EP0308669A1 - Procédé pour utiliser une matière de base contenant de l'hydrocarbure halogéné - Google Patents

Procédé pour utiliser une matière de base contenant de l'hydrocarbure halogéné Download PDF

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Publication number
EP0308669A1
EP0308669A1 EP88113743A EP88113743A EP0308669A1 EP 0308669 A1 EP0308669 A1 EP 0308669A1 EP 88113743 A EP88113743 A EP 88113743A EP 88113743 A EP88113743 A EP 88113743A EP 0308669 A1 EP0308669 A1 EP 0308669A1
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EP
European Patent Office
Prior art keywords
heavy oil
pyrolysis
fluidized bed
starting material
oil
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP88113743A
Other languages
German (de)
English (en)
Inventor
Monika Dr. Betz
Beatrix Bäuml-Klott
Hinrich Dr.Rer.Nat Timmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ABB AG Germany
ABB AB
Original Assignee
Asea Brown Boveri AG Germany
Asea Brown Boveri AB
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asea Brown Boveri AG Germany, Asea Brown Boveri AB filed Critical Asea Brown Boveri AG Germany
Publication of EP0308669A1 publication Critical patent/EP0308669A1/fr
Withdrawn legal-status Critical Current

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    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/40—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by heating to effect chemical change, e.g. pyrolysis
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20—Organic substances
    • A62D2101/22—Organic substances containing halogen
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20—Organic substances
    • A62D2101/28—Organic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2203/00—Aspects of processes for making harmful chemical substances harmless, or less harmful, by effecting chemical change in the substances
    • A62D2203/10—Apparatus specially adapted for treating harmful chemical agents; Details thereof

Definitions

  • the invention relates to a process for utilizing halogenated hydrocarbons, in particular starting material containing chlorinated hydrocarbons, in particular waste oil, oil distillation residue, oil sludge, water-oil mixtures, oil-containing residue or the like.
  • the invention is therefore based on the object of specifying a simple and inexpensive process for recycling halogenated hydrocarbons, in particular liquid or semi-solid to solid starting material containing chlorinated hydrocarbons, of the type mentioned at the outset.
  • the starting material containing halogenated hydrocarbons is introduced in a pumpable state into an indirectly heated fluidized bed and is pyrolytically decomposed in the presence of at least one basic additive in a reducing atmosphere at a temperature of 400 to 900 ° C, and that the pyrolysis gas formed passed through at least one cooling stage and high-boiling hydrocarbon constituents of the pyrolysis gas are separated as heavy oil by partial condensation of the pyrolysis gas, and that the heavy oil is returned to the fluidized bed and subjected to pyrolysis again.
  • the weakly basic additive that is simultaneously introduced into the fluidized bed surprisingly at least partially dehalognizes the harmful components of the starting material that are considered to be very thermally stable, in particular polychlorinated dibenzodioxins (PCDDs), dibenzofurans (PCDFs) and biphenyls (PCBs).
  • PCDDs polychlorinated dibenzodioxins
  • PCDFs dibenzofurans
  • PCBs biphenyls
  • a particularly preferred embodiment of the invention is characterized in that the heavy oil is continuously returned to the fluidized bed. This ensures continuous operation without interruptions.
  • Another advantageous development of the invention consists in the fact that the heavy oil obtained is stored and that after the attack a sufficient amount of heavy oil is introduced into the fluidized bed instead of the starting material in a pumpable state.
  • a sufficient amount of heavy oil expediently such an amount that is sufficient for the operation of the plant of at least 3 hours, has been generated and stored, the supply of the starting material to the fluidized bed is interrupted.
  • the heavy oil is introduced into the fluidized bed and subjected to the same pyrolytic treatment as the starting material.
  • the added aggregate binds the further or the remaining portion or traces of hydrogen halide that are still organically bound in the heavy oil.
  • the pyrolysis gas formed in this way is then further treated as described above.
  • the heavy oil that may be obtained and cleaned by pyrolysis is collected for itself, because it is largely free of halogenated hydrocarbon compounds and is therefore particularly suitable for further processing.
  • the system is switched back to operating with raw material and the process described above begins again.
  • the procedure described above is called discontinuous recycling of the heavy oil.
  • halogenated hydrocarbon-free starting material also has to be used, this can advantageously be done by introducing this halogenated hydrocarbon-free starting material into the fluidized bed together with the heavy oil for pyrolytic decomposition in the discontinuous procedure. As a result, recycling of the halogen-free hydrocarbon starting material is achieved without great effort.
  • At least one metal oxide and / or one metal carbonate is used as the basic additive, since these weakly basic additives are sufficient for binding the pollutants and are inexpensive to obtain.
  • the corresponding compounds of the alkali and alkaline earth metals preferably calcium oxide, calcium carbonate, magnesium carbonate or calcium magnesium carbonate, are introduced into the fluidized bed as the metal oxide or metal carbonate.
  • These substances are expediently introduced into the fluidized bed in granular form, the grain size being in particular 0.2 to 10 mm.
  • a fine-grained fluidizing material expediently sand or aluminum oxide with a grain size of at most 0.5 mm, is usually used for the formation of the fluidized bed.
  • a granular carrier material is used as the vortex material, which is loaded with the metal oxide or metal carbonate.
  • the grain size of the carrier material is preferably at most 0.5 to 10 mm.
  • the carrier material as such preferably consists of amorphous silicates, zeolites or ceramic material.
  • the fluidized bed In order to be able to supply the fluidized bed with as much heat as possible in the unit of time with the aim of achieving a high mass throughput of starting material and / or heavy oil, it is expedient to indirectly heat the fluidized bed by means of gas-fired heating pipes.
  • the pyrolysis gas generated is preferably used as the gas.
  • the standing pyrolysis reactor 10 has a circular cylindrical upper region 12 and a circular conical region 14 which adjoins and tapers downwards.
  • the fluidized bed 16 is formed in this pyrolysis reactor 10 in such a way that a free gas space 18 remains above the fluidized bed, the height of which is approximately 10 to 20% of the height of the pyrolysis reactor.
  • the fluidized material with which the fluidized bed is formed is fine-grained and expediently consists of sand, aluminum oxide or carrier material.
  • a storage container 20 is arranged, into which the granular metal oxide and / or metal carbonate, which serves as an additive for the dehalogenation, is introduced through the pipeline 22 with the shut-off element 24 inserted.
  • the storage container 20 is connected by a line 26 with an inserted shut-off and throttle element 28 with a gradient to the fluidized bed 16 of the pyrolysis reactor.
  • a discharge line 32 is connected to the pyrolysis reactor 10, into which a throttle and shut-off device 34 is inserted.
  • At least one gas-fired heating tube 36 is inserted horizontally or vertically into the fluidized bed from the outer space 38.
  • this heating tube is connected to the pyrolysis gas line 40, which carries pyrolysis gas generated in the system.
  • a supply line 42 for combustion air and an exhaust line 44 for the discharge of the exhaust gas into the outside are connected to the heating pipe 36.
  • Eddy gas lines 46 which are connected to the gas line 48, open into the circular conical region 14 of the pyrolysis reactor.
  • the gas line 48 itself is connected to the pyrolysis gas line 40 with the interposition of a shut-off and throttling element 50.
  • the pipeline 52 also opens, which starts from the bottom region of a container 54, a pump 56 and a throttle and shut-off device 58 being inserted into the pipeline 52 one behind the other, as seen in the flow direction.
  • the container 54 serves to receive the starting material provided for the pyrolysis, which is introduced in the direction of arrow 60 from above into the closed container by suitable means.
  • a heating device 62 which is expediently designed in the form of a heating coil.
  • a heat transfer medium, preferably steam, is supplied or discharged through the connections 64 of the heating coil.
  • An electrically or gas-heated heating coil can also be used advantageously.
  • a single pipeline 52 is shown, but several pipelines are advantageously introduced into the pyrolysis reactor evenly distributed over the cross section and connected to the container 54 via the shut-off and throttle element 58 and the pump 56.
  • a spray nozzle 53 is advantageously arranged, the spray direction of which points into the fluidized bed 16, preferably upwards.
  • a raw gas line 78 leads from the gas space 18 of the pyrolysis reactor to the cooling stage 80, a cyclone separator 82 being inserted into the raw gas line.
  • the cooling stage 80 works with direct cooling and has a cooler 84 on.
  • the raw gas line 78 opens into the upper region of a vertical, circular-cylindrical cooling channel 75 of the cooler 84.
  • a closed separating container 86 is connected to the lower end of the cooling channel 75.
  • the lower area of the separating container serves as space 88 for the heavy oil, the remaining free space above serves as gas space 90.
  • a line 92 with an inserted shut-off device is connected to the space 88 near its bottom, which is used to empty the separating container 86 and, if necessary, for removal excess heavy oil is used.
  • a line 77 is connected at the bottom, which leads to at least one spray nozzle 79 leading in the upper end region of the cooling channel 77.
  • the spray nozzle is arranged in the center of the cooling channel, its spray direction is vertically downwards.
  • a pump 81 and a cooler 83 are inserted into line 77 and are supplied with cooling medium, preferably cooling water, through lines 85.
  • a line 55 is also connected to space 88 below, into which, starting from space 88, a pump 59 and a shut-off and control element 57 are inserted.
  • the line 55 leads to the pipeline 52 and is connected there downstream of the shut-off and control element 58. It is also advantageous to have the line 55 open into the container 54. This is indicated in FIG. 1 by the line 61 shown in broken lines. In this case there is no connection to the pipeline 52.
  • a pipeline 98 leads from the gas space 90 of the cooling stage 80 to the entrance of a further cooling stage 100 which works with indirect cooling.
  • the further cooling stage 100 has a standing, circular-cylindrical further cooler 102, at the upper end of which the pipeline 98 and at the lower end of which a further separation container 104 is connected.
  • the lower space of the further separation container has a further space 106 for receiving the condensate obtained in the form of low-boiling pyrolysis oil, above which there is another gas space 108.
  • a cooling coil 112 is provided, through which a cooling medium, preferably water, is passed.
  • the starting material which consists in particular of the substances or mixtures of these substances mentioned at the outset, is introduced into the container 54 in the direction of the arrow 60.
  • hot water or steam is passed through the coil of the heating device 62 and the starting material, which is usually viscous or semi-solid to solid, is heated to such an extent that it is thin and pumpable, that is to say that it is pumped 56 easily conveyed and sprayed in the flushing nozzle 53 without difficulty.
  • the temperature at which this is the case, depending on the starting material is usually between 50 and 150 ° Celsius.
  • the pumpable starting measure material is then introduced with the help of the pump 56 through the pipeline 52 into the pyrolysis reactor.
  • the flow of the starting material through the shut-off and throttle member 58 is adjusted to the appropriate level.
  • the liquid starting material is sprayed into the fluidized bed 16 through the spray nozzle 53.
  • the starting material is expediently sprayed through several lines and spray nozzles.
  • the heavy oil collecting in the room 88 is pumped by means of the pump 59 with the shut-off and regulating element 57 open sufficiently through the line 55 into the line 52 or into the container 54, so that the heavy oil together with the Starting material is introduced into the fluidized bed 16. It should be noted here that as much heavy oil remains in room 88 as is necessary for the operation of cooling stage 80.
  • the fluidized material introduced into the pyrolysis reactor is swirled using pyrolysis gas.
  • the pyrolysis gas is removed from the pyrolysis gas line 40 through the fluidizing gas lines 46 and the gas line 48.
  • the flow of the fluidizing gas through the shut-off and throttle member 50 is set to the required level.
  • pyrolysis gas is likewise fed from the pyrolysis gas line 40 to the heating tube 36 and burned, the gas flow through the shut-off and throttle element 45 being adjusted to the heating power of the heating tube 36.
  • Combustion air is supplied to the heating pipe 36 through the supply line 42, and the exhaust gases are passed through the exhaust line 44 into the outer space 38, advantageously with the aid of a fireplace, not shown.
  • the fluidized bed is indirectly heated by the heating tube 36 to the temperature of 400 to 900 ° Celsius required for the pyrolysis. Several heating pipes are advantageously provided.
  • the mixture of heavy oil and sprayed-in starting material mixes with the additive supplied from the storage container 20 while heating to the intended pyrolysis temperature. Since this takes place in a reducing atmosphere, the starting material is thermally decomposed to form pyrolysis gas, which collects in the gas space 18, whereas the pyrolysis residues are drawn off through the discharge line 32.
  • the harmful constituents of the supplied material are dechlorinated with the aid of the additives and there are largely landfill-capable compounds which are then discharged from the pyrolysis reactor together with the pyrolysis residue through the discharge line 32.
  • the unpurified pyrolysis gas is fed to the cooling stage 80 at approximately the pyrolysis temperature by the cyclone separator 82, in which entrained solids are separated.
  • pumpable heavy oil is removed from the space 88 and conveyed into the cooling channel 75 by the pump 81 and the cooler 83 and sprayed through the spray nozzle 79.
  • the pyrolysis gas is introduced into the cooling channel, so that it, together with the sprayed heavy oil, goes down to the bottom separator tank 86 flows.
  • the hot pyrolysis gas is cooled to a temperature of approximately 150 to 250 ° C. by direct heat exchange with the supplied, colder heavy oil.
  • the pyrolysis gas collecting in the gas space 90 is fed through the pipeline 98 to the further cooling stage 100.
  • the pyrolysis gas flows downward in the further cooler 102, the pyrolysis gas is cooled by the further cooling coil 112. Cooling water serves as the cooling medium.
  • partial condensation of hydrocarbon fractions of the pyrolysis gas easily results boiling pyrolysis oil (boiling point approximately 80 to 110 ° C), which separates from the pyrolysis gas in the further separation container 104.
  • the low-boiling pyrolysis oil collects in the further space 106 and is removed through the further line 110 for further processing. Its temperature is between 20 and 60 ° Celsius, the pyrolysis gas, which collects in the further gas space 108, has the same temperature.
  • the low-boiling pyrolysis oil is largely free of the pollutants mentioned above and is sent for further processing.
  • the cooled pyrolysis gas is discharged from the further gas space 108 to the pyrolysis gas line 40 and brought to the pressure required by the compressor 114 for the generation of the fluidized bed and the supply of the gas burner 72 and the heating tube 36.
  • the pyrolysis gas not required for the operation of the pyrolysis system is taken through line 116 of the pyrolysis gas line 40 and used as an energy source, for. B. used for heating living spaces.
  • the pyrolysis gas is now free of the pollutants mentioned at the beginning.
  • the starting material containing halogen, in particular chlorinated hydrocarbons is pyrolyzed in a very simple manner, the addition of the additives from the storage container 20 preventing or at least largely preventing the formation of toxic decomposition products such as polychlorinated biphenyls, dioxins and furans.
  • the return of the heavy oil to the fluidized bed for pyrolysis is of particular importance.
  • the heating of the starting material in the container 54 to the point of pumpability allows the starting material to be introduced into the fluidized bed in a very simple manner and to be distributed evenly there.
  • FIG. 2 shows an embodiment variant of the system according to FIG. 1.
  • the individual components in FIG. 2 are provided with reference numerals only to the extent that this is necessary for understanding.
  • Components in FIG. 1, which are also present in FIG. 2 are provided in FIG. 2 with reference numerals that are 200 times larger than the reference numerals in FIG. 1.
  • the pyrolysis plant according to FIG. 2 has a collecting container 118 which is arranged below the separating container 286 of the cooling stage 280.
  • the bottom region of the separating container 286 is connected to the upper region of the collecting container 118 by a line 120 with an inserted flow control element 122.
  • a shut-off device 123 is also inserted.
  • a pipeline 124 leads from the lower region of the collecting container 118 to the pipeline 252, which connects the container 254 to the pyrolysis reactor 210.
  • the pipe 124 is connected downstream of the shut-off and throttling member 258 to the pipe 252.
  • a pump 126 and a shut-off and throttle element 128 are also inserted one after the other into the pipeline 124, as seen in the direction of flow.
  • a heater 130 in the form of a heating coil is provided in the collecting container 118, through which, if necessary, a liquid heat transfer medium, preferably hot water or steam, is passed.
  • a level controller 287 is connected to the separating tank 286 and is operatively connected to the flow control member 122 through a control line 289.
  • the level controller ensures that there is always as much heavy oil in the separating tank 286 as is necessary for cooling the pyrolysis gas in the cooling channel 275.
  • the level controller 287 opens the flow control element 122 and this excess heavy oil which is produced flows into the collecting container 118.
  • the throttle and shut-off device 128 is closed, the pump 126 is at rest and the shut-off device 123 is opened.
  • the starting material containing hydrogen halide is then introduced in the direction of arrow 260 into the closed container 254 and heated by the heater 262 to such an extent that the starting material is flowable and pumpable.
  • the further process sequence is now similar to the exemplary embodiment according to FIG. 1. Accordingly, the starting material from the container 254 is introduced into the fluidized bed 216 of the pyrolysis reactor 210. At the same time, aggregate from the storage container 220 is introduced into the fluidized bed. The fluidized bed is heated by the heating tube 236 to a temperature of 400 to 900 ° Celsius and the starting material is thermally decomposed in the fluidized bed in a reducing atmosphere. At the same time, pollutants are bound.
  • the pyrolysis gases produced are led to cooling stage 280, where they are cooled by direct cooling to a temperature of 120 to 250 ° Celsius.
  • the heavy oil condensing here is passed through the separating tank 288 and the line 120 into the collecting tank 118.
  • the level controller 287 in conjunction with the flow control member 122 ensures that there is always a sufficient amount of heavy oil for the direct cooling of the pyrolysis gas in the separating tank 286 and only the excess of heavy oil in the collecting tank 118 flows.
  • the cooled pyrolysis gas is fed to the further cooling stage 300 and cooled to a temperature of 20 to 60 ° Celsius.
  • the low-boiling pyrolysis oil obtained here is collected in the separating tank 304, while the pyrolysis gas is fed to the pyrolysis gas line 240 for supplying the pyrolysis system and for further use.
  • the shut-off device 123 Since the shut-off device 123 is open, the heavy oil flows from the separating tank 286 into the collecting tank 118 and is stored there.
  • the size of the collecting container 118 is preferably selected so that it can hold the heavy oil accumulating during an operating period of approximately 2 to 8 hours.
  • the collecting container 118 is largely filled with heavy oil, the supply of starting material containing hydrogen halide compounds into the container 254 is interrupted.
  • the pump 256 is switched off, the throttle and shut-off device 258 and the shut-off device 123 are closed.
  • the pump 126 is then started up and the throttle and shut-off device 128 is opened sufficiently. If the heavy oil stored in the collecting container 118 is not pumpable, the heavy oil is heated with the aid of the heater 130 until it is flowable and pumpable.
  • the heavy oil stored in the collecting container 118 is fed to the fluidized bed 216.
  • the heavy oil is subjected to a further pyrolysis under the same conditions as the starting material.
  • This has the advantage that traces or residues of halogen, preferably chlorinated hydrocarbon compound dung that was not fully bound by the aggregates during the pyrolysis of the starting material and got into the heavy oil, is now bound.
  • the pyrolysis gas formed in the pyrolysis reactor is passed through the cooling stages 280 and 300, as described in connection with FIG. In the cooling stage 280, a heavy oil which is at least largely free of hydrogen halide compounds is obtained.
  • shut-off and throttle element 128 is closed, the shut-off element 123 and the throttle and shut-off element 258 are opened, the pump 126 is shut down and the pump 256 is started up again.
  • the system is now ready to process starting material containing halogenated hydrocarbons until the collecting container 118 is filled with heavy oil again. Then the process described above begins again.
  • the plant according to FIG. 2, which is operated as described above for the alternate pyrolysis of starting material or heavy oil (discontinuous recirculation of the heavy oil), can advantageously also be used for continuous recirculation of the heavy oil into the fluidized bed or for the pyrolysis of excess heavy oil alone.
  • FIG. 3 shows an embodiment variant of the plant according to FIG. 2. This embodiment variant is intended for the additional utilization of starting material free from halogenated hydrocarbons.
  • the main raw material to consider as a hydrogen halide is raw material of the type mentioned at the beginning, as well as some plastics that are to be used here in the form of plastic waste.
  • FIG. 2 The components of FIG. 2, which recur in identical form in FIG. 3, are provided with reference numbers which are enlarged by the amount 400 compared to FIG.
  • the differences between the plant according to FIG. 3 and the plant according to FIG. 2 essentially consist in the fact that the plant according to FIG. 3 is additionally provided with a second container 135 for liquid to semi-solid starting material free from halogen hydrogen.
  • the second container 135 is connected by a line 137 with an inserted pump 139 and a downstream shut-off and throttle element 141 to the pipeline 652, which leads from the container 654 to the fluidized bed 616.
  • the line 137 is connected downstream of the shut-off and throttle element 658, which is located in the pipeline 652.
  • the closed second container 135 is provided with a heater 143 just like the container 654.
  • the halogen-free hydrocarbon starting material is introduced into the second container 135 in the direction of the arrow 145 and is brought into a pumpable state by the heater 143.
  • the prerequisite here is that the starting material can be brought into the pumpable state by heating.
  • This starting material preferably consists of waste oil or semi-solid to solid oil-like products.
  • This halogenated hydrocarbon-free starting material now flows under the influence of the pump 139 through the line 137 with the shut-off and throttle element 131 open to the line 652 and mixes there with the heavy oil containing pollutants, which is conveyed from the collecting container 518 through the line 524 to the pipeline 652.
  • This mixture is now introduced into the fluidized bed 616 and subjected to pyrolysis, the traces or residues of halogenated hydrocarbon compounds which are still present in the polluting heavy oil being chemically bound. This is done with the help of the additives mentioned above, which are introduced from the storage container 620 into the fluidized bed 616. Because the feedstock from the container 135 is free of halogenated hydrocarbon compounds, the pollutant binding is concentrated on those halogenated hydrocarbons that are present in the heavy oil of the collecting container 518. These halogenated hydrocarbons, which are gaseous in the fluidized bed, are now largely bound to the landfill-compatible, non-toxic residue by the additive and removed from the pyrolysis reactor by the discharge line 632.
  • the pyrolysis gases formed are therefore practically free of hydrogen halide gases and are then fed to cooling stages 680 and 700 in the manner described above.
  • a heavy oil is now produced in the separating container 686, which is largely free from contamination by halogenated hydrocarbons and which is referred to as a low-pollutant heavy oil.
  • This pyrolytically cleaned, low-pollutant heavy oil is then drawn off from the separating container 686 through the line 692 and fed to a further utilization.
  • the heavy oil is advantageously subjected to pyrolysis several times.
  • the process described above has the essential advantage that, in addition to pyrolytic work-up of the pollutant-containing heavy oil, the off in cooling stage 680 in the pyrolysis of halogenated hydrocarbon compounds initial material is obtained, at the same time raw material is processed that is free of hydrogen halide compounds. This measure considerably increases the usability, utilization and economy of the method according to the invention.
  • Figure 4 shows the detail IV of Figure 3 as a variant.
  • the individual parts of FIG. 3 that recur identically in FIG. 4 are provided with reference numerals, which are enlarged by an amount of 100 compared to FIG.
  • an insertion device 147 is provided instead of the second container 135 together with line 137, through which solid, halogenated hydrocarbon-free starting material is introduced into the fluidized bed 716.
  • the entry device 147 has a horizontally arranged entry screw 149 which is driven by a motor 151.
  • the feed screw is provided with an inlet lock (not shown) and an indicated funnel 153, into which the solid, small-sized halogenated hydrocarbon-free starting material is poured and then introduced into the fluidized bed 716 in solid form by the feed screw.
  • the pollutant-containing heavy oil is introduced in a pumpable state through line 624 into fluidized bed 716 and is sprayed there with the aid of nozzle 753.
  • the input device 147 introduces the solid, halogen-free hydrocarbon starting material into the fluidized bed 716, so that both are simultaneously pyrolyzed.
  • the operation of the pyrolysis plant according to FIG. 4 proceeds exactly as it was explained above, so that no further explanations are required for the person skilled in the art.
  • the main raw material used for the operation of the pyrolysis plant according to FIG. 3 is halogenated hydrocarbon-free, waste oils, oil sludges and the like which are free of pollutants.
  • the pyrolysis plant according to FIG. 4 is suitable for the processing of solid, small pieces of halogenated hydrocarbon-free starting material which cannot be brought into the pumpable state or only with great difficulty. Some plastics can be considered as such a material.

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EP88113743A 1987-08-29 1988-08-24 Procédé pour utiliser une matière de base contenant de l'hydrocarbure halogéné Withdrawn EP0308669A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE3728870 1987-08-29
DE3728870 1987-08-29
DE3739171 1987-11-19
DE3739171 1987-11-19

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EP0308669A1 true EP0308669A1 (fr) 1989-03-29

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0371201A1 (fr) * 1988-12-01 1990-06-06 Ruhrkohle Aktiengesellschaft Procédé d'hydrogénation des composés organochlorés et de neutralisation du gaz chlorhydrique en résultant ainsi qu'un agent de neutralisation pour le gaz chlorhydrique résultant des composés organochlorés
DE19517096A1 (de) * 1995-05-10 1996-11-14 Daniel Engelhardt Zeolithkatalysierte Pyrolyse von Kunststoffen
WO1997027273A1 (fr) * 1996-01-26 1997-07-31 Heshui Yu Procede et dispositif pour le traitement des huiles usees
US5707592A (en) * 1991-07-18 1998-01-13 Someus; Edward Method and apparatus for treatment of waste materials including nuclear contaminated materials
US6132596A (en) * 1997-01-24 2000-10-17 Yu; Heshui Process and apparatus for the treatment of waste oils
EP1224956A2 (fr) * 1995-03-22 2002-07-24 NKT Research Center A/S Méthode de traitement des déchets contenant de l halogène

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4364796A (en) * 1980-01-18 1982-12-21 Seiichi Ishizaka, President Of Agency Of Industrial Science And Technology Method and system for disposing pyrolysis gas
EP0167702A1 (fr) * 1984-06-08 1986-01-15 Krupp Koppers GmbH Procédé pour le traitement ultérieur d'un gaz provenant de la pyrolyse de déchets
US4588477A (en) * 1984-05-11 1986-05-13 Habib Ikram W Traveling fluidized bed distillation of scrap tires and rubber vulcanizate
DE3443722A1 (de) * 1984-11-30 1986-06-12 Foerster Guenther Verfahren zur thermischen beseitigung von halogenverbindungen, insbesondere dioxine, phosgen und polychlorierte biphenyle bildende chlorverbindungen enthaltenden abfaellen sowie wirbelschicht-reaktor zu seiner durchfuehrung
EP0226895A2 (fr) * 1985-12-23 1987-07-01 Asea Brown Boveri Aktiengesellschaft Procédé d'amélioration pyrolytique de matériaux de départ

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4364796A (en) * 1980-01-18 1982-12-21 Seiichi Ishizaka, President Of Agency Of Industrial Science And Technology Method and system for disposing pyrolysis gas
US4588477A (en) * 1984-05-11 1986-05-13 Habib Ikram W Traveling fluidized bed distillation of scrap tires and rubber vulcanizate
EP0167702A1 (fr) * 1984-06-08 1986-01-15 Krupp Koppers GmbH Procédé pour le traitement ultérieur d'un gaz provenant de la pyrolyse de déchets
DE3443722A1 (de) * 1984-11-30 1986-06-12 Foerster Guenther Verfahren zur thermischen beseitigung von halogenverbindungen, insbesondere dioxine, phosgen und polychlorierte biphenyle bildende chlorverbindungen enthaltenden abfaellen sowie wirbelschicht-reaktor zu seiner durchfuehrung
EP0226895A2 (fr) * 1985-12-23 1987-07-01 Asea Brown Boveri Aktiengesellschaft Procédé d'amélioration pyrolytique de matériaux de départ

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0371201A1 (fr) * 1988-12-01 1990-06-06 Ruhrkohle Aktiengesellschaft Procédé d'hydrogénation des composés organochlorés et de neutralisation du gaz chlorhydrique en résultant ainsi qu'un agent de neutralisation pour le gaz chlorhydrique résultant des composés organochlorés
US5015457A (en) * 1988-12-01 1991-05-14 Ruhrkohle Ag Process for the hydrogenation of organochlorine compounds, neutralization of the hydrochloric acid obtained and a neutralization agent for hydrochloric acid obtained from organochlorine compounds
US5707592A (en) * 1991-07-18 1998-01-13 Someus; Edward Method and apparatus for treatment of waste materials including nuclear contaminated materials
EP1224956A2 (fr) * 1995-03-22 2002-07-24 NKT Research Center A/S Méthode de traitement des déchets contenant de l halogène
EP1224956A3 (fr) * 1995-03-22 2003-05-28 NKT Research Center A/S Méthode de traitement des déchets contenant de l halogène
DE19517096A1 (de) * 1995-05-10 1996-11-14 Daniel Engelhardt Zeolithkatalysierte Pyrolyse von Kunststoffen
WO1997027273A1 (fr) * 1996-01-26 1997-07-31 Heshui Yu Procede et dispositif pour le traitement des huiles usees
AU719165B2 (en) * 1996-01-26 2000-05-04 Heshui Yu Process and apparatus for the treatment of waste oils
CN1074454C (zh) * 1996-01-26 2001-11-07 余河水 废油处理的方法和装置
US6132596A (en) * 1997-01-24 2000-10-17 Yu; Heshui Process and apparatus for the treatment of waste oils

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