DE2748510A1 - METHOD OF RECYCLING WASTE MATERIALS WITH COMBUSTIBLE COMPONENTS - Google Patents

Description

J ₀ > ₂₈ . Qkt. 1977

βυθό MCNCHEN 3

3930-1-10.145

R. SPLANEMANN Dr. C. REITZNER L -ING. j. JUDGE

Patent application

Pexlmooser Zementwerke Aktiengesellschaft in Vienna (Austria)

Process for the recovery of waste materials with combustible components

The steep rise in the price of conventional fuels makes it necessary to develop new energy sources. Of special Of interest are waste materials that contain combustible components have, i.e. have a calorific value, but their utilization has not yet been possible, for example

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.. ice because it saves in a conventional incineration suitable condition can be brought because their calorific value is subject to large fluctuations or because they are high Have combustion residues, the composition of which usually fluctuates greatly and whose use or landfill is problematic.

Examples of the first group of waste materials with a high calorific value are industrial waste made of plastic or old and scrap tires. Here the calorific value is in the same order of magnitude as that of high-quality conventional fuels, but the waste materials can only be shredded and freed from disruptive components such as steel inserts at very high costs. Once they have not been comminuted, they cannot be used in conventional burning devices. Attempts have been made to crush as tires using liquid carbon dioxide or nitrogen in the supercooled state at -60 ⁰ C, however, this method has not been able HConsult major. The possibilities of recycling shredded tires, for example for heat-insulating floor coverings, bath mats, shoe soles and the like, are also unsatisfactory for various reasons. On the other hand, for reasons of environmental protection, it is not possible to store old tires and plastic waste in landfills in the very large quantities currently occurring.

Examples of the second group are household waste, oil sludge, used oil, paint residues, animal carcasses, digested sludge, etc. These substances have a strongly fluctuating, at times relatively low calorific value in common, and there are also often combustion residues , the amount and composition of which are also subject to strong fluctuations are.

Because of the difficulties mentioned, it usually is

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necessary the waste materials, possibly after more costly Processing, to be incinerated in our own facilities, without the inherent energy could be used. In the case of waste materials that fluctuate greatly in their calorific value, it is often the case necessary, at least temporarily, the combustion process through additional heating, for example with fuel oil or natural gas is operated to maintain · It can not only not be used in these cases, but the energy of the waste materials high-quality energy must also be supplied. Such additional heating is for environmental reasons mostly indispensable to prevent incomplete combustion, which is the case with plastic waste, tires and other organic materials Substances not only represent an odor nuisance, but are harmful to health, which must be avoided with absolute certainty. Even with complete incineration, the storage of the incineration residues usually prepares further considerable amounts Difficulty finding an outdoor storage is in view of groundwater pollution or air pollution problematic due to dustiness. The further processing of the incineration residues comes from this particular importance to.

There have already been many ways of using the above-mentioned waste materials or disposing of them safely suggested.

For example, attempts have been made to use household waste as a raw material in the cement industry, with household waste in the Incinerator is entered. In doing so, the inherent Calorific value can be used, the remaining ash reacts with the raw material already in the furnace Cement clinker. Difficulties arise in this process

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However, the fact that both the calorific value of household waste and the composition of the combustion residues are strong vary. For this reason, both the calorific value of the household waste and the exact composition of the incineration residues must be determined Be known before use in order to adjust the amount of conventional fuel supplied and the residues Take this into account when coordinating the raw cement clinker mass to be able to. This naturally entails high costs and at least requires large stores of waste and complex homogenizing systems.

In DT-OS 2 41o 32o a method for burning off rubber and plastic layers on metal bodies is under full preservation of the metal properties described. This process uses the calorific value of the pyrolysis gases outside of the proceedings does not take place. It is either the heat content or the calorific value of the pyrolysis gases at all not used or only used to preheat the metal body or to maintain the smoldering process. The entire The method is therefore exclusively aimed at the disposal or incineration of a, otherwise very special small group of waste materials, namely plastic layers on metal bodies, to accomplish, u.zw. in a special facility equipped for this purpose. It serves the process stage of the pyrolysis of the waste materials only to get in better more controllable and regulated than is possible with a normal combustion, the burning of this Undertake substances and thus avoid the release of an excess of harmful exhaust gases into the atmosphere. It will at the same time, a relatively large technical effort with simultaneously high losses of the calorific value inherent in these substances operated, a specific use of the heat for a technical purpose is not intended. It is in this

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drive a large part of that inherent in the pyxolysis gases Calorific value or the V / arm amount released during combustion in a cooling section downstream of the combustion chamber destroyed by the injection of air or "water.

The DT-OS 2 51o 339 describes a method in which halogen and / or sulfur-containing waste materials from pyrolysis are subjected, after which the gases formed during pyrolysis are first cleaned and then only burned are supplied for their destruction. The pyrolysis is only carried out there to reduce the amount of gas from the exhaust gas removed harmful halogens or sulfur compounds reduce. The device used to carry out the process accordingly consists of a pyrolysis chamber, a separate device for the removal of halogens or sulfur compounds and a Bxennex for abxennen the Pyrolysis gas.

The energy inherent in the pyxolysis gas is not or only increased in a manner similar to that in accordance with the DT-OS treated above a very small part, such as to maintain the pyrolysis itself odex to heat the separate Device for removing dez halogens or S-compounds utilized. It is not intended to use the pyrolysis gases outside the waste incineration plant. The procedure also works discontinuously.

The aim of the present invention is to include a process in which a / complete incineration of the waste material takes place, e.g. a pyrolysis process, possibly after appropriate adaptation to create a new advantageous method which makes it possible to use the

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released from (combustible) waste materials of any kind Pyrolysis gases, inherent considerable calorific values (and also the amount of heat from the pyrolysis process) in an industrial one Process outside of the waste incineration process to use, but at the same time and without additional effort - e.g. without the interposition of a not costly only in the acquisition / but also in the operation Cleaning stage - also the requirements of environmental protection to fully comply with the purity of the waste gases from waste incineration.

According to the invention, the waste materials themselves are not fed to the heating device of an industrial process, but are first ^{incompletely incinerated in a separate device, which will be referred to below for the sake of simplicity as "smoldering furnace 11.} The gases produced during this heating process in the smoldering furnace are then passed through , which, depending on the nature of the waste materials used, have a more or less high calorific value, to the heating or burning device, where they are completely burned, possibly together with conventional fuels and continue to be used.

The invention thus provides a method for the recovery of waste materials with combustible components that possibly fluctuations in the composition and quality, especially in the water content, in the content of constituents, which are endothermic when heated Subject to reaction and / or fluctuations in the calorific value, for example plastic waste, in particular polyethylene, Polyvinyl acetate, polyamide, polyvinyl chloride, etc.,

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especially cords, stockings, jerseys, genrest and others heavy Plastic waste to be shredded, natural or artificial Rubber products, especially car and scrap tires, Rubber, garbage, especially household garbage and / or bulky goods, Slaughterhouse waste, fats, animal carcasses, waste acids / textiles, Paper, wood, straw, sulphite waste liquor, phenol-containing waste products, oily waste products from wastewater treatment plants of refineries or petrochemical plants, as well as sediments from oil tanks, oil separators, oily Grinding sludge, floating sludge from sewage treatment plants, oil emulsions, waste from gasoline separators, used oils, waste solvents, Paint residue, porous rocks soaked with oil, paint or similar organic products, especially perlite contaminated earth

/ or quicklime, for example from tanker accidents, refinery sludge, Printing ink, digested sludge, fresh sludge, primary sewage sludge and / or excess sludge, in which process the Waste materials in the absence of air or in the absence of air decompose with the release of their volatile components and / or incomplete combustion, and the resulting gases, possibly with the interposition a storage tank or buffer, possibly together with conventional fuels, are burned »the

curse,
indicates that the decomposition and / or incomplete incineration of the waste materials takes place in a first process stage, which is directly combined with a second process stage, within which the waste materials that have arisen during the decomposition and / or incomplete incineration Pyrolysis gases, optionally together with conventional fuels, are burned in a heating chamber, in particular a combustion chamber, for heating, in particular for burning, starting raw materials for building materials, preferably for hydraulic or non-hydraulic binders, whereby

- 7 *) oxidizable substances, e.g. those with cyano compounds

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if necessary further for regulation, adjustment and if necessary required or desired maintenance of the

Volatilization,

Total calorific value of the supplied, by the / decomposition and / or incomplete combustion, gases and the conventional fuels the amount of conventional fuel supplied Fuels, preferably by measuring the temperature and / or the heating state, in particular the Degree of deacidification of the building material subjected to the heating, in particular binding agent, within the heating space, in particular Combustion chamber, the second process stage is controlled or regulated.

The method according to the invention combined for the first time and in a previously not described way a process in which an incomplete incineration of waste occurs, In a technically advanced manner with a process for Production of building materials, especially binders, the most important component of which is a heating, in particular a burning process.

When carrying out the method according to the invention, it has been found shown quite unexpectedly that not only those that were not used or even destroyed in previous waste destruction processes present in the waste materials or the pyrolysis gases Energy can be used to the greatest possible extent in an advantageous manner it can also be done with environmentally hazardous substances, such as sulfur oxides, zinc, lead or halogens / ν he impure ized Pyrolysis gases - u.zw. surprisingly again - completely independent of the type of waste used - the sensitive ones Reactions in the burning processes of building material production, such as those in the burning of cement clinker - in none May interfere, and that ultimately an exhaust gas is obtained,

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that in comparison to one of the previously common ones conventional fuels operated combustion process originating exhaust gas does not differ in its composition or, even is purer, and that in this simple and at the same time useful way the environmentally hazardous substances from waste incineration have been rendered completely harmless.

Another x side effect is that which can be achieved if necessary Improvement of the strength properties of a cement clinker which is exposed when heated with pyrolysis gases Effects consist in the fact that the (after) combustion chamber provided according to the prior art can be omitted because it becomes formed by the directly connected furnace for heating or burning the building material. Own cooling or dedusting dex vex burned pyrolysis exhaust is superfluous, they takes place practically in the heating process or burning process for the building materials themselves and / or in the downstream, necessary for this pio process and therefore from the outset Existing equipment for cooling or dedusting. Even the reduction in the risk of explosion should not be unmentioned here stay.

Since the gases produced in the smoldering furnace, for example Unsaturated hydrocarbons are fed directly to the heating device, in which they are completely incinerated can cause environmental nuisance (odor nuisance, damage to health due to unsaturated hydrocarbon fission products etc.) as they feared in previous waste incineration processes wax, do not occur. at The Vexfahxen according to the invention it is therefore not necessary, as in the previous methods, to use them under all circumstances to operate with excessively excessive air in order to get a

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sudden increase in calorific value, for example due to plastic components in household waste and / or in the event of a sudden decrease the content of substances which enter into endothermic reactions when heated, to prevent with certainty that it too environmentally harmful, incomplete combustion occurs. On the contrary, the waste materials are used for complete Combustion with too little air excess, heated if there is insufficient air or if there is no air. So it will always be when heated aimed at and achieved an incomplete combustion. There is a high excess of air that is usually required for combustion the method according to the invention already brings about an extremely strong deterioration in the thermal efficiency because of this, a better yield of the waste materials inherent energy and it can be based on high quality supplementary energy be waived. Fluctuations in the water content and / or in the content of substances which are endothermic when heated Suffering reactions and / or affecting the calorific value of the waste materials in the method according to the invention only to the degree the incompleteness of the combustion, which is of no great importance, since in the method according to the invention there is always one incomplete incineration of the waste is sought. An afterburning chamber, as is the case with the currently known processes arranged for the recovery or disposal of waste materials must be omitted in the process according to the invention Completely. The heating or incomplete incineration of the waste materials according to the method according to the invention Accruing gases are, as they are immediately available for further use of the heating device of a building material production process are fed, completely burned there. They therefore do not have to be cooled, cleaned or dusted or processed in another way. The warmth inherent in them is also fully used. With the incomplete

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Combustion in the 1st stage of the process according to the invention Furthermore, explosions by highly flammable, low-boiling substances can be avoided in a much better way than in the previously known processes, in that the vaporized gases are immediately and continuously withdrawn from the smoldering furnace and fed to the heating chamber or combustion chamber, where they are completely burned.

It is preferred that the gases formed from the waste materials in the first process stage are burned directly in a second process stage provided for heating or for burning raw materials for cement clinker in their high temperature range. Under high-temperature region is a temperature range of about 600 ⁰ C, in particular about 85o ° C, advantageously over lloo ° C and more preferably about 12oo ° C understood. Very good results are achieved with regard to the purity of the exhaust gases.

Volatilization, The waste materials are advantageously decomposed

and / or the release of incomplete combustion resulting gases promoted in that a negative pressure, in particular in the waste heating device provided for this purpose a pressure between 0.2 and 0.8 ata is maintained.

A preferred embodiment of the method .is

Liquefaction, marked as the temperature in the for / decomposition and / or incomplete incineration of the waste materials is set and / or kept essentially constant that the gas withdrawal when the temperature rises is promoted, meanwhile, when the temperature drops the gas withdrawal is throttled.

If the temperature rises in the smoldering furnace, for example

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by decreasing the water content of the waste materials, if necessary automatically, more gases are withdrawn from the smoldering furnace v / ground and thereby a further increase in the temperature in the smoldering furnace is avoided. If the Temperature in the smoldering furnace can be throttled to remove the gas, causing the temperature to drop Standstill comes. The temperature set or evened out in this way is ensured in the waste heating furnace making the best use of those inherent in waste Energy. This preferred procedure can also be used in the currently known methods in the event of sudden Changes in the composition and / or nature of the Waste materials relatively frequent overheating of the waste smoldering furnace, that lead to the formation of melts, deposits, the above-average escape of volatile components, such as alkali, sulfur, chlorine or fluorine compounds, as well as signs of corrosion, especially on the Refractory lining of the waste smoldering furnace, leads with Security to be avoided.

A favorable embodiment of the process consists in that the heating device of the first process stage provided for the incomplete combustion of the waste materials is additionally supplied with heat. This can be done, for example, by direct heating with conventional fuels that are burned in conventional burners. It is preferred in which the volatilization.
/ First process stage comprising decomposition and / or incomplete incineration of the waste materials to supply additional heat by introducing hot starting raw material, in particular cement clinker or quicklime, heated within the second process stage, in particular in a combustion chamber. According to a further advantageous variant, the heat is supplied

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by supplying hot gases, in particular by a separate

v sw train or else derten process taken from hot exhaust gases / have a temperature of up looo 2oo ° C, advantageously from 3oo to 800 C, in particular of 4oo to 600 ⁰ C. According to a particularly preferred embodiment, it is provided that in the first process, which includes the decomposition and / or incomplete combustion, the kiln exhaust gases produced within the second process stage when burning the starting materials for hydraulic or non-hydraulic binders, in particular for cement clinker, and / or during cooling of the burnt materials, in particular cement clinker, hot gases or hot air, especially at the above-mentioned temperatures, are supplied through direct and / or indirect heat exchange to be supplied if a bypass has to be arranged in the area of the heat exchanger for reasons of alkali, sulfate or chloride pollution in the second process stage. By changing the heat supplied in this way, the temperature prevailing in the smoldering oven can be set and regulated in the desired manner and, if necessary, also kept constant. This is particularly useful in the initial period of commissioning or when the furnace is to be throttled or accelerated from time to time, or when waste materials of very different properties or with only a low calorific value are to be used. Such hot gases with temperatures as specified above generally occur in many branches of industry as inferior gases which cannot be used at all or can only be used inadequately. One example is the cooling air that is produced when the hot Portland cement clinker is cooled using the currently known methods and which can only be partially used, for example to preheat the air supplied to the burner, while the rest is often a recycling option or area of application is missing.

As heating devices ("smoldering ovens") in which

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the heating and incomplete incineration of waste materials is carried out, rotary kilns are suitable, such as those for example used in the cement industry, shaft furnace, Four-bed ovens, deck ovens, grate ovens, sintering belts An embodiment variant is advantageous here in the temperature inside the heating device intended for the incomplete incineration of the waste material thereby adjusted and / or kept essentially constant is that the waste materials in the heating device with a different or adjustable speed introduced or carried out by them. If the temperature rises, for example, the Migration speed increased, decreased if it fell, the migration speed can be set, for example in a rotary kiln by changing the speed of rotation, in a shaft furnace by changing the extraction of the combustion residues, in a grate furnace or sinter belt by changing the speed of movement of the grate or sintering belt and, in the case of a multiple-hearth furnace, by changing it the speed of rotation of the agitator arms. Another way to increase the temperature in the heating device influence is the amount of waste that is fed into the machine to be changed, e.g. in grate ovens or sintered belts by varying the layer height on the grate or sintered belt.

Of course, two or all of the above-mentioned measures for setting and, if necessary, can also be used Uniformity of the temperature in the smoldering furnace can be used simultaneously and side by side. It can also be beneficial be to provide for the supply of 'heat only intermittently and when required, for example only during commissioning.

If necessary, to improve the economic

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The vas serge also has the potential for incomplete combustion certain waste materials before being introduced into the smoldering furnace by mechanical dewatering, for example with the help of rotary vacuum filters, centrifuges, filter presses and the like and / or by chemical means, e.g. by adding quicklime and / or calcium hydroxide and / or by drying, can be reduced, where any hot exhaust gases or other excess heat can be used.

As in the process according to the invention in the second process stage any conventional fuels introduced Examples include natural gas, heating oil, coal dust or their mixtures.

It can be used when using additional / conventional fuels

in the second procedural stage, caused by the incomplete Combustion generated gases and the at least one conventional Fuel can be fed to the heating chamber, in particular the combustion chamber, via a common burner.

Favorable with regard to the effectiveness of the combustion is a procedure in which it is provided that the through the incomplete combustion resulting gases, possibly with additional air, as a carrier medium for the conventional Fuel, especially for coal dust and / or to improve the atomization of a conventional liquid Fuel, for example heating oil, and / or as a second gaseous one Fuel content in a gaseous fuel, e.g. Natural gas is used in particular to regulate the shape of the Fläramen will.

The method according to the invention ensures the high

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Temperature in the furnace of the second process stage, which is about 145o ° C when burning cement and about 115o ° C when burning lime (whereby the furnace chamber temperature is still a few loo ° C higher) that the fission products formed in the incomplete combustion in the first stage are certain burn completely, whereby environmental damage can be excluded. The gases can either be fed directly into the Oven are blown in or they can be particularly advantageous, as mentioned, also as a carrier medium for the conventional Fuels, are used. Another advantage is that the gases from the waste smoldering furnace are also harmful volatile constituents, such as sulfur and / or Alkali compounds, as the gases usually contain after their combustion as furnace exhaust gases in a known manner

ζ Β
for drying the raw materials / grinding-drying systems are used, where the volatile constituents condense on the raw material or react with it and are therefore no longer released into the atmosphere. Of particular interest in this context are, for example, the zinc oxide-rich gases which arise when rubber products are heated, in particular old and scrap tires, and which represent a significant nuisance to the environment. When using the method according to the invention in connection with a cement clinker production process, the zinc oxides introduced into the kiln with the incompletely burned gases are deposited on the cement clinker meal, where they combine to form calcium zincate. This connection is not only completely harmless, but increases the strength-building value of the clinker significantly.

With regard to the desired simplicity of the regulation of the heating process in the second process stage, it is favorable if a mixture of at the incomplete Combustion produced gases into conventional fuel

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Nm Exd gas equivalents in a ratio of 1: 3o to 1: I _1, preferably from 1: 2o to 1: 2.5 _t, in particular from 1: Io to 1: 4, added wixd.

A very simple and effective regulation dex heating in the second Vexfahxensstufe, with complete freedom in the Process design in the heating of waste materials with combustible Shares also allow a process variant in which within the second process stage, in particular of the heating chamber, in particular the combustion chamber, by measuring the temperature and / odex the heating state of the heated one Starting raw material in the sintering zone of the combustion chamber, the ratio of in the first process stage during the decomposition and / or incomplete combustion of gases produced with conventional fuel is adjusted and regulated wixd. The firing zone temperature or the heating state can be used be kept essentially constant.

According to a further variant, it is provided that within the second process stage, in particular of the combustion chamber, by measuring the temperature and / or determining the heating state the raw materials to be burned, preferably by determining the degree of deacidification, at the end of the calcining zone of the combustion chamber (especially in the case of heat exchangers and Lepolöfen in the furnace inlet) the ratio of in the first Process stage in the decomposition and / or incomplete Combustion produced gases adjusted to conventional fuel and wixd wixd ·

In the method according to the invention used in the building materials industry, a device for determining the degree of deacidification is preferred as the device for determining the heating state of the Exhitzungsgut.es. Those mentioned as "measuring sensor ¹¹

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Serving devices can accordingly be arranged in the sintering zone of a rotary kiln, but preferably, in particular In the case of devices for determining the degree of deacidification, they are at the end of the calcining zone, the combustion chamber, in particular at V / ärmetauschöf en and Lepolöfen, arranged in the furnace inlet.

It is of further importance that the incomplete combustion in the smoldering furnace of the first stage if necessary accruing heating residues when carrying out the method according to the invention in the building material-producing industry can be recycled without any particular difficulties. The heating residues are usually in the mainly from compounds of lime, silicic acid, clay and iron oxide. According to one embodiment of the method They can therefore be used, if necessary after homogenization, as a raw material, for example for cement clinker, hydraulic lime, highly hydraulic lime or Roman lime can be used. So there will be those in the incomplete incineration of the waste materials accruing heating residues or a part thereof advantageously added to the raw mass, which is in the second combustion device is burned. This variant is particularly advantageous if the heating residues are still small Contain quantities of unburned constituents which are no longer of interest for thermal reasons, but which lead to difficulties if the residues are used for other purposes.

The ash that may have been removed from the smoldering furnace with the gases created in the smoldering furnace of the first stage and dust particles can be used immediately and directly in the coordination of the raw mass, for the heating of which these gases will be taken into account. If necessary, however, they can

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also after the smoldering oven, but before further use removed from the gas by one of the usual methods and optionally be added to the raw mass before it enters the kiln.

According to a further variant, the incineration residues resulting from the incomplete incineration of the waste materials can be used particularly advantageous as latent hydraulic or pozzolan-like ingredients or additives in the Production of hydraulic binders (containing pulp), in particular cement with pulp, mixed binders, Plaster and Mauex tapes, masonry mortars, containing grit White lime or hydraulic lime, ready-made plasters, plasters containing gypsum or binders, etc. and / or as an additive the processing of these binders are used.

An apparatus for carrying out the invention The method is explained using the schematic sketch in the drawing.

The device is essentially formed by a possibly provided with a heat supply device 3, first heating device 1 for volatilization, decomposition and / or incomplete incineration of waste materials with combustible constituents, a second heating device 2, in particular a furnace, furthermore a first line 4 for discharging the gases produced in the first heating device 1, which is connected to a burner 5 arranged within the second heating device 2, if necessary a second line 6 for feeding the conventional fuels into the second heating device 2, as well as optionally one, preferably discontinuously operating, arranged in or on the first heating device 1

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Discharge device 8 for removing the when heated Waste materials from heating residues.

Within this basic system, there are now various options for even better use of heat and heat Waste materials.

For example, the burnt hot material, e.g. cement clinker, is removed from the outlet 13 of the kiln 2 and reaches via the discharge 14, for example a shaft, either into the cooling device 15, e.g. a clinker cooler, the cooling air heated there by the hot material can be discharged directly or indirectly from the cooling device 15 via a line 16 Heating the waste materials of the first heating device 1 are supplied.

Another possibility is to remove the hot material from the discharge 14 before it reaches the cooling device through the feed 14a in the first heating device branch off where it is the inherent warmth content to the can give off waste materials that are to be charred.

The waste materials A itself can go to the heating device 1 either added directly via the inlet la or first passed via a line 9 via the heat exchanger 17, VJO they are (pre) heated. As a heating medium for the heat exchanger 17 can be taken via lines 18, 18a of the second heating device 2, in particular a furnace hot exhaust gases are used, which then also, if necessary, also directly, to heat the waste materials can be introduced into the first heating device 1.

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The combustion residues graze on a heating device 1 taken from entwedex via the display device 8 odei abex they graze over the line 2o dem over the Line 19 from dex Kühleinxichtung 15 sensed, in the cooler 15 chilled goods from the Biennpio process, e.g. chilled clinker, added or mixed in in the desired ratio. the Disposal residues V can be abex as already mentioned above felt via a line dex, not shown, into the heating device 2 fed and doxt, for example, to be added raw mass. Such an addition of Residues on the raw meal is particularly beneficial if the volatile components are set in the pyrolysis oven, and coke-like ones that are still difficult to escape in the residues Residues are included. For any desired The waste materials are heated with conventional fuels via a feed line 3a with an in dex exheating device arranged burner 3 is provided.

The first heating device 1 is advantageous for Volatilization, decomposition and / or incomplete combustion of waste materials as a shaft furnace, Dxehxohxofen, Wixbelschichtofen, Deck oven, roasting oven odex designed as Sintex belt.

For controlling and regulating the total calorific value of conventional Fuel and dex from dex from an exheating device 1 originating exhaust gases is inside the second heating device 2 provided that in the second line for feeding dex conventional fuels into the second Heating device 2 one by a Tempexatux measuring device lo, loa and / odei a unit lo, loa for detecting the heating state of the material to be heated, possibly via a line 12, influenceable Duichflussiegeleiniichtung 11 is arranged.

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The temperature measuring device lo, loa and / or that is preferred Device lo, loa for detecting the exheating condition of the material to be heated, in particular a device for determining the deacidification factor of the material to be heated, at the end of the kettle one, especially in the case of heat exchange ovens and Lepol ovens in the furnace inlet arranged.

It is particularly preferred if the first line 4 for discharging the heat generated in the first heating device 1 Gases with the second line 6 for supplying the conventional fuels before they open into the burner or are brought together in the burner 7 itself, in particular at the burner nozzle. The corresponding line is in the Fig. Designated with 4a. As mentioned above, it can be achieved by using these gases either as a carrier medium for solid conventional fuel, such as coal dust, or to improve the atomization of a conventional fuel liquid fuel, for example heating oil, and / or as a second gaseous fuel component in one gaseous fuel, e.g. natural gas, especially to regulate the shape of the flame.

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fKii.v ^ i; ■

Application example 1:

A cylindrical pyrolysis vessel, which was provided with a gas-tight lid, was used in an electrically heated oven. The top of the cover had a thermally insulated over conduction nozzle, which was led to a semi-technical cement kiln and there opened into a gas burner. In parallel to this burner, a second burner was arranged in the kiln, with which a conventional natural gas-oxygen mixture could be burned. The cement rotary kiln, which was designed in the form of a tub, had no inclination. This made it possible to leave the items to be fired in the furnace until sintering was complete. Downstream of the rotary kiln was a bed of raw meal granules in the form of a Lepol grate, through which the hot kiln exhaust gases leaving the kiln were passed. The grate on which the raw meal granules were located was moved slowly so that the furnace exhaust gases cooled down considerably during the entire experiment after passing through the grate. The raw meal granules were then burned to cement clinker in the usual way, which will be returned to later. 8 kg of granulated car tires with a grain size of 3 mm were added to the pyrolysis vessel as waste. The temperature in the pyrolysis vessel was set to 700 ° C. The pyrolysis gases escaping at this temperature were then fed to the first burner of the cement rotary kiln in the manner described above. The furnace had already been brought to temperature with the conventional natural gas-fired burner and immediately before the experiment with about 7 kg of raw meal tablets pressed from pre-cooked marl (approx. Io mm in height, approx. 0 % CaO, 20.8 % SiO ₂ , 1.1% and 2.6 % Fe ₂ O ₃ ). During the trial

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the mixing ratio of pyrolysis gas - conventional natural gas in the fuel fed to the furnace was adjusted so that the temperature in the furnace remained practically constant. After leaving the furnace, the exhaust gases, which now consist of the burned pyrolysis gas and the burned conventional natural gas, were passed through the bed of raw meal granules in the manner described. The composition of the raw meal granules corresponded to that of the kiln feed material, but these raw meal granules were not calcined and accordingly had a loss on ignition of 36.2 % and a moisture content of lo.4 % .

The pyrolysis gases were burned in this way over a period of 60 minutes in the kiln. After this time, the clinker produced in the kiln had a free lime content of 2.7 % . This clinker was ground in the laboratory mill with the addition of 5 % raw gypsum stone (34.5 % SO-) cement to a grinding fineness corresponding to 31oo cm / g according to Blaine.

At the same time, clinker with the same composition was produced, but instead of using pyrolysis gas, only conventional natural gas was used to fire the furnace. This clinker, which had a free lime content of 3.0 % , was also ground in the Laboxatorium mill to 310 cm / g according to Blaine.

The test according to the Austrian cement standard ON B 33Io gave the following results:

*) OE-NORM

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π 2748510 "Pyrolysis clinker" "Exdgas clinker" Fineness of grind after Blaine 3loo cm / g 31oo cm / g Onset of solidification 2 ^h 35 min 2 ^h 20 min End of solidification 3 ^h 50 min 4 ^h 00 min Compressive strength after 3 days 212 kp / cnr 2o3 kp / cnr η 28 " 396 kgf / cm 374 kgf / cm ²

Dex had "Pyxolyseklinkex", which was found according to the invention with it some high strengths.

As mentioned on both sides, the gxanalia, by which the exhaust gases were routed after leaving the furnace, were burned to clinker in the usual way and this was ground to clinker, again with 5 % raw gypsum stone (34.5 % SO ₃ ) in a laboxatoxium mill. The following differences were found between the Klinkex ex produced from "pyrolysis waste gas granules" and the "conventional waste gas treated granules" when tested in accordance with ON B 331ο:

Klinkex out

"Pyrolysis off-gas" with conventional gianaiien "exhaust treated

Gxanalia "

after Blaine 3170 cm ² / g Q 318o cm ² / g Onset of solidification 3 ^h 25 min 2o4 kp / cmr 3 ^h 05 min End of solidification 4 ^h 15 min 425 kgf / cm ² 3 ^h 55 min Compressive strength after 3 days 2ol kp / cm • 1 28 ^st 366 kgf / cm ²

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Meanwhile, the solidification times and initial strengths are practically the same, the clinker from the "pyrolysis waste gas granules" has significantly higher 28-day strengths on.

It is believed that this is due to the zinc content that these granules have absorbed from the pyrolysis waste gases. The pyrolysis waste gas granules had a zinc content corresponding to 0.3 % ZnO; no zinc was analytically detectable in the granules treated with conventional waste gas.

In the same way, clinker was produced using pyrolysis gases obtained from the following waste materials became:

a) Used tire granulate 8 mm

b) Used tire granulate 1 mm

c) Cutlets made from polyethylene, polyamide, polypropylene, polyvinyl acetate and latex

d) chips made of polyvinyl chloride

e) Fat-soaked waste bleaching earth

f) Textile exests (stockings, plastic cords, etc.)

g) slaughterhouse waste
h) sulphite waste liquor

i) foundry sand containing phenol

k) contaminated waste oil

1) oil contaminated earth

m) plastic paint

n) digested sludge

In all of these cases, similarly favorable results were obtained as when using the used tire granulate

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described example

In detail, the following results were obtained from
Standards test according to ON B 331o. All test mixtures contained
% Raw gypsum with a content of 345% SO ₃ , the fineness according to Baine was 3050-315o cm / g.

Waste solidification solidification compressive strength

start end in kp / cm ²
h min h min after 3 days after 28 days

a) 2 4o 3 5o 2o5 4o5

b) 2 45 4 00 214 396

c) 2 35 3 45 199 388

d) 1 35 2 2o 243 427

e) 3 oo 4 Io 188 4o2

f) 2 3o 3 4o 2oo 389

g) 3 o5 4 Io 191 '39o h) 2 55 4 oo 216 421 i) 2 55 3 45 177 383 k) 3 Io 4 o5 199 394 1) 3 oo 3 5o 2o6 411 m) 3 45 4 4o 162 432 n) 2 5o 3 4o 185 4ol

The strength development of the with

Granules of burnt clinker treated with pyrolysis gases were favorably influenced, provided that the waste materials chloride and zinc he contained lead compounds and absorbed them on the way via the pyrolysis gases from the clinker or the raw meal granules became.

809818/0955

27Λ851

The investigation of the pyrolysis residues occurring during the pyrolysis of the scrap tire chips showed that 47 % of the scrap tire granulate was converted into pyrolysis gases. In a separate experiment, these pyrolysis gases were condensed and the lower calorific value (raw) was determined on them as Io21o kcal / kg.

total kcal / kg

Damii / i and 3839o / were added to the kiln,

3 which corresponds to a saving of natural gas in the amount of approx. 4.5 Nm natural gas.

Since the pyrolysis was carried out under the exclusion of air, the pyrolysis residue 7o% carbon and 3o% contained metallic iron. The iron could be picked out by hand, the coke-like residue could be used as fuel for a shaft furnace raw meal.

Examination of the furnace exhaust gas after it had passed through the raw meal showed that the exhaust gas was off in all cases Carbon dioxide (H ^ O) and nitrogen as well as traces of oxygen existed, regardless of whether pyrolysis gases were also burned or not.

In no case could carbon monoxide or hydrocarbon compounds be found in the experiment according to Example 1 and experiments a) -n) or compounds of chloride, sulfur, zinc, Pb or other heavy metals can be detected.

Application example 2:

In the pyrolysis vessel described in Example 1 was fat-soaked fuller's earth (calorific value 568o kcal / kg) heated,

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however not like doxt with exclusion of air, but with lack of air. In doing so, enough air was always supplied to the pyrolysis vessel that some oxygen could be detected in the corresponding "pyrolysis gases". It was found that, regardless of this excess of oxygen, the pyrolysis gases ¹¹ still contained substantial amounts of hydrocarbon compounds and carbon monoxide. An attempt was now made to burn these oxidizable constituents of the pyrolysis gases in an afterburner had to have a temperature of at least 900 ° C. and an excess air ratio of at least 1.8 for about 15 minutes in order to ensure complete oxidation of the "pyrolysis gases".

The pyrolysis residue formed under these conditions had the following composition:

Loss on ignition (looo ° C) 0 %

SiO ₂ 69.6 %

Al ₂ O ₃ 18.3 %

Fe ₂ O ₃ 4.2 %

CaO 2.6 %

MgO 2, o? 6

SO ₃ o.1 %.

Remainder 3.2 %

This residue, just under 50 % of the dry starting substance, was then ground to a grinding fineness corresponding to a residue on the sieve 0.06 DIN 4188 (mesh size 6o ₇ µm) and mixed with Portland cement PZ 375 (grinding fineness 3680 cm / g according to Blaine) test according to the Austrian cement standard oN B 331o there were the following results ver - aligned with the current standard grinding additive blast furnace slag

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«SW

same fineness:

Cement composition

"Pyrolysis residues" blast furnace slag

Start of solidification End of solidification Compressive strength (kp / cm ² )

after 3 days after 28 days after 9ο days 572 595 577 554

The addition of the "pyrolysis residue" to the PZ 375 has therefore does not have a damaging effect, but even improves the strengths at the late appointments, in particular compared to the currently used additive.

In the tests according to Example 2, fuel savings and the purity of the exhaust gases were essentially achieved the same results as in Example 1 and in the experiments a) - n) there.

loo % 85 % 85 % 7o % 7o% 0 % 15th % - 3o % - 0 % - 15th % - 3o % 3.1o ^h 3.25 ^h 3.15 H 4.oo ^h 4.l5 ^h 4.25 ^h 4.3o ^h 4.4o H 5.1o ^h 5.25 ^h 273 221 229 175 168 464 442 445 4ol 4o3

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Claims (1)

27Α85Ί0 Pat ent a-n spray: / Process for the recovery of waste materials with combustible Components that may have fluctuations in the Composition and quality, especially in the 'water content, in the content of components that are subject to endothermic reactions and / or fluctuations when heated, im Have calorific value, for example waste plastic, in particular Polyethylene, polyvinyl acetate, polyamide, polyvinyl chloride, etc., in particular cords, stockings, leftover tricot and other plastic waste that is difficult to shred, natural or artificial Rubber products, in particular car and scrap tires, rubber, garbage, in particular household garbage and / or bulky goods, Slaughterhouse waste, fats, animal carcasses, waste acids, oxidizable toxins, e.g. those with cyano compounds, textiles, Paper, wood, straw, sulphite waste liquor, phenol-containing waste products, oily waste products from waste water refineries or petrochemical plants, as well as sediments from oil tanks, oil separators, oil-containing Grinding sludge, Schwirara sludge from sewage treatment plants, oil emulsions, Waste from gasoline separators, waste oils, waste solvents, Paint residue, porous rocks soaked with oil, paint or similar organic products, especially perlite c ontamin xert e nrae / or quicklime, for example from tanker accidents, refinery sludge, printing ink, digested sludge, fresh sludge, primary sewage sludge and / or excess sludge, in which process the waste materials in the absence of air or in the absence of air eaner / 2 volatile constituents or incomplete combustion, and the gases produced in the process, optionally with the interposition of a storage device or buffer, optionally together with conventional fuels, are burned, thereby 809818/0955 ORIGINAL INSPECTED Z 274Ö510 V c-x volatile ar. «Y, indicates that the / decomposition and / or incomplete incineration of the waste materials in a first process stage takes place, which is directly combined with a second process stage. Volatilization, is linked, within which the / decomposition and / or complete incineration of the waste materials Pyrolysis gases, optionally together with conventional fuels, in a heating room, in particular one Combustion chamber, for heating, in particular for burning, starting raw materials for building materials, preferably for hydraulic or non-hydraulic binders, are incinerated, whereby possibly also for the regulation, setting and, if necessary, required or desired keeping the Volatilization,. Total calorific value of the supplied, due to / decomposition and / or incomplete combustion, gases and the conventional fuels the amount of conventional fuel supplied Fuels, preferably by measuring the temperature and / or the heating state, in particular the Degree of de-acidification of the building material subject to heating, in particular binders, controlled within the heating chamber, in particular combustion chamber, of the second process stage or is regulated. 2. The method according to claim 1, characterized in that the gases formed in the first process stage from the waste materials are fed directly to a second process stage provided for heating or for burning raw materials for cement clinker and in its high temperature range, in particular at temperatures above 600 ^° C , advantageously above 85o ° C, preferably above 100 ° C and particularly preferably above 1200 ° C, 3. The method according to claim 1 or 2, characterized in that the decomposition of the waste materials and / or the release dex in αer / decomposition and / or incomplete combustion gases are promoted in that in 809818/0955 the first process stage a negative pressure, in particular a Pressure between 0.2 and 0.8 ata is maintained. 4. The method according to any one of claims 1 to 3, characterized Volatilization, characterized in that the temperature in the intended for the / decomposition and / or incomplete incineration of the waste materials first procedural stage set and / or substantially is kept constant by the gas withdrawal is promoted when the temperature rises, while at a drop in temperature, the gas extraction is throttled. 5. The method according to any one of claims 1 to 4, characterized in that in the event of fluctuations in the composition and / or nature of the waste materials, the temperature is set and essentially within the first process stage provided for dxe / Zersexzun'g and / or incomplete combustion of the waste materials is kept constant by the waste materials in this first process stage with a
different or adjustable speed are introduced or carried out by this. 6. The method according to any one of claims 1 to 5, characterized .Religibility, marked that in the the / Zersetziing and / or incomplete Incineration of the waste materials, including the first process stage, additional heat through the introduction of hot, Within the second process, step e, in particular in a combustion chamber, heated starting raw material, in particular cement clinker or quicklime, is added. 7. The method according to any one of claims 1 to 5, characterized Authorization, characterized that in the the / decomposition and / or incomplete Comprehensive first stage of the incineration process 809818/0955 within the second process stage when burning the starting materials for hydraulic or non-hydraulic binders, in particular for cement clinker, kiln exhaust gases and / or during the cooling of the burnt materials, in particular the cement clinker, hot gases or hot air resulting from direct and / or indirect heat exchange , in particular at temperatures of 2oo - looo C, advantageously 3oo - 800 ⁰ C, preferably 4oo - 600 ⁰ C, are fed. 8. The method according to any one of claims 1 to 7, characterized in that within the second process stage, in particular of the combustion chamber, by measuring the temperature and / or the heating state of the heated starting raw material in the sintering zone of the combustion chamber, the ratio of • j,. ,,, Λ. r ^ - volatilization. in the first stage of the procedure for the replacement and / or Incomplete combustion resulting gases to conventional fuel is adjusted and regulated. 9. The method according to any one of claims 1 to 7, characterized in that in particular within the second process stage the combustion chamber, by measuring the temperature and / or determining the heating state of the raw materials to be burned, preferably by determining the degree of deacidification, at the end of the calcination zone of the combustion chamber (especially at tVärrnetauschöfen and Lepolöfen in the furnace inlet) the ratio of in the first process stage in the decomposition and / or incomplete combustion to conventional gases Fuel is adjusted and regulated. lo. Method according to one of Claims 1 to 9, characterized Volatilization, characterized in that the / decomposition and / or incomplete Incineration of waste materials in the first process 809818/0955 pyrolysis residues at least partially Aucgangsxohstoff s for the building materials, especially binders, are added in the second process stage heated, in particular fired. 11. The method according to any one of claims 1 to lo, characterized Volatilization, characterized in that the / decomposition and / or incomplete Incineration of the waste materials in the first process stage as additional pyrolysis residues Additives in the production of hydraulic binders, especially cement with additives, mixed binders, plaster and wall ties, mason jars, whitish lime containing pulp or hydraulic liming, ready-made plasters, plasters containing gypsum or binders, etc. and / or as an additive to dex Vexaxbeitung these binders are added. 12. Provision for the implementation of the Vexfahxens after a dex claims 1 to 11, marked duxch a possibly provided with a heat supply device (3), first exheating device (1) ζux / decomposition and / odex incomplete Discrimination of waste materials with bxennbaxen components, a second exheating device (2), in particular a furnace, and a first line (4) for discharge the gases generated in the most exheating exposure (1), with a second heating device inside (2) anoxdneten Brennex (5) is veibunden, possibly one second line (6) for feeding the conventional fuels into the second heating device (2), and optionally a, preferably discontinuously working, in or on dex eisten Exhitzungseinxichtüng (1) anoxdnetauseinxichtung (8) to remove dex when heating dex waste materials pyiolysis residues. 809818/0955 13. The device according to claim 12, characterized in that . . Volatilization,. that the first heating device (1) for / decomposition and / or incomplete incineration of waste materials as a shaft furnace, Rotary kiln, vortex oven, deck oven, roasting oven or is designed as a sintered belt. 14. Apparatus according to claim 12 or 13, characterized in that in the second line (6) for supplying the conventional fuels in the second heater (2) one by a temperature measuring device (lo, loa) and / or one Device (lo, loa) for recording the heating state of the raw materials subjected to heating, if necessary A flow control device that can be influenced via a line (12) (11) is arranged. 15. Device according to one of claims 12 to 14, characterized in that the temperature measuring device (lo, loa) and / or the device (lo, loa) for detecting the heating state the raw materials subjected to heating, in particular a device for determining the degree of deacidification of these substances, at the end of the Kalziniexzone, in particular at ■ / heat exchanger furnaces and Lepol furnaces in the furnace inlet. 16. Device according to one of claims 12 to 15, characterized in that the first line (4) for discharge of the gases produced in the first heating device (1) with the second line (6) for supplying the conventional Fuels before they flow into the burner (7) or in Burner (7) itself, in particular at the burner nozzle, are brought together. • 8 09818/0955