KR100315906B1 - Method of treating chlorine-containing plastic wastes - Google Patents

Abstract

Drying chlorine-containing plastic waste in a non-oxidizing atmosphere to convert chlorine into a non-sublimation metal oxide by the action of metal dust, and to prevent the generation of harmful chlorine compounds by fixing chlorine by leaving chlorine in the residue, if necessary dry It is a treatment method for producing fuel by treatment of chlorine-containing plastic waste containing vinyl chloride, which may further include a step of sending the residue to a smelter for recovery. This method allows the plastic waste to be treated harmlessly and, in addition to producing fuel by recycling, recovers metal components mixed in the plastic waste. This is an appropriate method for treating debris dust before landfilling.

Description

METHODS OF TREATING CHLORINE-CONTAINING PLASTIC WASTES}

The present invention relates to a method for treating a chlorine-containing plastic waste harmlessly. In particular, the present invention relates to a method for treating chlorine-containing organic substances such as chlorine-containing plastics made of vinyl chloride. For example, plastic parts of the waste can be reused as fuel and metal parts can be easily recycled into recycled materials prior to disposal without generating dioxins or other harmful chlorine compounds. In particular, the present invention relates to a method for treating debris dust generated when pulverizing waste vehicles, household appliances, or when crushed for reducing the volume or recycling. More specifically, the present invention relates to a recycling process for fully utilizing debris dust as a resource. When the debris dusts are treated to be recycled as fuel, the present invention is dechlorinated to recover these metal components using existing smelting furnaces, and oil components and gases recovered as heat sources, fuels, etc. of smelting furnaces. It is about reusing components, carbides.

In recent years, the amount of urban waste and industrial waste is rapidly increasing, and their disposal by landfilling or incineration has become a social problem. In particular, it is required to prepare urgent countermeasures against the increase in the amount of debris dust generated from the crushing of used automobiles and home appliances. These debris dusts are a mixture of waste plastics made of vinyl chloride, etc., used as a covering material for wiring. Most of these are currently handled by landfills. On the other hand, for the plastic waste contained in industrial waste, research on the use as a fuel (solid, oil, gaseous fuel) from the point of view of recycling has been made, and a typical method for this is oil from plastic waste or rubber waste. Dry distillation (dry distillation) to recover the components and gas components (Japanese Patent Publication No. 48-O0067, 49-90773, 50-04168, 50-85573).

However, the prior art method has a problem in that when chlorine-containing plastics containing vinyl chloride and the like are treated, chlorine is volatilized to hydrogen chloride during pyrolysis, and the hydrogen chloride causes corrosion of the device or is mixed with recovered fuel. . In addition, the method of incineration in air has a problem of generating harmful chlorine compounds such as dioxins.

The existing method proposed as a countermeasure for this problem of chlorine-containing plastic waste has a method of separating chlorine as hydrogen chloride by applying hot steam before incineration to dry at low temperature (Japanese Patent Laid-Open No. 48-60466). Another method is to add iron or iron oxide to a vinyl chloride resin, heat-treat and react chlorine with iron, convert it to ferric chloride (FeCl ₃ ), a trivalent iron compound, and vaporize iron chloride by gas separation (Japan Patent Publication No. 50-32264).

However, the former method still has the problem of corrosion by hydrogen chloride, and the latter method is designed to convert chlorine to ferric trichloride (III), which is easy to sublimate, but due to pyrolysis at low temperature, gaseous chlorine is vaporized. It is the same as the conventional method in that it is separated, and thus a process for separating the generated gas and the ferric chloride (III) gas is complicated, the processing process is complicated, the efficiency of recycling to fuel and resources is low.

In addition, since the debris dust containing a large amount of metal dust is not recycled and remains as an incineration ash, regardless of the above-described method used to treat it, the incineration ash is hardened and buried or cast into hard slugs to prevent recycling into resources. To form a substance.

Currently, most of the dust is treated by landfill, but landfills are decreasing due to the increasing amount of dust, and an effective treatment method other than landfill is required. In addition, the treatment by landfill according to the prior art is causing environmental pollution, a serious social problem due to the leakage of heavy metals and oil. A viable solution to this problem is to incinerate the debris to reduce the volume of debris dust during heat recovery.

However, since the debris dust is a mixture of chlorine-containing plastic waste material made of polyvinyl chloride or the like used as a coating material for the wiring and the metal dust, combustion of the debris dust directly into the combustion furnace produces a large amount of incineration material that cannot be directly processed by heavy metals. Post-treatment such as melt-solidification is required. In addition, since chlorine is present in the waste material, the conventional heat treatment method may generate dioxins, and there is a problem of corrosion of equipment such as hydrogen chloride. As described above, it is not possible to solve these problems by simply incineration of debris dust.

An object of the present invention is to overcome the problems of the treatment method according to the prior art, the configuration of the chlorine-containing plastic waste material made of vinyl chloride, etc. by dry distillation to produce fuel by the reaction with chlorine metal dust to make fuel Distilling a waste comprising a mixture of metal dusts in a non-oxidizing atmosphere to convert the to a non-sublimated metal chloride, and separating the metal chloride from the gas generated by leaving the metal chloride in the residue. By fixing chlorine, it is possible to prevent the generation of harmful chlorine compound gas and make the waste material harmless, on the other hand, to obtain fuel from the plastic waste material, and to increase the practicality by recycling the metal components mixed in the plastic waste material as resources.

It is an additional object of the present invention to overcome the problems of the conventional treatment for debris dust at the stage prior to discarding the debris dust so that the debris dust is harmless and recycled as a resource. More specifically, the present invention provides a treatment method for dechlorination of debris dust during pyrolysis to use an existing smelting furnace. In the treatment method of the present invention, carbide, oil and gas components recovered by treating debris dust by pyrolysis as a heat source such as a smelting furnace are reused, and the metal component of the dust is recovered by using a smelting furnace to make debris dust harmless. And recycle it as a resource.

More specifically, the present invention is characterized in that the chlorine-containing plastic waste material containing a mixture of metal dust in a non-oxidizing atmosphere, carbonized, water-soluble metal that does not volatilize at dry temperature by reacting chlorine and metal dust present in the waste material Chlorine is fixed to the residue by generating chloride to separate chlorine from dry gas, and the dry residue is washed to remove soluble metal chlorides.

The present invention also hydrates chlorine-containing plastic waste material in the presence of a metal dust mixture in a low temperature non-oxidative atmosphere at 300 to 450 ° C., and makes the chlorine present in the waste material react with the metal dust so that it does not volatilize at dry temperature. The chlorine is fixed in the residue to separate the chlorine from the dry gas, the metal residue is dissolved and removed to clean the dry residue for dechlorination, and the dried residue is dried at a high temperature of 450 to 600 ° C. It provides a method for treating chlorine-containing waste material comprising pyrolyzing organic material and recovering metal material from residue after hot distillation.

In the above-mentioned treatment method, the suitable distillation temperature is 300 to 600 ° C, the atmosphere for dry distillation is an oxygen concentration of 16 vol% or less, and preferably less than 4 vol%. The preferred method is the process of washing dry residues with alkali and recovering metal components leaked from residues with hydroxides, washing dry residues, grinding the residues and separating them magnetically to recover iron dust. It consists of recovering carbides from residues, separating and recovering dry gas and reusing them, or adjusting pH within the legally permitted range for the discharged water.

The present invention is to dry the chlorine-containing waste material containing a mixture of metal dust in a non-oxidative crisis to react the chlorine and metal dust present in the waste material to produce a water-soluble metal chloride not volatilized at the drying temperature, and to fix the chlorine in the residue Chlorine is separated from the dry gas, the dry residue is washed, the metal chloride is dissolved and removed, and dechlorinated, and the metal residue in the residue is dissolved and recovered during the smelting process of the cleaned residue. It provides a method for treating chlorinated waste material comprising the.

In the above-described method, any nonferrous smelting furnace, more specifically, a smelting furnace for making copper or lead may be used. The treatment method enables efficient treatment of debris dust. The above treatment method is a process for reusing dry gas and the dry liquid obtained by concentrating it as a fuel, and supplying the dry liquid obtained by concentrating the dry gas to an oil / water separator to recover dry oil and use it as fuel. Process of recovering carbides from scrubbing residue and dry gas to reuse non-concentrated portion of gas as fuel, process of recovering metal components from residue in smelting mat, or smelting slug produced in nonferrous smelting furnace as cement resource. Recycling may be included.

(Ⅰ) Dechlorination

The treatment method according to the invention is shown in FIG. Although the treatment method shown here consists of a single step of dry distillation, the dry distillation process may be carried out in a multi-process manner described below.

Throughout this specification and claims, the term "chlorine-containing plastic waste material" means waste of plastic (resin) represented by a chlorine-containing resin such as vinyl chloride. Vinyl chloride, which is commonly used as a coating material for wiring, theoretically contains about 56% by weight of chlorine (hereafter referred to as%), but polyolefin and polystyrene resins exhibit different properties when oxidized or pyrolyzed. At the same time, pyrolysis occurs at relatively low temperatures (above about 200 ° C).

In order to solve the problem of generating hydrogen chloride, the treatment method according to the present invention is to dry the chlorine-containing plastic waste material in the presence of mixed metal dust in a non-oxidizing atmosphere at a temperature of 300 ~ 600 ℃, to react the metal dust and chlorine It is designed to fix the chlorine in the residue by producing it as a metal chloride that does not volatilize at dry temperature. Although metal dust is theoretically present in an amount sufficient to convert all the chlorine present in the plastic to metal chlorides, it is better to exceed the stoichiometric reaction equivalent from a practical point of view such as reactivity. A typical example of a mixture of chlorine-containing plastic waste and metal dust is the above mentioned debris dust. Fragment dust generally contains 10 to 30% by weight of metal dust, and the remainder is mainly composed of resin components. The treatment method according to the present invention allows direct treatment of debris dust consisting of a mixture of metal dust and a resin component.

In the case where the coating material of the wiring mainly composed of vinyl chloride is dried at 300 to 600 ° C. without a metal dust mixture in an atmosphere of nitrogen gas, 80% or more of the chlorine present is volatilized to hydrogen chloride when the temperature reaches 300 ° C. . On the other hand, if debris dust containing mixed metal dusts is dried at the same temperature, hydrogen chloride generated from decomposition of vinyl chloride reacts with metals such as iron, copper, aluminum, zinc, magnesium, calcium, sodium, and lead in the dust. Produces metal chlorides that do not volatilize at dry temperatures. Metal chlorides remain in the solid residue as solids, reducing chlorine gas and hydrogen chloride gas.

Instead of the metal dust or together with the metal dust, a calcium-containing basic inorganic compound may be added to the debris dust. As calcium-containing basic inorganic compounds, slaked lime, quicklime, calcium carbonate and the like can be used. Here, chlorine generated by the decomposition of plastics reacts with these calcium compounds to produce calcium chloride fixed in the residue. Therefore, when the waste material has a low metal content, these calcium compounds can be added to fix chlorine to the residue simply and inexpensively.

Preferably, the range of the dry distillation temperature is preferably 300 ° C. or higher at which chlorine is separated from the resin and 600 ° C. or lower at which most of the resin components in the waste material are separated. Dechlorination is impeded at temperatures below 300 ° C., and some of the metal chlorides volatilize above 600 ° C. and migrate to gas, so temperatures outside this range are undesirable.

The distillation time proceeds to a sufficient degree for the decomposition reaction of the resin and continues for a sufficient time until the formation of the metal chloride is completed. It takes about 200g of plastic waste material. It takes 30 ~ 60 minutes depending on the volume and temperature of the processed waste material.

Drying is also carried out in a non-oxidative atmosphere made by introducing an inert gas such as nitrogen to exhaust the air. Here, "non-oxidizing atmosphere" means that the oxygen concentration is 16 vol% or less. Preferably, an inert gas atmosphere having an oxygen concentration of 4 vol% or less is suitable. It is not preferable to dry carbon in air (oxidation atmosphere) because iron or the like is oxidized in dry carbon to produce volatile chlorides having high oxidation number. For example, when dried in air, iron reacts with chlorine in organic waste to produce ferric chloride (FeCl ₃ ). Since the ferric chloride has a boiling point of about 317 ° C., the ferric chloride is volatilized at a temperature significantly lower than the boiling point of ferric chloride (FeCl ₂ ) (about 1023 ° C.). .

Drying is preferably carried out in a multistage manner. For example, primary dry distillation (low temperature dry distillation) is performed at 300 to 450 캜, preferably 300 to 350 캜, where most of the chlorine is separated, and then at 450 to 600 캜, where most of the resin constituting the coating material is decomposed. Secondary distillation (hot distillation) is performed.

In the stage of primary dry distillation, almost all of the chlorine is separated and reacted with the metal dust to remain in the current residue as metal chloride, and the amount of volatilized into the dry gas is extremely small. In primary dry distillation and the like, most of the resin is thermally decomposed at the same time as the chlorine is separated and volatilized to dry gas. The dry gas is led to a concentrator, cooled and concentrated, and the resulting dry liquid is recovered and separated by oil or water by centrifugation or the like. On the other hand, the non-concentrated portion of the gas is led to an alkaline solution to collect, separate and recover a very small amount of chlorine remaining in the gas by alkaline washing. Dry gas is mainly composed of hydrocarbon gas that can be reused as fuel gas.

Most of the metal chlorides in the primary dry distillation residue are water soluble and the metal chlorides are dissolved by washing the residue. For washing, alkaline washing may be performed by using water or by adding sodium hydroxide, lime, or the like to water. Since the cleaning liquid is neutralized by adding sodium hydroxide, lime, or the like, the metal ions filtered out from the residue can be precipitated as a hydroxide, separated and recovered. Here, the alkali content of the cleaning liquid is adjusted to be in the pH range in which the filtered metal component is precipitated as a hydroxide. The appropriate pH range may vary depending on the type of metal, and the alkali content may be appropriately adjusted according to the type of metal.

If the pH of the rinsing water discharged after the recovery of the metal hydroxide exceeds the legal limit, the pH of the rinsing water is adjusted again so as not to exceed the legal limit for the effluent. For example, if the pH of the rinsing water discharged exceeds pH 5.8-8.6, which is a legally acceptable range of effluent water, after the metal hydroxide is recovered, the pH is adjusted again to fall within the above range.

Alternatively, the metal chloride filtered out by washing with water can be separated and recovered by any conventional method. Examples thereof include electrodialysis, a method using an ion exchange resin, or a method of crystallizing a washing liquid by evaporation and concentration.

The primary dry residue is washed and then secondary dried. Most resins are pyrolyzed into gas by secondary distillation. Since chlorine fixed in the primary dry residue is removed by washing the dry residue, the secondary dry gas contains almost no chlorine gas and hydrogen chloride gas. Therefore, most of the secondary distillate gases consist of hydrogen and hydrocarbons. Secondary distillate gas is introduced into the cooling section as the primary distillate gas is concentrated and recovered as dry distillate. On the other hand, the non-concentrated portion of the gas is led to an alkaline solution, where a small amount of chlorine component is collected and separated by alkaline washing.

In the same manner as the primary distillate, the secondary distillate is removed by water by centrifugation or the like to recover the oil component. The recovered dry gas and oil components can be recycled as fuel. Dry distillation is not limited to two processes, it can be carried out by varying the dry distillation temperature by process several times. Examples of dry gas composition (vol%) are as follows.

H ₂ : 51%, CH ₄ : 17%, CO ₂ : 0.05%

CO: 7.6%, C ₂ H ₄ : 0.6%, C ₂ H ₆ : 2.6%

C ₃ H ₈ : 1.1%, nC ₄ H ₁₀ : 1.0%

Secondary residues are washed to remove residues of metal chlorides, dried and crushed, and magnetically separated to separate and recover iron dust. The iron dust can be recycled as scrap. Iron-free dry residue is separated into carbide and nonferrous metal dust by separation method such as specific gravity classification or heavy liquid separation, carbide is recovered as fuel, and nonferrous metal dust is recovered as raw material for metal smelting. The method of separating and recovering carbides is not limited to the above methods using their inherent specific gravity differences, and any method using differences in shape, particle size and the like can be used. As a washing solution of the residue, water or an alkaline solution may be used. The recovery of the metal component by washing of the secondary dry residue can be carried out in the same manner as the method applied in the cleaning of the primary dry residue.

According to the treatment method described above, at least 70%, preferably at least 80%, more preferably at least 99% of the chlorine present in the plastic waste is fixed to and removed from the residue without volatilization. The ratio of fixed chlorine is much higher than that of the conventional incineration method (30 to 80% of chlorine is vaporized and volatilized point), and the above-described treatment method is easy because the metal chloride fixed in the dry residue is easily filtered out by washing. Does not require post-processing.

(II) Recovery of Metal Components Using Smelting Furnace

The treatment method according to the present invention includes a smelting process in which dry residue is introduced into a smelting furnace to recover metal components after the dechlorination / drying treatment which is recycled as fuel by dechlorination and dry drying of chlorine-containing plastic waste. can do.

(Iii) dechlorination process

The dechlorination process prior to the smelting process has been described above. The dry gas and dry oil recovered in this drying process can be recycled as fuel for the smelting process.

Here, before sending the dry gas to the thickener, it is sent to the dust trap to collect and collect the carbide mixed in the gas, and the carbide contained in the dry residue can be recovered as a fuel and reused. After the dry residue is washed and pulverized, the carbides contained in the dry residue are separated and recovered according to the difference in their specific gravity. Separation and recovery can be done according to differences in their shape or particle size.

(Ii) smelting process

After rinsing, the distillate residue enters a smelting furnace for making non-ferrous metals such as copper and lead, and is recovered into the smelting mat during smelting, while iron and calcium are recovered as smelting slugs.

If debris dust enters the smelting furnace directly without going through the above-mentioned dry distillation process, chlorine gas or hydrogen chloride gas is generated by the decomposition of plastic, which causes corrosion of facilities such as smelting furnace and flue, and damage to working environment as described above. Will be coated. However, in the treatment method according to the present invention, the dry residue is subjected to the smelting process after being treated by the dry distillation process, and thus does not cause such a problem.

The type of smelting furnace applied to the dry residue is not limited to any particular one. Available smelting may include various smelting furnaces used for flame refining, smelting, etc., to melt selected ores or concentrates according to the characteristics of certain dry residues. Examples include furnaces, flash furnaces, reduction furnaces, reflection furnaces, conversion furnaces, refining furnaces, smelting furnaces used for continuous copper production, separation furnaces and conversion furnaces.

2 is a flowchart of a smelting step for producing copper, which is an example of the smelting step used in the treatment method according to the present invention.

According to the smelting process for producing copper shown in the drawing, the copper concentrate is dissolved in the reflection furnace 21 and separated into a copper sulfide mat containing FeO—CaO—SiO ₂ slugs and iron sulfide. ), Air enters the melted mat, oxidizes iron, releases it into slugs, and converts copper sulfide to Blister Copper. The slug is returned to the reflection furnace 21 and processed again to recover the copper component, but the coarse copper obtained in the conversion furnace 22 is sent to the purification furnace 23 to remove impurities by oxidation and volatilize to reduce the purified copper. . This purified copper is used as the anode of the electrosmelting. Exhaust gas having sulfurous acid gas and the like generated in the reflection furnace 21 and the conversion furnace 22 is led to the boiler 24 and the Cotrell precipitator to remove the fuel material.

The dry residue of the debris dust is introduced into the reflection furnace 21 or the conversion furnace 22 depending on whether it is dissolved with copper concentrate or with the mat. Iron and calcium contained in the residue are oxidized, slugized and separated from the mat. The precious metal is dissolved in a mat together with copper, contained in crude copper, and sent to a refining furnace 23, and finally recovered through an electrolysis process. In addition, lead oxide and zinc oxide contained in the fuel material generated in the reflection furnace 21 and the conversion furnace 22 are recovered from the exhaust gas in the boiler 24 and the coater settler 25. Carbide recovered from dry / clean residues and off-gases is used as fuel along with dry gas and dry oil. The slug produced in the conversion furnace 22 is returned to the reflection furnace 21 for reuse or for use as a cement raw material and adhesive.

As described above, according to the treatment method including the dry distillation process and the smelting process, in the case of treating debris dust containing a large amount of chlorine-containing plastic such as vinyl chloride resin, the chlorine problem due to thermal decomposition of the plastic Is overcome and the metal is recovered inexpensively in the smelting furnace. Heat recovery is also carried out using carbides, dry gas, and dry oil produced by pyrolysis of plastics as fuel. Furthermore, since the slug produced in the smelting process can be used as a raw material for cement or the like, no waste material to be buried is left, and the problem of treating debris dust has been completely solved.

Although the invention is illustrated by the following examples, these examples are for illustrative purposes only and do not limit the scope of the invention.

Example 1

A debris dust (car dust) 195g (metal: 45g, resin: 121g, chlorine in the resin: 4.8g, 29g) using a distillation apparatus shown in FIG. 3 was maintained at 300 ° C in a nitrogen atmosphere. In (1), the mixture was heated for 1.5 hours and dried firstly. As a result, dry gas was guided into the concentrator 2 to recover the dry liquid (26 ml) from the container 3. The non-condensed portion of the dry gas is sent to a solution of sodium hydroxide (1% concentration, 100 ml) for alkaline cleaning. The distillate is separated into water and oil (8 ml). Most of the oil is equivalent to "heavy oil A", and after alkaline washing, dry gas (17 ml) mainly consists of hydrogen and methane. Both can be recycled as fuel and the chlorine content is very small.

On the other hand, the residue (162 g) of the primary dry distillate was washed with 500 ml of purified water, and the chlorine content of the washing liquid was measured to be 4.02 g. The residue washed in the primary distillate is heated for 1.5 hours at 560 ° C with the same apparatus for the secondary distillation, and the dried gas is cooled and condensed in the concentrator 2 for concentration, recovering 23 ml of distillate and 18 liters of distillate gas. It was. The distillate was separated into oil and water by centrifugation, and the distillate gas was washed with alkali. The residue (87 g) of the secondary distillate was washed with an integer of 500 mL, and the chlorine content of the wash was measured at 0.62 g. It became. On the other hand, when measuring the chlorine content of dry gas, chlorine was hardly seen. The main constituents of the secondary distillate gas are hydrogen and methane, like the primary distillate gas, and the obtained distillate oil corresponds to "A heavy oil".

As previously described, all chlorine present is fixed to the primary dry distillation residue by primary dry distillation and about 82% of the fixed chlorine is removed by washing with water. Furthermore, the recovered distillate and dried gas contained little chlorine, and the main components were hydrogen and methane, useful as fuel oils and fuel gases. The results of this example are shown in Table 1.

Comparative Example 1

The dust (8.1 g) of the vinyl chloride resin covering the wiring is first carbonized and heated to 300 ° C in a furnace equipped with an alumina tube furnace free of metal dust while nitrogen gas is introduced into the furnace. Heated to 占 폚, and secondarily distilled. 10% sodium hydroxide (100 ml) was introduced into the primary and secondary dry gas respectively, and chlorine in the gas was captured as ions, and the chlorine concentration thereof was measured. The dried residue was washed with purified water 200 ml for 60 minutes and the chlorine concentration of the washing water was measured. The results are shown in Table 2.

As can be seen from Table 2, the chlorine content of alkaline clean water used for primary dry and secondary dry gas is 2.Og and 0.01g, and the chlorine content of dry residue is 0.34g and 85 of chlorine present. The percentage is vaporized and mixed into the primary dry gas, so chlorine cannot be separated.

Second to Fourth Embodiments

The debris dust of different composition is dried in a distillation apparatus constructed in the same manner as used in the first embodiment, except that a furnace equipped with an alumina tube is used at the temperature and atmosphere conditions shown in FIG. Samples 1 to 6 of the second example show the debris dust having an average content of Fe, Cu and Ca. Samples 7 to 8 of the third example have a high Fe content, and samples 9 to 10 of the fourth example show Cu. It indicates that the content of is high.

As described in Table 3, the chlorine content in the dry gas of Samples 1 to 10 of all of these examples is less than 1%, and most of the chlorine remains in the residue, and 96 to 98 of the remaining chlorine when the residue is washed. % Was collected.

Comparative Examples 2-5

A sample of debris dust having the composition shown in Table 4 was used as a raw material and dried in the temperature and atmosphere of Table 4 using a distillation apparatus as used in the second embodiment. The results are shown in Table 4. In the second comparative example, sample 11 corresponds to the second embodiment, and sample 12 corresponds to the fourth embodiment, wherein the two samples are dried at 700 ° C. In the third comparative example, sample 13 corresponds to the second embodiment, and sample 14 corresponds to the fourth embodiment, wherein the two samples are dried at 250 ° C. In the fourth comparative example, Samples 15 and 16 correspond to the second embodiment, and drying is performed at 300 ° C or 560 ° C while air is introduced into the furnace. The fifth comparative example is a case where the nonmetallic sample is dried under the same conditions as the sample 1 of the second embodiment.

When dry distillation is carried out at a temperature of 700 ° C. as shown in the samples of the second comparative example, 3 to 4% of the chlorine is vaporized and incorporated into the distilled gas. On the other hand, as shown in the third comparative example, since chlorine is hardly decomposed at a dry distillation temperature below 250 ° C, 71 to 74% of the chlorine remains in the washed residue. In addition, according to the fourth comparative example, according to the conventional pyrolysis method including the convection of air, 38 to 52% of the chlorine present is vaporized and incorporated into dry gas or dry oil. Further, according to the fifth comparative example, when no metal is present, 77% of chlorine volatilizes into dry gas or dry oil.

5th Example and 6th Comparative Example

Raw materials having Fe, Cu, and Ca content of less than half of the debris dust on average are added with calcium oxide, calcium hydroxide, or calcium carbonate (Example 5, Samples 19, 20, 21) or not added thereto. (Sixth Comparative Example) The process is carried out in the same manner as in the first embodiment. Table 5 shows the results.

In Comparative Example 6 (Sample 18), in which no calcium compound was added, 10% of chlorine was mixed as dry gas, but 99% of chlorine was added by adding calcium oxide, calcium hydroxide, or calcium carbonate as in the second to fourth embodiments. It is fixed to the residue of Example 5 (Samples 19 to 21).

Seventh embodiment

(1) Drying process

The debris dust of the composition of Table 6 was continuously carbonized at 550 ° C. to treat 2 tons per hour in an internally heated continuous distillation furnace. The dry residue produced at this time was washed with 5 m ³ / hr of water, dehydrated and dried in a sunny place. The dry gas was concentrated and cooled in the concentrator, and the resulting dry liquid was recovered. The non-drying portion of the gas was led to an alkaline solution, trapped a small amount of ions left in the gas by alkaline washing, and was separated and recovered. On the other hand, the distillate is separated from oil / water by centrifugation, and the dried distillate oil is recovered. Table 7 shows the residues washed, dry gas and dry oil recovered after alkaline cleaning, their chlorine content and their calorific value. Here, lime is added to the dry residue partially by reprecipitation of dissolved metal ions while being washed to neutralize.

The total heat generated from dry distillate produced from debris dust is 1060 kg / hr, converted to coal, and recovered by subtracting the amount of heat (140 kg / hr) required to dissolve incombustibles (490 kg / h) such as metal remaining in the residue. The final calorific value is 900kg / hr in terms of coal. The chlorine content of the drying process and the cleaning residues are shown in Table 7 below. The problem of chlorine does not arise when the cleaned residue enters the smelting furnace.

(2) Smelting Process

The dry / clean residues obtained in the above-mentioned dry distillation process have the composition shown in Table 8, 0.5 kg of which is sent to the smelting process for making copper, and slag (1.7 kg) and copper mat (2.0) having the composition shown in Table 3. kg) and enter the smelting furnace with flux (FLUX: 0.04 kg). The mixture is heated at 1350 ° C. for 1 hour and the composition of the resulting copper mat and slug is analyzed and the results are shown in Table 9. The composition of flue residues from the furnace is also shown in Table 9.

As a result, when the dry / clean residue is added to the copper mat at a ratio of 1: 4, the amount of the copper mat and slug increases in proportion to the amount of the added residue. It absorbs and collect | recovers with this copper mat and slug. However, the smelting process for making copper can be connected to the conventional process since the component ratio of the copper mat and the slug is not significantly different from the composition before addition of the residue, and thus is not affected by the addition of the dry residue.

Eighth Embodiment

In the first embodiment, the cleaning residue obtained by the distillation treatment is introduced in a continuous copper production process capable of treating copper concentrate at 70 tons / hr with flux (flux: 14 tons / hr) at 0.86 tons per hour. The composition of the mat and slug produced was compared with the case where no cleaned residue was added. The results are shown in Table 10, and there was no difference in the composition of the washed residues with and without addition. Subsequently, a smelting process for producing stable copper can be performed.

9th Example and Comparative Example

0.5 g sample (A) of the dry / clean residue of the debris dust obtained in the first embodiment, and 0.5 kg sample (B) of the debris dust not treated with dry matter were prepared, and the flux (0.04 kg) added thereto, A copper mat (2.Okg) and slug (1.7 kg) were heated to 1350 ° C. for 1 hour in the same manner as in the first embodiment. Here, the generated gas is led to a scrubber (washer) to cool the sprayed water. In this experiment, samples A and B were repeated 15 times to examine the corrosion of the pipe section (manufactured by SIS 316) and the washing water spray unit (manufactured by SIS 316).

As a result, fine corrosion of the pipe and the nozzle was not seen in Sample A. In particular, the mass of the nozzles used did not decrease as compared to the new nozzles after the test. On the other hand, some fading in pipes and nozzles was observed in Comparative Sample B. In addition, it was confirmed that the nozzle portion has a mass reduction of 0.07% compared to the mass of the new nozzle.

1 is a process flow diagram illustrating an embodiment of a treatment method according to the present invention.

2 is a process flow diagram illustrating an embodiment of a smelting method according to the present invention.

3 is a schematic diagram of the distillation apparatus used in the embodiment of the present invention.

Claims (30)

Drying plastic waste material containing chlorine in a non-oxidative atmosphere in the presence of metal dust to react chlorine contained in the waste material with metal dust to produce metal chlorides which do not volatilize at dry temperature, thereby fixing chlorine in residues Separating said chlorine from A method for treating chlorine-containing plastic waste, characterized in that the step of washing the dried residues to dissolve and remove the water-soluble metal chloride. The method for treating chlorine-containing plastic waste according to claim 1, wherein the distillation temperature is 300 to 600 ° C. The method of claim 1, wherein the dry residue is alkali washed to recover the metal component as a hydroxide from the residue. Plastic waste containing chlorine is distilled in a non-oxidative atmosphere in the presence of metal dust to react chlorine contained in the waste with metal dust to produce metal chlorides that do not volatilize at dry temperature, thereby fixing chlorine in the residue to dry gas. Separating said chlorine from Washing the dry residue to dissolve and dechlorinate the water-soluble metal chloride; And pulverizing and magnetically separating the dry residue to separate and recover iron dust, and separating and recovering non-ferrous metals and carbides from the residue. Plastic waste containing chlorine is dried at low temperature in a non-oxidizing atmosphere at a temperature of less than 300 ~ 450 ° C. to react chlorine contained in the waste with metal dust to produce metal chlorides which do not volatilize at dry temperature. Fixing chlorine to the residue thereby to separate the chlorine from the dry gas; Dechlorination by washing the low-temperature dry residue to dissolve and remove the water-soluble metal chloride; Recovering the chlorine-containing plastic waste material comprising the step of recovering the metal component from the high-temperature dry residue by thermal decomposition of the organic matter by hot-drying the cleaning residue at 450 ~ 600 ℃. 6. The method for treating chlorine-containing plastic waste according to claim 5, further comprising alkali washing the residues of the low temperature dry and the high temperature dry and recovering the leached metal component as a hydroxide. Plastic waste containing chlorine is dried at low temperature in a non-oxidizing atmosphere at a temperature of less than 300 ~ 450 ° C. to react chlorine contained in the waste with metal dust to produce metal chlorides which do not volatilize at dry temperature. Fixing chlorine to the residue thereby to separate the chlorine from the dry gas; Dechlorination by washing the low-temperature dry residue to dissolve and remove the water-soluble metal chloride; Recovering the metal component from the hot distilled residue by thermally decomposing the cleaning residue at high temperature and dried at 450 to 600 ° C., And recovering iron dust by grinding and magnetically separating the high-temperature dry residue, and separating and recovering non-ferrous metals and carbides from the residues. The method for treating chlorine-containing plastic waste according to claim 1, wherein the dry distillation is performed in a non-oxidizing atmosphere having an oxygen concentration of 16 vol% or less. The method for treating chlorine-containing plastic waste according to claim 5, wherein the dry distillation is performed in a non-oxidizing atmosphere having an oxygen concentration of 16 vol% or less. 9. The method for treating chlorine-containing plastic waste according to claim 8, wherein the dry distillation is performed in a non-oxidizing atmosphere having an oxygen concentration of 4 vol% or less. 10. The method for treating chlorine-containing plastic waste according to claim 9, wherein the dry distillation is performed in a non-oxidizing atmosphere having an oxygen concentration of 4 vol% or less. Drying plastic waste material containing chlorine in a non-oxidative atmosphere in the presence of metal dust to react chlorine contained in the waste material with metal dust to produce metal chlorides which do not volatilize at dry temperature, thereby fixing chlorine in residues Separating said chlorine from Washing the dry residue to dissolve and dechlorinate the water-soluble metal chloride; A method for treating chlorine-containing plastic waste, characterized in that it comprises the step of recovering and recycling the dry gas. Plastic waste containing chlorine is dried at low temperature in a non-oxidizing atmosphere at a temperature of less than 300 ~ 450 ° C. to react chlorine contained in the waste with metal dust to produce metal chlorides which do not volatilize at dry temperature. Fixing chlorine to the residue thereby to separate the chlorine from the dry gas; Dechlorination by washing the low-temperature dry residue to dissolve and remove the water-soluble metal chloride; Recovering the metal component from the hot distilled residue by thermally decomposing the washing residue at 450 to 600 ° C. by thermal decomposition of the organic matter; A method for treating chlorine-containing plastic waste, characterized in that it comprises the step of recovering and recycling the dry gas. Plastic waste containing chlorine is dried in a non-oxidative atmosphere in the presence of metal dust and the chlorine contained in the waste is reacted with metal dust to produce ferric chloride (FeCl ₂ ), cuprous chloride (CuCl) and calcium chloride (CaCl). ₂ ), non-volatile metal chlorides of lead chloride (PbCl ₂ ), zinc chloride (ZnCl ₂ ), sodium chloride (NaCl), magnesium chloride (MgCl ₂ ) and aluminum chlorite (AlOCl) to produce chlorine in the residue Fixing and separating the chlorine from dry gas; A method for treating chlorine-containing plastic waste, characterized in that it comprises the step of washing the dry residue to dissolve and remove the water-soluble metal chloride. Plastic waste containing chlorine is dried at low temperature in a non-oxidizing atmosphere at a temperature of less than 300 ~ 450 ° C. to react chlorine contained in the waste with metal dust to produce ferric chloride (FeCl ₂ ) and chloride. Non-volatile properties of cuprous (CuCl), calcium chloride (CaCl ₂ ), lead dichloride (PbCl ₂ ), zinc chloride (ZnCl ₂ ), sodium chloride (NaCl), magnesium chloride (MgCl ₂ ), aluminum chlorite (AlOCl) Fixing the chlorine to the residue by producing a metal chloride to separate the chlorine from the dry gas; Washing the low-temperature dry residue to dissolve and remove the water-soluble metal chloride to dechlorinate the method. Plastic waste containing chlorine is dried in a non-oxidative atmosphere in the presence of metal dust to react chlorine contained in the waste with metal dust and calcium-containing basic inorganic compounds to produce metal chlorides that do not volatilize at dry temperature. Fixing to water to separate the chlorine from the dry gas; A method for treating chlorine-containing plastic waste, characterized in that it comprises the step of washing the dry residue to dissolve and remove the water-soluble metal chloride. Plastic waste containing chlorine is dried at low temperature in a non-oxidizing atmosphere at a temperature of less than 300 ~ 450 ° C. to react chlorine contained in the waste with metal dust and basic inorganic compounds containing calcium to volatilize at dry temperature. Separating the chlorine from the dry gas by fixing chlorine to the residue by producing a metal chloride which is not present, The method for treating chlorine-containing plastic waste material comprising the step of washing the low-temperature dry residue to dissolve and remove the water-soluble metal chloride. The method of claim 16, wherein the calcium-containing basic inorganic compound is calcium hydroxide, calcium oxide or calcium carbonate. 18. The method for treating chlorine-containing plastic waste according to claim 17, wherein as the calcium-containing basic inorganic compound, calcium hydroxide, calcium oxide or calcium carbonate is used. The method for treating chlorine-containing plastic waste according to claim 5, wherein the dried residue is alkali-washed to recover the eluted metal component as a hydroxide. The method for treating chlorine-containing plastic waste according to claim 3, wherein the pH of the discharged water after alkali cleaning is adjusted to a range of pH 5.8 to 8.6. The method for treating chlorine-containing plastic waste according to claim 20, wherein the pH of the discharged water after alkali cleaning is adjusted to a range of pH 5.8-8.6. Drying plastic waste containing chlorine in a non-oxidizing atmosphere in the presence of metallic dust and reacting chlorine contained in the waste with metallic dust to produce metal chlorides that do not volatilize at the drying temperature. Separating the chlorine from, Dechlorination by washing the low-temperature dry residue to dissolve and remove the water-soluble metal chloride; A method for treating chlorine-containing plastic waste, characterized in that it comprises the step of inducing the cleaning residue in the smelting furnace to melt recovery the remaining metal components in the smelting process. The method for treating chlorine-containing plastic waste according to claim 23, wherein the mixture of the chlorine-containing plastic waste and the metal dust is debris dust. Drying plastic waste material containing chlorine in a non-oxidative atmosphere in the presence of metal dust and reacting the chlorine contained in the waste material with metal dust to produce metal chlorides which do not volatilize at the drying temperature. Separating the chlorine from, Dechlorination by washing the low-temperature dry residue to dissolve and remove the water-soluble metal chloride; Inducing the cleaning residue in the smelting furnace to melt recovery the remaining metal components in the smelting process, A method for treating chlorine-containing plastic waste, characterized in that it comprises the step of recycling the dry distillation oil obtained by the thin-film dry gas or its concentration as fuel. Drying plastic waste material containing chlorine in a non-oxidative atmosphere in the presence of metal dust and reacting the chlorine contained in the waste material with metal dust to produce metal chlorides which do not volatilize at the drying temperature. Separating the chlorine from, Dechlorination by washing the low-temperature dry residue to dissolve and remove the water-soluble metal chloride; A method for treating chlorine-containing plastic waste, characterized in that it comprises the step of inducing the cleaning residue to the non-ferrous smelting furnace to melt recovery the remaining metal components in the smelting process. Drying plastic waste material containing chlorine in a non-oxidative atmosphere in the presence of metal dust and reacting the chlorine contained in the waste material with metal dust to produce metal chlorides which do not volatilize at the drying temperature. Separating the chlorine from, Dechlorination by washing the low-temperature dry residue to dissolve and remove the water-soluble metal chloride; Including the cleaning residue to the non-ferrous smelting furnace, including the step of melt recovery of the remaining metal components in the smelting process, The non-ferrous smelting furnace is a non-ferrous smelting furnace for the smelting of copper or lead, characterized in that the chlorine-containing plastic waste treatment method. Drying plastic waste material containing chlorine in a non-oxidative atmosphere in the presence of metal dust and reacting the chlorine contained in the waste material with metal dust to produce metal chlorides which do not volatilize at the drying temperature. Separating the chlorine from, Dechlorination by washing the low-temperature dry residue to dissolve and remove the water-soluble metal chloride; Including the cleaning residue in the smelting furnace and melting recovery of the remaining metal components in the smelting process, Carbide is recovered from the residue and the dried gas which has been washed after the drying, and used as fuel. The dried liquid obtained by concentrating the dried gas is separated by oil and water to recover the dried oil. A method for treating chlorine-containing plastic waste, characterized in that it is recycled as fuel. Drying plastic waste material containing chlorine in a non-oxidative atmosphere in the presence of metal dust and reacting the chlorine contained in the waste material with metal dust to produce metal chlorides which do not volatilize at the drying temperature. Separating the chlorine from Dechlorination by washing the low-temperature dry residue to dissolve and remove the water-soluble metal chloride; Including the cleaning residue to the non-ferrous smelting furnace, including the step of melt recovery of the remaining metal components in the smelting process, In the smelting step, the cleaning residue is dissolved in a non-ferrous smelter like smelting raw material, and the metal component in the residue is recovered into a smelting mat. Drying plastic waste material containing chlorine in a non-oxidative atmosphere in the presence of metal dust and reacting the chlorine contained in the waste material with metal dust to produce metal chlorides which do not volatilize at the drying temperature. Separating the chlorine from, Dechlorination by washing the low-temperature dry residue to dissolve and remove the water-soluble metal chloride; Including the cleaning residue to the non-ferrous smelting furnace, including the step of melt recovery of the remaining metal components in the smelting process, And the cleaning residue is dissolved in a non-ferrous smelting plant as a smelting raw material in the smelting step, and the resulting smelting slug is recycled as a cement raw material.