam can greatly improve the handling of oil mud and promote the effective use of oil mud, which was difficult to handle as fuel, thus greatly reducing the amount of fossil fuel used. There is.

  Further, according to the present invention, at the time of production / supply of the above-mentioned solid fuel, that is, at the time of production of a synthetic resin foam containing chlorofluorocarbon or chlorofluorocarbon-like substances, at the time of mixing with crushed synthetic resin foam with oil mud, , And the chlorofluorocarbon or chlorofluorocarbon-like substance generated at the time of storage, transportation, etc. of the produced solid fuel is sucked, and the sucked gas is introduced into the firing furnace as combustion air for cement firing. The chlorofluorocarbon or chlorofluorocarbon-like substance generated at the time of production and supply is exposed to a high temperature of 1500 ° C. or higher in a firing furnace, and is reliably decomposed. Therefore, even when the solid fuel is manufactured and supplied, the release of CFCs or CFC-like substances into the atmosphere is prevented. Moreover, the crushing step of the synthetic resin foam may be rough crushing that can be mixed with oil mud and can be input to the firing furnace as auxiliary fuel, and the crushing cost does not increase.

Hereinafter, a method for treating a synthetic resin foam containing a fluorocarbon or a fluorocarbon-like substance according to the present invention will be described in detail with reference to the drawings.
Here, FIG. 1 is a diagram conceptually showing an embodiment of a cement firing facility for carrying out a method for treating a synthetic resin foam containing a fluorocarbon or fluorocarbon-like substance according to the present invention. 1 is a rotary kiln for firing cement raw material, 2 is a burner provided in front of the kiln of the rotary kiln 1, 3 is a hood provided in front of the kiln of the rotary kiln 1, 4 is provided below the hood 3 and is rotary kiln 1 Clinker coolers 5a, 5b, 5c,... For cooling air while transporting the cement clinker generated in the above, 5 are intake blowers for introducing cooling air into the clinker cooler 4, and 6 is a synthetic resin containing Freon or Freon-like substances A crusher for crushing the foam W, 7 is a supply device for supplying the crushed material Wc of the synthetic resin foam to the mixer, and 8 is supplied from the supply device 7 A mixer for mixing the crushed material Wc and the oil mud O, 9 is a supply facility comprising a series of devices for transferring, storing, weighing, and supplying the produced solid fuel WO to the fuel transfer pipe, A transport blower 11 for supplying solid fuel WO quantitatively cut out from the supply facility 9 to the burner 2 as an auxiliary fuel, 11 is a dust collector for removing dust sucked from the crusher 6, the supply device 7 and the like.

  In the present invention, a synthetic resin foam W containing chlorofluorocarbon or a chlorofluorocarbon-like substance is crushed by a crusher 6, and the crushed synthetic resin foam Wc and oil mud O are mixed by a mixer 8 to produce a solid fuel WO. At the time of manufacture and supply of the solid fuel WO, that is, at the time of crushing by the crusher 6, at the time of manufacture by mixing with the mixer 8, and at the time of supply at the time of storage and transportation of the solid fuel WO Fluorocarbons or chlorofluorocarbon-like substances generated from the synthetic resin foam W are sucked, and the suction gas is introduced into the rotary kiln 1 as combustion air for cement firing, and the produced solid fuel WO is used as auxiliary fuel for cement firing in the rotary kiln 1. It is to be input to.

Here, to illustrate the chlorofluorocarbon referred in the present _{invention, CFC11 (CCl 3 F),} CFC12 (CCl 2 F 2), CFC113 (CCl 2 F-CClF 2), CFC114 (CClF 2 -CClF 2), CFC115 (CClF 2 -CF ₃₎ there is. In addition, chlorofluorocarbon-like substances referred to in the present invention include halon (1211: CF ₂ ClBr, 1301: CF ₃ Br, 2402: CF ₂ BrCF ₂ Br), alternative chlorofluorocarbon HCFC (22: CHF ₂ Cl, 123: CHCl ₂ CF ₃ , 141b: CH ₃ CCl ₂ F), alternative CFC HFC (134a: CH ₂ FCF ₃ ), halogen-containing organic solvents (carbon tetrachloride, 1,1,1-trichloroethane, trichlorethylene, etc.), etc. A substance used as a foaming agent that is concerned about the impact on the global environment.

In the present invention, wastes such as synthetic resin foam W using the above-mentioned Freon or Freon-like substance as a foaming agent, for example, urethane foam, styrene foam, and the like are targeted. In particular, a synthetic resin foam containing a fluorocarbon or fluorocarbon-like substance used as a heat insulating material for building materials,
In the future, it is expected to occur in large quantities at the time of building dismantling, etc., and unlike the home appliances in which the synthetic resin foam is enclosed in a member such as metal, the synthetic resin foam alone or one member of the tatami mat Therefore, it can be easily crushed, and all the crushed materials can be used as auxiliary fuel for cement firing. Therefore, it is preferably used in the present invention.

  As the crusher 6 for crushing the synthetic resin foam W containing the above-mentioned chlorofluorocarbon or chlorofluorocarbon-like substance, for example, a cutter mill, a shredder, a disintegrator, an edge liner, a pin mill, a screen mill, etc. can be used. May be used alone, or may be configured in multiple stages. For example, the synthetic resin foam W may be first roughly crushed with a cutter mill and then crushed to a target particle size with a screen mill.

  The crushed particle size of the synthetic resin foam W by the crusher 6 is such that the crushed material Wc can be well mixed with oil mud O, which will be described later, and the solid fuel WO that is the mixture is burner 2 of the rotary kiln 1 for cement firing. What is necessary is just to be crushed into the particle size of the grade which can be supplied more easily as auxiliary fuel. Specifically, a solid fuel burner for cement firing is usually a pipe having an inner diameter of 60 mm to 100 mm, and a maximum of about 50 mm can be blown into a cement firing furnace, so that it is crushed to an average particle size of 40 mm or less. However, it is more desirable to set the average particle size to 30 mm or less in consideration of ensuring high combustion efficiency as a result of the combustion test for each particle size and the mixing property with oil mud O. I understood. On the other hand, it has been found that even if the average particle size is less than 3 mm, no significant improvement in the combustion effect is observed, and making it finer further reduces the crushing efficiency. In particular, when the average particle size is less than 0.1 mm, the risk of dust explosion increases, so it has been found that the average particle size is preferably 0.1 mm or more for safety. That is, it is only necessary to be crushed to an average particle diameter of 0.1 mm or more and 40 mm or less, and it is even better if the average particle diameter is crushed to be 3 mm or more and 30 mm or less.

  As the oil mud O mixed with the crushed synthetic resin foam Wc, oil sludge (for example, heavy oil sludge, crude oil sludge, etc.), waste oil regeneration residue (residue remaining after regenerating waste oil using distillation equipment, etc.), waste Examples include those containing one or more oily substances such as paint, waste ink, waste solvent, grease, waste vegetable oil, waste edible oil, waste glycerin, dehydrated organic sludge and the like. Among these, oil sludge and waste oil regeneration residue are mainly composed of hydrocarbons with large molecular weight, high viscosity, and easy to separate solids. It has been disposed of and is preferably used in the present invention from the viewpoint of promoting the use of waste.

  The mixing ratio of the synthetic resin foam crushed material Wc and the oil mud O is preferably 50 to 400 parts by weight of oil mud with respect to 100 parts by weight of the synthetic resin foam crushed material. This is not preferable from the viewpoint of promoting utilization of waste oil mud when the amount of oil mud is less than 50 parts by weight. On the other hand, when the blending amount of the oil mud exceeds 400 parts by weight, a large amount of oil remains on the surface of the obtained solid fuel particles, and it is difficult to improve the adhesion. From this viewpoint, the blending ratio of the oil mud is preferably 50 to 400 parts by weight with respect to 100 parts by weight of the crushed synthetic resin foam. In addition to the synthetic resin foam crushed material Wc that functions as the absorbent material mixed with the oil mud O, waste crushed material, wood chips (for example, crushed material of construction waste wood), wood powder, sawdust, etc. It is good also as mixing with the oil mud O with the crushed material Wc of a synthetic resin foam. However, in this case, the oil mud is mixed in the above ratio with respect to a total of 100 parts by weight of the synthetic resin foam crushed material Wc and other absorbent crushed crushed material, wood chips and the like.

  As the mixer 8 for mixing the crushed synthetic resin foam Wc and the oil mud O, for example, an omni mixer, a nauta mixer, a V-type mixer, a biaxial mixer or the like may be used. Preferably, the mixer is simply A structure having a strong shearing force is preferable, not a stirring blade. This can be well mixed with a highly viscous material such as oil mud O and a material with low bulk density such as a crushed synthetic resin foam Wc, and the oil mud O does not accumulate in a part of the container. Therefore, it is preferable. Examples of such a mixer include an intensive mixer manufactured by Eirich and an HF corn mixer manufactured by Taiheiyo Kiko.

  In the present invention, chlorofluorocarbons generated at the time of producing the solid fuel WO, such as when the synthetic resin foam W containing the chlorofluorocarbon or chlorofluorocarbon-like substance is crushed and when the crushed synthetic resin foam Wc is mixed with the oil mud O, etc. Alternatively, chlorofluorocarbon-like substances are sucked from the crusher 6 and the mixer 8, and the sucked gas is introduced into the rotary kiln 1 as combustion air for cement firing through the dust collector 11. Therefore, the crusher 6 and the mixer 8 need to be installed in the vicinity of the cement firing facility. Moreover, the introduction position of the suction gas to the rotary kiln 1 is specifically introduced from the first chamber 4a or the second chamber 4b of the clinker cooler 4 installed in front of the kiln of the rotary kiln 1.

  The air chambers of the clinker cooler 4 are sequentially referred to as a first chamber 4a, a second chamber 4b, a third chamber 4c,... From the air chamber closer to the rotary kiln 1, and the first chamber 4a, second chamber The air introduced into the air chamber of the chamber 4b is supplied to the rotary kiln 1 as combustion air, but the air introduced into the air chamber after the third chamber 4c is supplied to a calcining furnace, a coal mill, etc. (not shown). This is because there is a possibility. Therefore, piping connected to the crusher 6 is connected to the intake blower 5a or 5b for introducing cooling air into the first chamber 4a or the second chamber 4b of the clinker cooler 4 (in the illustrated embodiment, to the intake blower 5a). The dust collector 11 is connected. Further, the solid content in the gas collected by the dust collector 11 is returned to the supply device 7. In addition, the exhaust of the dust collector 11 may be directly introduced into the first chamber 4a or the second chamber 4b of the clinker cooler 4 by the pressure of a fan attached to the dust collector 11.

  In addition, since chlorofluorocarbon or chlorofluorocarbon-like substances may be gradually released from the synthetic resin foam after crushing or mixing, from the viewpoint of completely preventing chlorofluorocarbon or chlorofluorocarbon-like substances from being released into the atmosphere. In the present invention, as in the illustrated embodiment, the supply device 7 for the crushed synthetic resin foam Wc, and also the supply equipment 9 for storing the supplied solid fuel WO and supplying it to the rotary kiln 1 are equipped with the intake blower 5a. Pipes communicating with each other are connected, and chlorofluorocarbons or chlorofluorocarbon-like substances generated from the crushed material Wc of the synthetic resin foam at the time of supply such as storage and transportation are sucked from the supply device 7 and the supply equipment 9 It was set as the structure which introduce | transduces gas into the rotary kiln 1 as combustion air for cement baking.

  The chlorofluorocarbon or chlorofluorocarbon-like substance introduced into the rotary kiln 1 as combustion air for cement firing is exposed to a high temperature of 1500 ° C. or higher, and is reliably decomposed. Since harmful hydrogen chloride (HCl), hydrogen fluoride (HF), etc. generated at that time reacts with the cement raw material and is taken into the cement raw material, it is rendered harmless without any other special treatment. Is done.

  In the present invention, the solid fuel WO, which is a mixture of the crushed synthetic resin foam Wc and the oil mud O, is charged into the rotary kiln 1 as an auxiliary fuel for cement firing. At this time, the solid fuel WO composed of the mixture of the crushed synthetic resin foam Wc and the oil mud O is absorbed by the synthetic resin foam Wc in which the oil mud O is crushed, and its handling property is greatly improved. It becomes the solid fuel which has the high energy with which the oil mud O and the synthetic resin foam W were equipped. Therefore, the solid fuel WO is charged into the rotary kiln 1 by quantitatively cutting out the solid fuel WO from the supply facility 9 and pneumatically sending the solid fuel WO to the burner 2 by the transport blower 10 as shown in the figure. Can do.

  The chlorofluorocarbon or chlorofluorocarbon-like substance remaining in the synthetic resin foam crushed material Wc in the solid fuel WO introduced into the rotary kiln 1 as auxiliary fuel is exposed to a high temperature of 1500 ° C. or higher and is reliably decomposed. And the synthetic resin foam W will combust and the thermal energy will be utilized effectively for cement baking.

  As mentioned above, although the preferred embodiment of the processing method of the synthetic resin foam containing a fluorocarbon or a fluorocarbon similar substance concerning the present invention was described, the present invention is not limited to the above-mentioned embodiment at all, It goes without saying that various modifications and changes can be made within the scope of the technical idea of the present invention described in the claims.

BRIEF DESCRIPTION OF THE DRAWINGS It is the figure which showed notionally one Embodiment of the manufacturing apparatus of the solid fuel which implement | achieves this invention, and the cement baking equipment which uses the solid fuel.

Explanation of symbols

1 Rotary kiln 2 Burner 3 Hood 4 Clinker cooler 4a, 4b, 4c ··· First, second and third chambers of clinker cooler
5a, 5b, 5c .. Air intake blower 6 Crusher 7 Supply device 8 Mixer 9 Supply equipment 10 Transport blower 11 Dust collector W Synthetic resin foam containing Freon or Freon-like substance Wc Synthetic resin foam crushed O Oil mud WO Solid fuel

Claims (5)

  CFC or chlorofluorocarbon-like substances are crushed, crushed synthetic resin foam and oil mud are mixed to produce solid fuel, and chlorofluorocarbon or chlorofluorocarbon-like is generated during production and supply of the solid fuel Fluorocarbon or chlorofluorocarbon-like, characterized by sucking a substance and introducing the suction gas into a firing furnace as combustion air for cement firing, and introducing the produced solid fuel into the firing furnace as an auxiliary fuel for cement firing A method for treating a synthetic resin foam containing a substance.   The synthesis containing CFCs or CFCs-like substances according to claim 1, wherein the crushing of CFCs or CFCs-containing synthetic resin foams is performed with an average particle size of 0.1 mm or more and 40 mm or less. Processing method of resin foam.   The Freon or Freon according to claim 1 or 2, wherein mixing of the crushed synthetic resin foam and oil mud is performed at 50 to 400 parts by weight of oil mud with respect to 100 parts by weight of the synthetic resin foam. A method for treating a synthetic resin foam containing a similar substance.   The synthetic resin foam containing a fluorocarbon or a fluorocarbon-like substance according to any one of claims 1 to 3, wherein the synthetic resin foam containing the fluorocarbon or a fluorocarbon-like substance is a heat insulating material for building materials. Processing method.   The synthetic resin foam containing chlorofluorocarbon or chlorofluorocarbon-like substance according to any one of claims 1 to 4, wherein the oil mud mixed with the crushed synthetic resin foam is oil sludge or waste oil regeneration residue. Processing method.

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