JP3671865B2 - Exhaust gas treatment agent and thermoplastic resin composition using the same - Google Patents

Description

【００２６】
廃プラスチック等の産業廃棄物を焼却する場合、燃焼室にリン酸三カルシウムを噴霧することにより、排ガス中のダイオキシン濃度を２５．２ｎｇ−ＴＥＱ／Ｎｍ³から４．２ｎｇ−ＴＥＱ／Ｎｍ³に低減することができた。このときのダイオキシン濃度の減少率は８３．４％であった。
【００２７】
【発明の効果】
本発明によれば、ダイオキシンまたはこの前駆体のような有機塩素系化合物に対し優れた分解作用を示す排ガス処理剤および熱可塑性樹脂組成物が提供される。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an exhaust gas treating agent and a thermoplastic resin composition using the same. Specifically, the present invention relates to an exhaust gas treating agent that exhibits a decomposition action on an organic chlorine compound in exhaust gas, and a thermoplastic resin composition using the same.
[0002]
[Prior art]
The exhaust gas generated from municipal waste and industrial waste incinerators may contain organochlorine compounds such as dioxins or their precursors. The organochlorine compounds are efficiently removed to remove the exhaust gas. There is a need for a detoxifying method.
[0003]
Conventionally, as a means for detoxifying exhaust gas, a method using activated carbon is known.For example, exhaust gas discharged from an incinerator is guided to a dust collector, exhaust gas that has passed through the dust collector is guided to an activated carbon packed tower, and an organic chlorine compound is introduced. A method for adsorption removal has been proposed.
[0004]
In the method using activated carbon, it is necessary to adsorb the organic chlorinated compound in the exhaust gas to the activated carbon, and then heat the activated carbon in a nitrogen atmosphere to decompose and remove the organic chlorinated compound adsorbed on the activated carbon. There was.
[0005]
[Problems to be solved by the invention]
An object of the present invention is to provide a suitable exhaust gas treating agent for simply and efficiently treating an organochlorine compound in exhaust gas and a thermoplastic resin composition using the same.
[0006]
[Means for Solving the Problems]
As a result of studying an exhaust gas treatment agent used for detoxifying exhaust gas, the present inventors have completed the present invention.
[0007]
That is, the present invention provides the following formula (I)
AaBbPcOd (I)
[In the formula (I), A is lithium, sodium, potassium, cesium, rubidium, magnesium, calcium, barium, manganese, iron, cobalt, nickel, copper, silver, bismuth, aluminum, gallium, indium, tin, zinc, lanthanum , Cerium, yttrium, ytterbium, tungsten, tantalum, niobium, B is sulfur, boron, silicon or germanium, P is phosphorus, O is oxygen, and the subscripts a, b, c and d are A, B, Represents the atomic ratio of P and O, where a = 1, 0 ≦ b ≦ 10, 0 <c ≦ 30, and d is a numerical value determined by the valence and atomic ratio of A, B, P, and O. . And a hydrate thereof, a monohydrogen phosphate or a dihydrogen phosphate, and an exhaust gas treating agent characterized by comprising:
[0008]
The present invention also provides a thermoplastic resin comprising a thermoplastic resin filled with the composite oxide represented by the formula (I), a hydrate thereof, a monohydrogen phosphate or a dihydrogen phosphate. A composition is provided.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in more detail. The exhaust gas treating agent of the present invention contains a specific phosphorus compound. The exhaust gas treating agent exhibits an excellent decomposing action on an organic chlorine compound such as dioxin or its precursor by containing a specific phosphorus compound.
[0010]
As a phosphorus compound used for the exhaust gas treating agent of the present invention, there is a composite oxide represented by the formula (I). Component A in formula (I) includes lithium, sodium, potassium, cesium, rubidium, magnesium, calcium, barium, manganese, iron, cobalt, nickel, copper, silver, bismuth, aluminum, gallium, indium, tin, zinc Lanthanum, cerium, yttrium, ytterbium, tungsten, tantalum or niobium. Among these, lithium, sodium, potassium, magnesium, calcium, barium, manganese, cobalt, nickel, aluminum, gallium, indium, tin, zinc, lanthanum, cerium or yttrium are preferable, and sodium, potassium, magnesium, calcium, barium are particularly preferable. Or the application of aluminum is recommended. Component B in formula (I) includes sulfur, boron, silicon, or germanium. In the formula (I), P represents phosphorus and O represents oxygen. A, b, c and d in the formula (I) represent atomic ratios of A, B, P and O, respectively, and when a = 1, 0 ≦ b ≦ 10 and 0 <c ≦ 30 . When b exceeds 10, or c exceeds 30, it becomes difficult to obtain an exhaust gas treating agent that exhibits a sufficient decomposition action on the organochlorine compound in the exhaust gas. D is a numerical value determined by the valence and atomic ratio of A, B, P, and O. The phosphorus compound may be a hydrate of the composite oxide represented by the formula (I). Specific examples of the composite oxide include trisodium phosphate [Na ₃ PO ₄ ], tripotassium phosphate [K ₃ PO ₄ ], trimagnesium phosphate [Mg ₃ (PO ₄ ) ₂ ], tricalcium phosphate [ Ca ₃ (PO ₄ ) ₂ ], tribarium phosphate [Ba ₃ (PO ₄ ) ₂ ], tricobalt phosphate [Co ₃ (PO ₄ ) ₂ ], trinickel phosphate [Ni ₃ (PO ₄ ) ₂ ] , Tritin phosphate [Sn ₃ (PO ₄ ) ₂ ], trizinc phosphate [Zn ₃ (PO ₄ ) ₂ ], aluminum phosphate [AlPO ₄ ], gallium phosphate [GaPO ₄ ], indium phosphate [InPO ₄ ], lanthanum phosphate [LaPO ₄ ], yttrium phosphate [YPO ₄ ], silver phosphate [Ag ₃ PO ₄ ], sodium pyrophosphate [Na ₄ P ₂ O ₇ ], calcium pyrophosphate [Ca ₂ P ₂ O ₇ ] Or aluminum pyrophosphate [ _{l 4 (P 2 O 7)} 3 ], and the like.
[0011]
Other phosphorus compounds used in the exhaust gas treating agent of the present invention include, for example, sodium monohydrogen phosphate [Na ₂ HPO ₄ ], potassium monohydrogen phosphate [K ₂ HPO ₄ ], rubidium monohydrogen phosphate [ Rb ₂ HPO ₄ ], cesium monohydrogen phosphate [Cs ₂ HPO ₄ ], magnesium monohydrogen phosphate [MgHPO ₄ ], calcium monohydrogen phosphate [CaHPO ₄ ], barium monohydrogen phosphate [BaHPO ₄ ], etc. Monohydrogen phosphate, or sodium dihydrogen phosphate [NaH ₂ PO ₄ ], potassium dihydrogen phosphate [KH ₂ PO ₄ ], magnesium dihydrogen phosphate [Mg (H ₂ PO ₄ ) ₂ ], diphosphate There are dihydrogen phosphates such as calcium hydrogen [Ca (H ₂ PO ₄ ) ₂ ] and barium dihydrogen phosphate [Ba (H ₂ PO ₄ ) ₂ ]. These monohydrogen phosphate and dihydrogen phosphate may be either anhydrous or those having crystal water.
[0012]
These phosphorus compounds are usually oxides, hydroxides, nitrates, ammonium salts, carbonates, chlorides, organic acid salts, alkoxides or metal acid ammonium salts of the element represented by component A in formula (I). , Triammonium phosphate, diammonium hydrogen phosphate or phosphoric acid and, if necessary, oxides, hydroxides, nitrates, ammonium salts, carbonates, chlorides of the element represented by component B in formula (I) The organic acid salt, alkoxide or metal acid ammonium salt is mixed, and the resulting mixture is evaporated to dryness, or the mixture is solid-liquid separated, dried, and then fired. For example, tricalcium phosphate can be obtained by adding and mixing phosphoric acid and aqueous ammonia into an aqueous calcium nitrate solution, then solid-liquid separating the resulting slurry, and drying and baking the solid content.
[0013]
The exhaust gas treating agent of the present invention differs depending on the type of phosphorus compound constituting it and is not unambiguous, but usually has an average particle size of 50 μm or less and a maximum particle size of 100 μm or less. The average particle size of the exhaust gas treating agent is preferably smaller from the viewpoint of improving the contact with the exhaust gas, preferably 15 μm or less, more preferably 10 μm or less, and more preferably 1 μm or more.
[0014]
This exhaust gas treating agent normally decomposes and removes organic chlorine compounds in the exhaust gas when brought into contact with the exhaust gas at a temperature of 300 ° C. or higher. The higher the temperature of the exhaust gas, the higher the decomposition effect of the exhaust gas treatment agent. However, if the temperature becomes too high, the exhaust gas treatment agent may deteriorate and its activity may decrease, so 1000 ° C. or less, further 950 ° C. or less. Is appropriate.
[0015]
In addition to the phosphorus compound described above, the exhaust gas treatment agent of the present invention includes aluminum hydroxide, activated alumina, calcium carbonate, talc, titanium oxide, iron hydroxide, boria, silica, magnesia, calcia, ceria, zeolite, zirconia, carbonized. It may contain an inorganic compound such as silicon. When the exhaust gas treating agent contains such an inorganic compound, it is preferable to contain a phosphorus compound and aluminum hydroxide or activated alumina.
[0016]
Further, the exhaust gas treating agent of the present invention is a thermoplastic obtained by filling a thermoplastic resin with a phosphorus compound and an optional inorganic compound in addition to those containing a phosphorus compound or a phosphorus compound and an inorganic compound. It may consist of a resin composition. When such a thermoplastic resin composition is put into an incinerator, it exhibits a decomposition action on the organochlorine compound as an exhaust gas treating agent, and before being put into the incinerator, it is a water-soluble phosphorus compound. Can be prevented from adhering due to moisture in the air, etc., and can be easily handled when thrown into the incinerator. Examples of the thermoplastic resin used at this time include ethylene, propylene, styrene, vinyl chloride, vinyl acetate, acrylonitrile, butadiene, vinyl alcohol, acrylic and acrylic derivatives homopolymers, copolymers or polyamides thereof, and polyethylene terephthalate. Such thermoplastic polyesters can be mentioned. The ratio of the thermoplastic resin in the exhaust gas treating agent is preferably 50 to 1000% by weight with respect to the total amount of the above-described phosphorus compound and the arbitrarily used inorganic compound. When the ratio of the thermoplastic resin is less than 50% by weight, the effect of preventing the phosphorus compound from being fixed by moisture or the like is not sufficient. On the other hand, when it exceeds 1000% by weight, the decomposition action on the organochlorine compound decreases.
[0017]
You may use the thermoplastic resin composition shown above shape | molded in a bag, a sheet | seat, a film, or another shape. Such a molded body made of a thermoplastic resin composition is prepared by, for example, kneading the above-described phosphorus compound and a part of the thermoplastic resin to prepare a master batch having a high phosphorus compound content. After kneading the remaining thermoplastic resin with a pressure kneader, Banbury mixer, single screw extruder or twin screw extruder, inflation molding machine, injection molding machine, blow molding machine, vacuum molding machine, press molding machine or T It can be produced by molding with an extrusion molding machine equipped with various dies such as a die, a ring die, a strand die, a pipe die or other dies for different shapes.
[0018]
Further, in the production of such a molded article, during the kneading of the phosphorus compound and the thermoplastic resin, a processing aid, a hygroscopic agent, a bubble buffer, an antioxidant, a pigment, a concealing agent, an antistatic agent, a deodorant, a deodorant An agent or a pest repellent may be added. In addition, the phosphorus compound may be surface-treated with a fatty acid such as stearic acid, a coupling agent such as a silane coupling agent or a titanate coupling agent, paraffin, wax, or a polysiloxane compound in advance.
[0019]
Molded products obtained by molding and processing thermoplastic resin compositions are home appliances / electrical parts, containers, packing supplies, transport machinery parts, office supplies, toys, building materials, sports equipment, agricultural supplies, daily necessities, industrial materials, or general Can be used as machine / precision machine parts. When these compacts are used and then disposed of by incineration, the phosphorus compounds contained in the compacts decompose the organochlorine compounds in the exhaust gas.
[0020]
For example, the home appliances and electrical parts shown above are structural parts such as housings, covers, casters and frames, precision parts such as gears and connectors, small parts such as switches, and electrical insulators such as wire covering materials. And there is a light fixture clear cover. Containers include stretch films, precision instrument storage containers, pharmaceutical containers, cold storage containers, tool boxes, clothing cases, accessory cases, plastic bags, and packing. Packing supplies include containers, boxes, wooden box replacement boxes, seafood cases, packing strings, packing tape, bubble cushioning materials, bubble sheets, packaging sheets, covers, shock cushioning materials, nets, beverage containers There is a packing container or collective cap. Transport machinery parts include soundproofing materials, heat insulation materials, ceiling materials, carpets, cushion materials, interior materials such as dashboards, exterior materials such as bumpers and wheel caps, engine covers, ducts, curved mirrors, electrical parts, and hulls. There are parts and buoys. Office supplies include writing utensils, binders, organizing trays, clips, name tags, pen cases, writing utensils, frames, 3D maps, underlays, rulers, erasers, bulletin boards, and organizing files. Toys include outdoor equipment such as tents and portable chairs, life-saving equipment such as floats, fishing gear parts, dolls, toy parts, models, and model parts. As building materials, furniture such as chairs and tables, flooring materials, carpets, heat insulating materials, wall materials, wallpaper, interior materials such as ceiling materials, exterior wall materials, signboards, wall materials when placing concrete, simple buildings Wall material, veneer board / plywood substitute board, construction site enclosure, shoji board, partition, tatami core, under-floor insulation board. Sports equipment includes various rackets, balls, shuttles, shoes, helmets, and protectors. Agricultural products include tunnel house films, containers, heat absorption films, watering hoses, fertilizer packing bags, and agricultural chemical packing bags. Household items such as flower pots, pet items such as trap collars, trash cans, garbage bags, plastic bags, fashion bags, plastic bags, product outer bags, cards, handle patterns, clothespins, futon tapping , Fly swatter, fan bone, chair / desk core, furniture backboard, reel, eyeglass parts, bag parts, shoes, hygiene products, non-slip rubber, per rubber, hook, handle, water tank, gloves, basket, There is a pick. Industrial materials include sheets, films, pipes, pipes, hoses, valves, display shelves, pallet side plates, trays, warehouse storage boxes, curing plates, belt conveyor floor plates, partition plates, slip sheets, transport pads, There are partition boards, cushioning materials, tape, product exterior bags, and screw / nail chains. General equipment and precision equipment parts include various industrial equipment parts, watch parts, and precision parts such as gears.
[0021]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited by these Examples.
Example 1
3 g of tricalcium phosphate (manufactured by Taihei Chemical Sangyo) and 18 g of silicon carbide (trade name: Shinano Random # 14, manufactured by Shinano Denki Smelting) were mixed, and the resulting mixture was charged into a glass reaction tube having an inner diameter of 15 mm. To this reaction tube, monochlorobenzene (hereinafter referred to as MCB): 100 ppm, oxygen: 17% by volume, nitrogen: the remaining mixed gas, reaction tube wall temperature: 703 ° C., pressure: normal pressure, space velocity: 100 , And the concentration of MCB in the inlet gas of the reaction tube and the concentration of MCB in the outlet gas of the reaction tube were measured by liquid chromatography, and the following decomposition rate (%) = [(inlet gas of reaction tube MCB concentration−MCB concentration of outlet gas of reaction tube) / (MCB concentration of inlet gas of reaction tube)] × 100
The activity of the exhaust gas treatment agent consisting of tricalcium phosphate and silicon carbide was evaluated based on the decomposition rate of monochlorobenzene calculated by the above. The MCB decomposition rate at this time was 91.3%.
[0022]
Example 2
Tricalcium phosphate (manufactured by Taihei Chemical Industry) 5.3 kg, aluminum hydroxide (trade name: CS-600, manufactured by Sumitomo Chemical Co., Ltd.) 47.3 kg, linear low density polyethylene (Sumitomo Chemical) with a melt flow rate of 2 g / min 22.4 kg) was put into a Banbury mixer whose temperature was set to 120 ° C. and kneaded for 8 minutes. The obtained mixture was put into a single screw extruder, and the extruded molded body was cut to obtain pellets. After mixing 42 kg of these pellets, 56 kg of high density polyethylene (manufactured by Sumitomo Chemical Co., Ltd.) with a melt flow rate of 0.05 g / min and a density of 0.95 g / cm ^{2 and 2} kg of a hygroscopic agent (manufactured by Shiroishi Calcium), A thermoplastic resin film was obtained by molding under the conditions of temperature: 180 ° C. and die temperature: 180 ° C.
[0023]
Example 3
Tricalcium phosphate (trade name: food additive) in the secondary combustion chamber of an industrial waste incinerator with a processing capacity of 72t / 24h (incinerator type: stalker type, operation method: 24h full continuous type, dust collector type: bag filter) While spraying tricalcium phosphate, average particle size: 5.1 μm, manufactured by Taihei Chemical Industry Co., Ltd.) at 10 kg / h, 70% by volume of waste plastic, 15% by volume of garbage, 15% by volume of waste plastic in the primary combustion chamber of the incinerator % Trash was added at 3 t / h and incinerated. From 20 to 24 hours after the start of spraying, exhaust gas was continuously sampled from the flue before the bag filter and analyzed. Table 1 shows the gas temperature in the secondary combustion chamber, the amount of exhaust gas during sampling, and the moisture and dioxin concentrations in the exhaust gas. In addition, the dioxin density | concentration in waste gas was measured by the method based on Ministry of Health, Labor and Welfare Notification No. 234 "Calculation method of dioxin density | concentration" on December 1, 1997. The gas temperature in the secondary combustion chamber and the moisture and dioxin concentrations in the exhaust gas were expressed as average values of continuously measured values.
[0024]
Comparative Example 1
Garbage was incinerated under the same conditions as in Example 3 except that the tricalcium phosphate was not sprayed into the secondary combustion chamber. The exhaust gas was continuously sampled and analyzed from the flue in front of the bag filter for 4 hours during the continuous incineration of garbage. The results are shown in Table 1.
[0025]
[Table 1]

[0026]
When industrial waste such as waste plastics is incinerated, the dioxin concentration in the exhaust gas is reduced from 25.2 ng-TEQ / Nm ³ to 4.2 ng-TEQ / Nm ³ by spraying tricalcium phosphate into the combustion chamber. We were able to. The reduction rate of the dioxin concentration at this time was 83.4%.
[0027]
【The invention's effect】
According to the present invention, there are provided an exhaust gas treating agent and a thermoplastic resin composition that exhibit an excellent decomposition action on an organic chlorine-based compound such as dioxin or a precursor thereof.

Claims (3)

A treatment agent for exhaust gas containing dioxin or a precursor thereof, characterized by containing tricalcium phosphate . Treatment agent according to claim 1, wherein the aluminum hydroxide or active alumina. A thermoplastic resin composition comprising a thermoplastic resin filled with tricalcium phosphate .