DE19606339A1 - Treating chlorine-contg. waste - Google Patents

Abstract

The process for treating chlorine-contg. waste comprises dry distilling the waste in the presence of a mixed metal dust in a non-oxidising atmos. to react the chlorine present in the waste with the metal dust, where water-soluble metal chlorides are produced which do not vaporise at the distillation temp.; and scrubbing the residue to dissolve and remove the metal chlorides so that dechlorination is completed. Other processes for treating chlorine-contg. waste are also claimed.

Description

Field of the Invention

The present invention relates to a method for Treatment of chlorine-containing plastic waste to this to render it harmless. In particular, it deals with one Process for the treatment of chlorine-containing organic substances like chlorine-containing plastics that are made from vinyl chloride put together, e.g. B. before their elimination without education of dioxins or other harmful chlorine compounds, the plastic components of the waste as fuel or Fuel is recycled and its metallic components can be easily recycled as raw materials.

In particular, the present invention relates to a ver drive to treat shredder dust from the Zer reduction of disposed cars, household electrical pre directions etc. results to render them harmless, reduce their volume and recycle them as raw materials. More specifically, the present invention relates to a method for Recycling treatment for full use of Shredder dust as a raw material, which includes: subjecting the Dechlorination treatment shredder dust when treated is going to be recycled as fuel, causing the back extraction of its metallic components using existing smelting furnaces and the reuse of Carbi the, oily and gaseous constituents, which are used as burning materials, as an energy source for the melting furnaces, etc. be won, allowed.

State of the art

The volume of urban waste and industry Waste has recently been increasing rapidly and its disposal by filling up the site or by treatment with combustion has become a social problem. In particular, are urgent Countermeasures required against the rapidly increasing Volume of shredder dust resulting from the crushing of disposed automobiles, household electrical appliances etc. results. Such shredder dusts are a mixture of  Plastic waste containing vinyl chloride or the like hold which as coating material for electrical lines serve, and metal dust, and most of it is against disposed of by filling up the site. On the other Side are plastic wastes belonging to the industrial Waste belongs to its suitability for use as Fuels (solid, oily or gaseous fuels) under from the point of view of recycling raw materials, and a typical known method therefor is one in which Plastic or rubber waste is dry distilled, their oily and gaseous components to recover (Japanese unexamined patent applications with the disclosure SHO no. 48-00067, 49-90773, 50-04168 and 50-85573).

Have these prior art processes the disadvantage, however, that if plastics containing chlorine, which contain vinyl chloride, etc., which Chlorine components during thermal decomposition Hydrogen chloride are evaporated and this hydrogen chloride the corrosion of the equipment caused or with that again obtained fuel is mixed. Procedures that the Incineration in the presence of air have that Problem that dangerous chlorine compounds such as dioxins form.

Known procedures used today as countermeasures against featured these problems of chlorine-containing plastic waste will include a process in which steam at high temperatures before the combustion treatment will give, and the dry distillation of the waste low temperatures takes place as the chlorine components Separate hydrogen chloride (Japanese unexamined patent Registration Disclosure Sho No. 48-60466), and a method in the iron or iron oxide added to the vinyl chloride resin which is then heat treated to convert the chlorine into iron (III) chloride (FeCl₃), a trivalent iron compound, by to convince the reaction with iron, and the iron chloride in the gaseous phase is transferred and separated (Japani  unexamined patent application Disclosure Sho No. 50- 32264). However, the former method still has that Corrosion problem due to the hydrogen chloride, during the The latter, although it is built so that it contains the chlorine easily sublimed iron (III) chloride transferred with the Result that the heat decomposition treatment at a lower heating temperature can be performed insofar as the other methods from the prior art corresponds to that as the chlorine constituents converted into gas and be separated, and thus the step of separation between the resulting gas and the iron (III) chloride gas after heat decomposition require what the treatment process complicated and the conversion efficiency of the fuels and of raw material recycling reduced.

In addition, a large volume of metal remains dust in the incineration ash without recovery, notwithstanding the procedures for its treatment mentioned above, because the shredder dust has a large volume of metal contains dust, and the combustion ashes are then cemented and disposed of by filling up the area, or too melted a stable slag, what its recycling as Raw material hindered.

Currently, most shredder dust is caused by railing discarded, but the increasing volume of the ge formed dust requires an effective disposal process, that differs from the terrain filling because one decreasing area for land filling is available. In addition, disposal has to be done by filling the site the state of the art due to the emergence of heavy metals and oils have led to pollution, which is a represents a significant social problem. It became a lot of speaking method proposed as a countermeasure, at the shredder dust is burned to produce heat, to decrease its volume.

However, since shredder dust, as mentioned above, a Mi Plastic waste management, including containing chlorine of plastics made from polyvinyl chloride or the like  composed mainly as a covering material for serves electrical cables, and represents metal dust remains when the shredder dust is burned directly into the Combustion chamber is given a large volume of burning ashes due to the heaviness contained therein metals cannot be disposed of directly, which is an afterthought action like fusion hardening requires. In addition exists because chlorine is present in these wastes at conventional heat treatment the risk of formation of Dioxins and also due to the hydrogen chloride Equipment corrosion problem, etc. As described above ben, it is impossible to solve these problems by a simple one Burn treatment to solve shredder dust.

Object and summary of the invention

The object of the present invention is a method of treating chlorine-containing art to provide waste that the problems of Be state of the art, and that for the production of fuels by treatment of chlorine-containing plastic waste, the vinyl chloride etc. contained or are composed of, by Dry distillation includes: The dry distillation of the Waste in the presence of mixed metal dust in one non-oxidizing atmosphere to remove the chlorine present non-sublimating metal chlorides through its reaction with Transfer metal dust, and separate the metal chlorides from the gas formed by remaining in the residue; the Fixing the chlorine prevents the formation of dangerous chlorine compounds, causing the waste become harmless while fuels made of plastic waste are made, and that with the plastic waste mixed metallic components recycled as raw materials which increases the practical utility of the process becomes.

It is an additional task of the present inventor dung, a process for the treatment of shredder dusts to provide to render them harmless, and to use them as  Recycle raw material that addresses the problems of conventional treatment of shredder dusts before their Disposal eliminates. More precisely, there is a task of the present invention in that a treatment method is ready the subject of shredding dust from the ent chlorination treatment during their heat decomposition, and allows the use of existing melting furnaces. The Be method of action of the present invention allows both reuse of carbides and oily and gas shaped components resulting from the treatment of the shredder Dust can be recovered as a result of heat decomposition Energy source for smelting furnaces etc., as well as the restoration recovery of the metallic components in the dusts Use a melting furnace, which reduces the shredder dusts become harmless and they are recycled as a raw material can.

More specifically, the present invention provides a method for the treatment of chlorine-containing plastic waste ready, which is characterized by dry distillation of chlorine-containing plastic waste in the presence of mixed metal dusts in a non-oxidizing atmosphere to remove the chlorine present in the waste with the Implement metal dust, creating water-soluble metal chlorides arise that do not at the dry distillation temperature evaporate, separating the chlorine from the dry style lation gas by fixing it in the residue and then washing the dry distillation residue for the dechlorination, the metal chlorides ent by dissolving be removed.

The present invention also provides a method for treating chlorine-containing waste, which includes: Dry distillation of chlorine-containing plastic waste in Presence of mixed metal dusts in a not oxidizing atmosphere at a low temperature of 300 to 450 ° C to the chlorine present in the waste implement the metal dust, creating water-soluble metal chloride arise during the dry distillation  Do not evaporate temperature, remove the chlorine from the Dry distillation gas by fixing in the residue, washing of the dry distillation residue for its dechlorination by dissolving and removing the metal chlorides and then eats dry distilling off the washed residue a high temperature of 450 to 600 ° C to the organic To decompose proportions in the heat, and to recover the metallic components from the residue after the high temperature dry distillation.

In the treatment method mentioned above are suitable te dry distillation temperatures 300 to 600 ° C and the The atmosphere for dry distillation is acidic substance concentration of 16% by volume or less, preferably 4 Vol% or less. The method preferably includes a washing step of the dry distillation residue with Alkali and the recovery of the metallic components, which are leached out of the residue as hydroxides, one Step to wash the dry distillation residue and subsequent crushing of the residue, which is then the magnetic separation is subjected to the iron dust separate and recover while non-ferrous metals and carbides separated from the residue and recovered be a step of recovery and reuse of the dry distillation gas or a step of Adjust the pH of the drain washes to one for Drainage waters permitted by law.

The present invention further provides a method for the treatment of waste containing chlorine, which the Dry distillation of chlorine-containing plastics in counter were mixed metal dusts in a non-oxidizing Atmosphere includes the chlorine present in the waste react with the metal dust, making water soluble Metal chlorides are formed during dry distillation temperature does not evaporate to remove the chlorine from the dry distillation gas by fixing it in the residue to separate, washing the dry distillation residue to to remove it by dissolving and removing the metal chlorides  chlorinate and insert the washed residue into a Melting furnace to the metallic components in the back stood during the melting process to melt and back to win.

In the treatment methods mentioned above, any a non-ferrous melting furnace, more precisely any melting furnace for Manufacture of copper or lead used as a melting furnace will. The treatment methods allow effective loading act of shredder dust. The treatment mentioned above can take a step of reusing the Dry distillation gas and condensation obtained dry distillation liquid as fuel include a step of carbide recovery from the washed residue and the dry distillation gases to use the same as fuel, the Dry distillation liquid obtained by condensing the Dry distillation gas is obtained, the oil / water Separation is subjected to the dry distillation oil win, and the dry distillation oil and the not condensed portions of the dry distillation gas as Reuse fuel, a melting step of the washed residue with a raw material for ver smelt in a non-ferrous furnace to the metallic Ingredients in the residue as inclusions in the melting stone to gain or take a step of recycling the enamel slag created in the non-ferrous smelting furnace as a cement raw material.

Brief description of the pictures

Fig. 1 is a flow diagram of the treatment, illustrating an example of the treatment method of the present invention;

Fig. 2 is a flow diagram of the treatment, illustrating an example of the smelting process of the present invention; and

Fig. 3 is a schematic representation of the dry distillation equipment used in the examples of the present invention.

Detailed description (I) dechlorination treatment

A treatment method according to the present invention is outlined in FIG. 1. Although the treatment process shown there includes a one-stage dry distillation, the dry distillation process can be carried out in several stages as described below.

Both in the description and in the claims the term "chlorine-containing plastic waste" means Wastes of plastics (resins), e.g. B. a chlorine containing resin such as a vinyl chloride resin, etc. Vinyl chloride or polyvinyl chloride, which is often used as a coating material used for electrical cables contains theoretically approximately 56% by weight (hereinafter only as% called) chlorine. It shows against other polyolefin resins and polystyrene resins behave differently, when subjected to combustion or heat decomposition is, and is subject to heat decomposition at relatively low temperatures (approximately 200 ° C or more), where chlorine hydrogen is formed. To solve this problem of education Avoiding hydrogen chloride is the treatment procedure of the present invention built to contain chlorine plastic waste in the presence of mixed metal dust in a non-oxidizing atmosphere at a Temperature of 300 to 600 ° C can be distilled dry to implement the existing chlorine with the metal dust, whereby Metal chlorides are formed during dry distillation temperature does not evaporate, causing the chlorine in the back stand is fixed. Although theoretically such an amount of Metal dust is sufficient to cover the entire existing To convert chlorine in the plastic into metal chlorides an excess over the stoichiometric reaction equivalent from a practical point of view, its Consider reactivity etc., preferred. A typical one Example of a mixture of chlorine-containing plastics felling and metal dust is, as mentioned above, shredder Dust. Shredder dust usually contains 10 to 30% by weight  Metal dust, and the rest consists mainly of resin share. The treatment method of the present Er allows the direct treatment of such shredder Dusts, the metal dust and resin components as a mixture contain.

If coating materials for electrical lines, the mainly consist of vinyl chloride, in the absence of ge mixed metal dusts in a nitrogen atmosphere at 300 are distilled dry up to 600 ° C, evaporate when errei Chen from 300 ° C 80% or a little more of the available chlorine as hydrogen chloride, while if shredder dusts with ge mixed metal dusts dry at the same temperature be hydrogenated by the decomposition of vinyl chloride is formed, with iron, copper, aluminum um, zinc, magnesium, calcium, sodium, lead and others in converts metals present in the dust, whereby metal chlorides arise in the above-mentioned dry distillation do not evaporate temperature. The metal chlorides remain in the Dry distillation residue back as solids, causing less chlorine gas and hydrogen chloride gas results.

A calcium-containing basic inorganic compound can the shredder dust as a replacement for the metal dust or be added as an additive. Calcium hydroxide, calcium oxide, Calcium carbonate or the like can be considered to contain calcium basic inorganic compound can be used. Here reacts that formed during the decomposition of the plastics Chlorine with these calcium compounds to make calcium chloride form, which is fixed in the residue. In cases where where the waste has a low metal content, therefore the addition of any of these calcium compounds serves that chlorine in the residue easily and with low Fix costs.

The dry distillation temperature is preferred at least 300 ° C at which the chlorine is released from the resin will, and up to 600 ° C at which most resin components be decomposed in the waste. Temperatures outside this range is not preferred because the dechlorination at  Temperatures lower than 300 ° C prevented while some of the metal chlorides are at temperatures Evaporates above 600 ° C and migrates into the gas phase.

The dry distillation is sufficient for a Period continued until the resin has decomposed, the Response has progressed to a sufficient degree and the production of the metal chlorides is completed. The time it takes to decompose about 200 g of plastic waste is required is on the order of 30 up to 60 minutes, of course, depending on the volume, the temperature etc. of the treated waste.

In addition, dry distillation is carried out in an atmosphere phere performed by introducing an inert gas such as Nitrogen was used to remove the air. Here be records the "non-oxidizing atmosphere" the one that Oxygen in a concentration of 16 vol% or less contains. An atmosphere of inert gas, which is an oxygen has a concentration of 4 vol% or less, be preferably used. Dry distillation in the air (in an oxidizing atmosphere) is not preferred because the mixed iron etc. during dry distillation oxi is volatile chlorides with high oxidation numbers arise. If e.g. B. Iron in the air chlorine reacts in the organic waste to form iron (III) chloride (FeCl₃). This iron (III) chloride, which has a boiling point of approximately 317 ° C sits, and therefore at a significantly lower temperature than the boiling point of iron (II) chloride (FeCl₂) (approx 1023 ° C) evaporates, thus evaporates during the dry style lation, and a fixation of the chlorine in the residue can cannot be reached.

Dry distillation can advantageously be carried out in several stages be performed; e.g. B., a primary dry distillation (Low temperature dry distillation) at a tempe temperature of 300 to 450 ° C, preferably 300 to 350 ° C where most of the existing chlorine is released is followed by a second dry distillation (high  temperature dry distillation) of the residue, which at a Temperature of 450 to 600 ° C is carried out at a large part of the remaining resins that the coating material lien include, be decomposed.

After completion of the primary dry distillation most of the entire available chlorine is released and reacted with metal dust, whereby metal chlorides ent were standing in the dry distillation residue remain while trace amounts of it in the dry Evaporate distillation gas. During the primary dry season Most of the resins are distilled in the heat sets while the existing chlorine is released, and evaporate as a dry distillation gas. This dry style Lation gas is introduced into a condenser, where it is used for Condensation is cooled, and the resulting drying Till liquid is extracted and then the oil / water separation by centrifugal separation or the like under throw. In the meantime, the uncondensed portions of the Gases introduced into an alkaline solution, and an alkali cleaning is carried out to remove trace amounts of chlorine, remaining in the gas to collect, separate and to recover. The dry distillation gas exists at all mainly from hydrocarbon gases that are used as fuel gases can be reused.

Most of the primary distilla's metal chlorides Residual residues are water soluble, and the metal chlorides are solved by washing the residue. The washing can a wash with water or it can be an alkaline Be wash using sodium hydroxide, lime or the like, which are added to the water. Since this washing liquids by adding sodium oxide, lime or similar can be neutralized, those from the back sediment washed out metal ions abge as hydroxides be separated and recovered. The alkali content of the wash liquid is adjusted so that a pH range arises, where the washed out metal components as hydroxides be canceled. The optimal pH range changes  depending on the metal types, and the alkali levels can depending on the respective types of metals as desired can be set.

In cases where the pH of the drain washes outside the legal restrictions on runoff waters is the pH of the washing liquids after the metal hydroxides were removed, again on the legally permissible area set for waste water. In cases where the pH the washing liquid outside the legally permissible loading is from 5.8-8.6, the pH is z. B. again on the Range set after the metal hydroxides are returned were won.

Alternatively, the metal chlorides can be made by washing washed out with water, separated and by conv tional processes are recovered, e.g. B. by the Electrodialysis, a procedure that involves the use of a Includes ion exchange resin, or a process which the washing liquids through evaporation up to the crisis tallization concentration are treated.

The primary dry distillation residue is washed and then a second dry distillation step throw. Most of the resins are in the heat by the second dry distillation step decomposed into gases. Since that Chlorine used in the primary dry distillation step was fixed, was removed by washing the residue, the secondary dry distillation gas contains a small amount Amount of chlorine gas and hydrogen chloride gas, and therefore settles most of the secondary dry distillation gas from water substance and hydrocarbons together. The secondary dry Distillation gas is in a cooling section in the same introduced quietly like the first dry distillation gas to to be condensed in a dry distillation liquid, which is then recovered. On the other hand uncondensed portions of the gas in an alkaline solution introduced, whereby trace elements of the chlorine components by alkaline cleaning collected, separated and returned be won.  

In the same way as for the primary dry distilla tion liquid becomes the secondary dry distillation subjected to centrifugal separation to the Remove water and recover the oily components. The obtained dry distillation gas and the oily stock parts can be recycled as fuel. The dry Distillation is not limited to a two-step process and can be carried out in several stages, the drying Distillation temperatures can be changed in the stages. On Example of a composition (% by volume) of dry distilla tion gas is as follows:

H₂: 51%
CO: 7.6%
C₃H₈: 1.1%
CH₄: 17%
C₂H₄: 0.6%
n-C₄H₁₀: 1.0%
CO₂: 0.05%
C₂H₆: 2.6%.

The secondary dry distillation residue is washed to remove trace amounts of metal chlorides, then dried, crushed and the magnetic separation under to recover the iron dust. That iron dust can be reused as scrap metal. The dry style Lation residue from which the iron has been removed is in a separation process, such as gravity screening or Sink separation into carbides and non-ferrous metal dusts separated, and the carbides are recovered as fuel while the non-ferrous metal dusts as raw material for the metal be recovered. The separation process and recovery of the carbides is not based on those mentioned above limited their differences in relative densities exploit, and any process that is based on differences in Shape, particle size, etc. can be used. The Washing the residue can be a water wash or a be alkaline laundry. The recovery of the metallic Components from the washing liquids of the secondary dryer Distillation residue can be processed in the same way leads as for the washing liquids of the primary Dry distillation residue.  

According to the treatment procedure described above are about 70% or more, preferably about 80% or more or more preferably 99% or more of that in art waste chlorine present in the residue without Ver steaming fixed and then removed. Since the ratio of the fixed chlorine compared to conventional burns treatment where approximately 30 to 80% of the previous existing chlorine is gassed and vaporized, is very large, and the metal chlorides found in the dry distillation back are fixed, easily leached out by washing, the treatment procedure described above does not require very complex post-treatment.

(II) removal of the metallic components under Use of a melting furnace

The treatment method of the present invention can after the dechlorination / dry distilla described above treatment, which is dechlorination and recycling Fuel by dry distillation of the chlorine-containing Completed plastic waste, a smelting process include in which the dry distillation residue in a furnace is loaded to the metallic inventory recover parts.

(i) Dechlorination treatment process

The dechlorination treatment procedure before contraception Treatment procedure is as described above. The Dry distillation gas and the dry distillation oil, the can be obtained in the dry distillation process can be recycled as fuel for the smelting process.

It is also possible to use the dry distillation gas before being placed in a condenser in a dust trap introduce the carbides that are mixed with this gas to catch and win, and that in the dry still tion residue contained carbides as fuel win and recycle. After the dry distillation residue has been cleaned and crushed, the in the Dry distillation residue containing carbides separated and because of their difference in relative densities  recovered. The separation and recovery can also due to the difference in shape or particle size be performed.

(ii) Smelting treatment process

After washing, the dry distillation residue in a melting furnace for non-ferrous metals such as copper or Lead loaded and together with a raw material for that Melt melted to the metallic components in the residue as inclusions in the melting stone, while iron, calcium etc. were obtained as smelting slag will.

In cases where shredder dust falls directly into the Melting furnace without passing through the drying described above distillation process causes chlorine gas or hydrogen chloride gas used in the decomposition of art is formed, as described above, the corrosion of the Melting furnace, fireplace and other connected equipment and the problem of damage to the work Surroundings. Since the dry distillation residue in the Melting process is introduced after first through the Dry distillation process has been treated Treatment method of the present invention this Problem not.

The type of furnace in which the dry distilla residue can not be loaded on any one special limited; possible ovens include a number of melting furnaces used for smelting processes, pyrometal lurgic refining processes etc. can be used Melt raw ores, concentrates, etc. B. Blow furnaces; Flash ovens; reducing ovens; Reverb ovens; Converter; Anode furnaces; Melting furnaces, separation furnaces and converter furnaces for the continuous copper production, etc. based on the Properties of the special dry distillation residue, etc. can be selected.

Fig. 2 is a flow diagram of the Verhüttungsverfahrens for the production of copper, an example of a smelting procedure that is used for the treatment method of the present invention.

According to the smelting process for producing copper illustrated in the figure, copper concentrate is melted in a reverb furnace 21 to separate into FeO-CaO-SiO₂ slag and a copper sulfide stone containing iron sulfide, and the stone is in the converter 22 introduced, in which air is blown into the molten stone to oxidize the iron components, which are then driven off as slag, and to blow the copper sulfide into raw copper. The slag is returned to the reverberation furnace 21 , where the slag is treated again to recover the copper components, while the raw copper obtained in the converter 22 is transferred to an anode furnace 23 , where the raw copper, after removal of its impurities by oxidation, evaporates to evaporate or as slag, is reduced to raffinate copper. This raffinate copper is used as an anode in electrical refining. Exhaust gas containing sulfur dioxide, etc., which is produced in the reverb furnace 21 and the converter 22 , is passed into the boiling vessel 24 and a Cottrell separator 25 in order to remove the fly slag.

The residue from the dry distillation of the shredder dust is mainly loaded into the reverb furnace 21 or the converter 21 , depending on its properties, melted with the copper concentrate or stone, while the iron and the calcium contained in the residue become slag be oxidized, which separates from the stone. Precious metals which are present are melted and mixed with the stone together with the raw copper, transferred to the anode furnace 23 as an inclusion in the raw copper and finally obtained by an electrolytic process. Lead oxide and zinc oxide contained in the fly ash contained in the reverb furnace 21 and converter 22 are recovered from the exhaust gas in the boiling vessel 24 and the Cottrell separator 25 , while the carbides are extracted from the dry distillation / washing residue and from the exhaust gas can be obtained as fuel together with the dry distillation gas and the dry distillation oil. The slag produced in the converter 22 is returned to the reverb furnace 21 for reuse or used as a raw material for cement and as an aggregate.

As described above, it will correspond to the treatment process that the dry distillation process and the Smelting process includes, in cases where shredder dust, which has a large volume of chlorine-containing plastics such as Contains vinyl chloride resins, the chlorine problem due to the Thermal decomposition of the plastic through the dry distilla tion treatment, and the metals in the contraception Processes are recovered at low cost. In addition, heat recovery is achieved using the Carbide, the dry distillation gas and the dry style lation oil caused by the heat decomposition of the plastics arise as fuel. Continue to emerge since the slag produced in the smelting process also as Raw material can be used for cement, etc., no Final waste that requires land filling, and so will the problem of disposal of shredder dusts, etc. fully constantly resolved.

Description of the preferred embodiment

The present invention is now made in view of the following examples explained. It should be noted that these examples are for illustration only and not limiting the scope of the present invention mean.

example 1

The dry distiller shown in Fig. 3 was used to prepare 195 g of shredder dust (auto dust) (metals: 45 g, resins: 121 g, chlorine in the resins: 4.8 g and other components: 29 g) subject to primary dry distillation by heating in an atmosphere of nitrogen gas at 300 ° C in a crucible furnace for 1 to 1.5 hours. The resulting dry distillation gas was introduced into a condenser 2 to obtain a dry distillation liquid (26 ml) in a collecting vessel 3 , while uncondensed portions of the dry distillation gas were blown into a solution of sodium hydroxide (1% concentration, 100 ml) for alkaline cleaning. The dry distillation liquid was separated into water and oil (8 ml). The majority of the oil was a "heavy oil" equivalent and the dry distillation gas (17 ml) after the alkaline purification consisted mainly of hydrogen and methane, which were fully recyclable as fuel and whose chlorine levels were extremely low.

On the other hand, the residue (162 g) of the primary dry distillation was washed with 500 ml of purified water, and the chlorine content of the washing liquids was determined to be 4.02 g. Then, the washed residue of the primary dry distillation was heated to 560 ° C for 1.5 hours in the same dry distiller for a secondary dry distillation, and the dry distillation gas was cooled for condensation in the condenser 2 to be 23 ml of a dry distillation liquid and 18 liters of one To gain drying still gas. The dry distillation liquid was separated into an oil and water by centrifugal separation, while the dry distillation gas was treated by alkaline cleaning. The residue (87 g) from the secondary dry distillation was washed with 500 ml of purified water, and the chlorine content of the washing liquid was determined to be 0.62 g. On the other hand, little chlorine was detected when the chlorine content of the dry distillation gas was measured in the same way. The main components of the secondary dry distillation gas were hydrogen and methane as in the primary dry distillation gas, and the dry distillation oil obtained from it was a "heavy oil" equivalent.

As described above, almost all of the above existing chlorine in the primary dry distillation residue fixed by the primary dry distillation, and approximately 82% of the fixed chlorine was removed by washing with water away. There was little chlorine in the recovered Dry distillation liquid and the dry distilla  tion gas, and its main components were water Substance and methane that are useful as fuel and fuel gas are. The results of the present example are in Table 1 shown.

Comparative Example 1

Dust (8.1 g) of a vinyl chloride resin was added to a Pri subjected to dry drying distillation by heating to 300 ° C, and then a secondary dry distillation by heating at 1000 ° C in an oven with an alumina tube furnace was equipped, in the absence of metal dust, while nitrogen gas was introduced into the furnace. The primary and secondary dry distillation gases were each in a 10% sodium hydroxide solution (100 ml) introduced to the chlorine in the gases as chlorine ions to collect and the chlorine concentration of the gases were measured. The dry distillation residue was 200 ml purified water washed for 60 minutes, and the chlorine Concentration of the washing liquids was measured. The Results are shown in Table 2.

As shown in Table 2, the chlorine levels were Alkaline washes used for the primary dry distilla tion gas and secondary dry distillation gas used , 2.0 g and 0.01 g, the chlorine content of the dry end Till residue was 0.34 g and approximately 85% of the existing chlorine was gassed and with the primary dry distillation gas mixed, and so the chlorine could not be separated.

Table 2

Results of Comparative Example 1

Examples 2-4

Shredder dust samples of various compositions were in a dry distillation device, which in the was constructed in the same way as in Example 1 dry style liert, except that an oven with an aluminum oxide tube was used among the Temperatures and atmospheric conditions shown in Table 3 are shown. Make samples 1 through 6 of Example 2 Shredder dust with average contents of Fe, Cu and Ca. while samples 7 through 8 of Example 3 represent cases with higher iron contents and samples 9 to 10 of Example 4 Represent cases with higher Cu contents.

As shown in Table 3, the chlorine levels of the Dry distillation gas from samples 1-10 of the present the examples all less than 1%; almost the whole existing chlorine remained in the residue and 96-98% of the remaining chlorine was drained when the residue was washed.

Comparative Examples 2-5

Shredder dust samples with those shown in Table 4 Compositions were used as raw materials and under the temperatures and atmospheres listed in Table 4 Phases dry distilled using the same Dry distillation device used in Example 2 has been. The results are shown in Table 4. In ver same as example 2, sample 11 is compared to example 2 and sample 12 is compared to example 4, wherein both samples were dry distilled at 700 ° C. In Comparative example 3, sample 13 is compared to example 2 and sample 14 is compared to example 4, wherein the two samples were dry distilled at 250 ° C. In Comparative Example 4, samples 15 and 16 become examples 2, where the dry distillation at 300 ° C. or 560 ° C was carried out while air in the furnace was blowing. Comparative Example 5 is the case where a metal free sample under the same conditions as for Sample 1 of Example 2 was dry distilled.  

As demonstrated by the samples of Comparative Examples 2 3 to 4% of the chlorine is gasified and with the Dry distillation gas mixes in cases where the dry distillation at a high temperature of 700 ° C was led. On the other hand, the samples demonstrate of Comparative Example 3, that 71 to 74% of the existing Chlors remain in the washed residue as most Chlorine has not been decomposed in cases where the dry distillation temperature was as low as 250 ° C. Continue are according to conventional heat decomposition procedures involving air blowing, such as Comparative example 4 shown, 38 to 52% of the existing Chlorine gasified and with the dry distillation gas or Dry distillation oil mixed. In addition, as by Ver same example 5 shown, 77% of the chlorine evaporate into the Dry distillation gas or the dry distillation oil in Absence of a metal.

Example 5 and Comparative Example 6

Raw materials with Fe, Cu and Ca contents that the Half or less of their average salaries in Shredder dust were treated in the same way as in Example 1 with the addition of calcium oxide, calcium hydroxide or Calcium carbonate treated (example 5: samples 19, 20 and 21) or without adding it (Comparative Example 6). The results are listed in Table 5.

In Comparative Example 6, in which no calcium compound was added (sample 18) 10% of the chlorine with the Dry distillation gas mixed while 99% of the chlorine in the residue from Example 5 (samples 19-21) when adding Calcium oxide, calcium hydroxide or calcium carbonate as in the Examples 2 to 4 were fixed.

Example 7 (1) Dry distillation process

A continuous dry distillation furnace with the inside horizontal heating was used for continuous Dry distillation of shredder dust of the compositions, which is listed in Table 6, with a load of 2 Tons per hour at 550 ° C and the resulting drying Till residue was washed with 5 m³ / h water, ent watered and then dried in the sun. The dry style lation gas was in a condenser for cooling by Kon densation introduced, and the resulting dry distilla tion fluid was recovered. The non-condensing portions of the gas were introduced into an alkali solution, traces of chlorine left in the gas by alkali to collect and separate the cleaning, and then back won. In the meantime, the dry distillation became liquid oil / water separation by centrifugal separation subjected, and the resulting dry distillation oil recovered. Table 7 is a list of the amounts of washed residue, dry distillation gas and Dry distillation oil after the alkaline wash recovered, their chlorine levels and their burning values. Here, while washing with water, became Neutralization, partial lime to the dry distillation residue, causing the dissolved metal ions again have been canceled. The total amount of heat from the dry distilla tion products from the shredder dust was 1060 kg / h on coal and after deducting the amount of heat (140 kg / h based on Coal), which is used for melting the non-combustible parts (490 kg / h), such as the metals present in the residue, the final amount recovered was required about 900 kg / h based on coal. The chlorine levels of Dry distillation products and the wash residue were listed in Table 7 below; it has been confirmed, that there was no chlorine problem even if the wash residue was loaded into the furnace.  

Table 6

Shredder dust composition (% by weight)

Table 7

Amount and calorific value recovered by the dry distillation treatment

(2) smelting process

A 0.5 kg portion of the dry distillation wash residue in the dry distilla described above tion method was obtained, and that in Table 8 had described composition, was contraception tion process supplied for the production of copper, and in a melting furnace together with a melting agent (0.04 kg) in addition to the poor copper stone (2.0 kg) and the slag  (1.7 kg) with the compositions listed in Table 3 given; the mixture was at 1350 ° C for one hour heated and the compositions of the resulting poor Kupferstein and the slag were analyzed with the Results listed in Table 9. The together settlement of the slag formed in the furnace also listed in Table 9.

As evidenced by the results shown, confirms that the addition of the dry distillation wash back to the poor copper stone in a ratio of 1: 4 die Amount of copper stone and slag proportional to Amount of the added residue increased and thus the metallic components and the non-metallic inventory parts of the residue by absorption in the poor copper stone or the slag are recovered; changed anyway the composition of the poor copper stone and the Slag compared to that before adding the residue, d. H. it was not affected by the addition of the dry distillation residue, and therefore the smelting process for the production of copper subsequently by conventional Proceeding.

Table 8

Composition before the smelting treatment (% by weight)

Table 9

Composition after the melt treatment

Example 8

The washed residue from the dry distillation Treatment of Example 1 was at a rate of 0.86 tons per hour of a continuous copper production Process that is capable of producing 70 tons / h of copper concentrate to be processed together with flux (14 tons / h) ten, and the compositions of the extracted stone and the Slag obtained were compared to those at to which no washed residues have been added. The Results are shown in Table 10. No difference in the composition was found between cases where the washed residue was added and the cases where no washed residue was added, and a continuous stable smelting process for manufacturing of copper was carried out in the two groups.  

Table 10

Effect on contraceptive treatment

Example 9 and Comparative Example

A 0.5 kg portion of dry distillation / wash back levels of shredder dust in the dry distillation method of Example 1 (Sample A) had been obtained, and 0.5 kg of shredder dust that is not by dry distillation treated (sample B), were prepared and at 1350 ° C for an hour together with flux (0.04 kg), poorer Copper stone (2.0 kg) and slag (1.7 kg) added were heated in the same manner as in Example 1. Here the gas formed was introduced into a scrubber in which a jet of wash water was directed at the gas to it to cool. This experiment was done 15 times for each of the samples A and B repeated to corrode the tube section (manufactured by SIS 316) and the wash water jet nozzle section (manufactured by SIS 316).

The result was that no macroscopic corrosion of the  Tubes and nozzles for sample A, by drying had been treated, observed, and especially after the test, no reduction in weight nozzle used compared to that of a fresh nozzle was found. On the other hand, it became weak Color turbidity of the tube and nozzle parts for comparison sample B observed. In addition, it was confirmed that the nozzle portion 0.07% of its weight compared to that of a fresh one Nozzle had lost.

Claims (30)

1. A method of treating chlorine-containing plastic waste, which comprises:
Dry distillation of chlorine-containing plastic wastes in the presence of a mixed metal dust in a non-oxidizing atmosphere in order to react the chlorine present in these wastes with the metal dust, whereby water-soluble metal chlorides are formed which do not evaporate at the dry distillation temperature to remove the chlorine from the dry distillation gas fix to separate in arrears; and
Washing the dry distillation residue to dissolve and remove the metal chlorides mentioned, thereby completing its dechlorination. 2. The treatment method according to claim 1, wherein the Dry distillation temperature is 300 to 600 ° C. 3. The treatment method according to claim 1, wherein the Dry distillation residue of an alkaline Cleaning is subjected to the from the residue as Hydroxides washed out metallic components to recover. 4. The treatment method according to claim 1, wherein the Dry distillation residue washed, crushed and subjected to magnetic separation to to separate and recover the iron dust, while non-ferrous metals and carbides from the residue be separated and recovered. 5. A method for treating chlorine-containing plastic waste, which comprises:
Dry distillation of chlorine-containing plastic waste in the presence of a mixed metal dust in a non-oxidizing atmosphere at a low temperature of 300 to 450 ° C, in order to react the chlorine present in the waste with the metal dust, where water-soluble metal chlorides are formed which do not evaporate at the dry distillation temperature, to separate said chlorine from the dry distillation gas by fixing it in the residue;
Washing the low-temperature dry distillation residue to dissolve and remove the metal chlorides mentioned and thereby complete the dechlorination; and
Dry distillation of the washed residue at a temperature of 450 to 600 ° C to decompose the organic components in the heat, and recovery of the metallic components from the high temperature dry distillation residue. 6. The treatment method according to claim 5, wherein the Low temperature and high temperature dry Distillation residues from an alkaline cleaning be subjected to the from the residues as Hydroxides washed out metallic components to recover. 7. The treatment method according to claim 5, wherein the high temperature-dry distillation residue washed, crushed and then under the magnetic separation is thrown to separate the iron dust and back gain while the non-ferrous metals and carbides be separated from the residue and recovered. 8. The treatment method according to claim 1, wherein the Dry distillation in a non-oxidizing atmosphere is carried out, which is an oxygen concentration tration of 16 vol% or less.   9. The treatment method according to claim 5, wherein the Dry distillation in a non-oxidizing Atmosphere is carried out which is an oxygen has a concentration of 16 vol% or less. 10. The treatment method according to claim 8, wherein the Dry distillation in a non-oxidizing Atmosphere is carried out which is an oxygen has a concentration of 4% by volume or less. 11. The treatment method according to claim 9, wherein the Dry distillation in a non-oxidizing Atmosphere is carried out which is an oxygen has a concentration of 4% by volume or less. 12. The treatment method according to claim 1, wherein the Dry distillation gas recovered and recycled becomes. 13. The treatment method according to claim 5, wherein the Dry distillation gas recovered and recycled becomes. 14. The treatment method according to claim 1, wherein the in the Plastic waste chlorine with the metal dust is implemented by dry distillation so as not volatile metal chlorides of iron (II) chloride (FeCl₂), Copper (I) chloride (CuCl), calcium chloride (CaCl₂), lead (II) chloride (PbCl₂), zinc chloride (ZnCl₂), sodium chloride (NaCl), magnesium chloride (MgCl₂) and aluminum hypochlorite (AlOCl). 15. The treatment method according to claim 5, wherein the in the Plastic waste chlorine with the metal dust is implemented by dry distillation so as not volatile metal chlorides of iron (II) chloride (FeCl₂), Copper (I) chloride (CuCl), calcium chloride (CaCl₂), lead  (II) chloride (PbCl₂), zinc chloride (ZnCl₂), sodium chloride (NaCl), magnesium chloride (MgCl₂) and aluminum hypochlorite (AlOCl). 16. The treatment method according to claim 1, wherein the Dry distillation in the presence of an inorganic calcium-containing basic compound in addition to the metal dust is carried out. 17. The treatment method according to claim 5, wherein the Dry distillation in the presence of an inorganic calcium-containing basic compound in addition to the metal dust is carried out. 18. The treatment method according to claim 16, wherein calcium hydroxide, calcium oxide or calcium carbonate as anorga niche calcium-containing basic compound used becomes. 19. The treatment method according to claim 17, wherein calcium hydroxide, calcium oxide or calcium carbonate as anorga niche calcium-containing basic compound used becomes. 20. The treatment method according to claim 5, wherein the Dry distillation residue with an alkaline Cleaning is treated to the from the residue as Hydroxides washed out metallic components to recover. 21. The treatment method according to claim 3, wherein the pH of the Drain water after the alkaline cleaning on the legally permissible area for runoff waters is set.   22. The treatment method according to claim 20, wherein the pH of the Drain water after the alkaline cleaning on the legally permissible area for runoff waters is set. 23. A method for treating chlorine-containing plastic waste, which comprises:
Dry distillation of chlorine-containing plastic wastes in the presence of a mixed metal dust in a non-oxidizing atmosphere in order to react the chlorine present in these wastes with the metal dust, where water-soluble metal chlorides are formed, which do not evaporate at the dry distillation temperature, to fix said chlorine from the dry distillation gas separate in arrears;
Washing the dry distillation residue to dissolve and remove the metal chlorides, thereby completing the dechlorination; and
Introducing the washed residue into a melting furnace to melt and recover the metallic components in the residue during the smelting process. 24. The treatment method according to claim 23, wherein the chlorine containing plastic waste mixed with it metal dust is shredder dust. 25. The treatment method according to claim 23, wherein the ge called dry distillation gas or the dry distillation oil obtained from it by condensation is recycled as fuel. 26. The treatment method according to claim 23, wherein the washed residue in a non-iron melting furnace is introduced.   27. The treatment method according to claim 26, wherein a Melting furnace for the production of copper or lead as Non-iron melting furnace is used. 28. The treatment method according to claim 23, which further includes: recovery of the dry distillation Carbides from the washed residue and the dry distillation gas to use as fuel while by condensing the dry distilla tion gas obtained dry distillation liquid the oil / water separation is subjected to the drying isolate distillation oil, and recycle this Dry distillation oil and the uncondensed Proportions of dry distillation gas as fuel. 29. The treatment method according to claim 26, the further comprises: melting the washed residue with a Raw melting material in a non-ferrous melting furnace to the metallic components in the residue as To gain inclusions in the melting stone. 30. The treatment method according to claim 26, the further comprises: melting the washed residue with a Raw melting material in the non-ferrous melting furnace and Reuse the resulting melt slag as Cement raw material.