EP0305847B1 - Procédé pour l'utilisation pyrolytique d'un résidu de distillation - Google Patents

Procédé pour l'utilisation pyrolytique d'un résidu de distillation Download PDF

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Publication number
EP0305847B1
EP0305847B1 EP88113623A EP88113623A EP0305847B1 EP 0305847 B1 EP0305847 B1 EP 0305847B1 EP 88113623 A EP88113623 A EP 88113623A EP 88113623 A EP88113623 A EP 88113623A EP 0305847 B1 EP0305847 B1 EP 0305847B1
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EP
European Patent Office
Prior art keywords
pyrolysis
distillation residue
fluidized bed
process according
gas
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EP88113623A
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German (de)
English (en)
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EP0305847A1 (fr
Inventor
Walter Prof. Dr. Kaminsky
Uwe Steffensen
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ABB AG Germany
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Asea Brown Boveri AG Germany
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/28—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid material
    • C10G9/32—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid material according to the "fluidised-bed" technique
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/02—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by distillation

Definitions

  • the invention relates to a process for the pyrolytic utilization of distillation residue, which is obtained in the thermal processing of waste oil and / or waste oil.
  • waste oils or waste oils From the internal state of the art it is known to subject waste oils or waste oils to chemical pretreatment and then to send them to fractional distillation.
  • the chemical pretreatment binds the pollutants present in the waste oil, and fractional distillation produces valuable, usable oils.
  • the residues from distillation, which are viscous or semi-solid to solid at ambient temperature, are pyrolytically decomposed.
  • the pyrolysis gas obtained in this way is preferably used as a heating gas for the fractional distillation, the pyrolysis oils formed are further processed or fed to the fractional distillation together with the waste oil.
  • the object of the invention is to specify a method of the type mentioned at the outset with which the distillation residues obtained can be processed in a simple and inexpensive manner.
  • the process should be trouble-free and easily adaptable to the consistency of the distillation residues.
  • the solution to this problem is that the distillation residue is in a flowable state, but at most with a limit temperature which is below the coking temperature of the distillation residue and has a safety margin from the coking temperature and is shielded against further heating in a pyrolysis reactor which exceeds the limit temperature introduced and subjected to pyrolysis in a fluidized bed heated indirectly to 400 to 900 ° C.
  • the distillation residue is therefore expediently brought into a flowable and pumpable state by heating, the degree of heating being selected in particular depending on the consistency and composition of the distillation residue.
  • the flowable distillation residue must not exceed a temperature above which the distillation residue tends to coke. Coking would make it very difficult or impossible to introduce the distillation residue into the pyrolysis reactor.
  • the distillation residue may only be heated up to a limit temperature that is a safe distance from the coking temperature.
  • the flowable distillation residue is shielded against unwanted further heating.
  • Adhesion is prevented by the fluidizing gas required for the formation of the fluidized bed entraining the suddenly evaporated distillation residue before coking and bonding of the fluidized bed occurs.
  • the fluidized bed is expediently formed by the intermingling of fine-grained fluidizing material, in particular sand, aluminum oxide or coke.
  • the coking temperature of the distillation residue varies depending on its composition. It is best determined by experiment. A safety distance is chosen as the limit temperature of the distillation residue, which is at least about 50 ° C lower than the coking temperature of the distillation residue.
  • the coking temperature of the distillation residue is generally dependent on the content of multinuclear aromatic hydrocarbon compounds in such a way that, in the case of a distillation residue with a low content of these hydrocarbon compounds, the coking temperature is higher than with a high content of polyaromatic hydrocarbon compounds.
  • the distillation residue of highly aromatic oils e.g. obtained from coal can have a coking temperature of approximately 350 ° C in the presence of metal parts.
  • the distillation residue of paraffin-rich oils, e.g. extracted from petroleum has a coking temperature of approximately 400 ° C or above.
  • the coking temperature is understood to be the temperature at which high-molecular hydrocarbon compounds crack into a carbon skeleton. This carbon structure (coke) occurs in solid or semi-solid form and leads to constrictions and blockages in pipes and pumps.
  • the distillation residue is expediently heated to the limit temperature and introduced at this temperature into the pyrolysis reactor. Because by preheating, the further heating of the distillation residue to pyrolysis temperature in the pyrolysis reactor is greatly facilitated and accelerated, so that its evaporation and decomposition takes place suddenly in the fluidized bed.
  • the process according to the invention achieves trouble-free pyrolysis with a high mass throughput.
  • the fluidized bed is heated by at least one gas-fired jet heating tube, in particular a jacket jet tube. Since these jacketed radiant heating tubes, which are known per se, reach temperatures of around 1000 to 1100 ° C., the distillation residue supplied is heated rapidly, even with a high throughput of distillation residue. Pyrolysis gas obtained from pyrolysis is advantageously used for heating the jacket radiant tubes.
  • distillation residue is introduced into the fluidized bed in a finely divided form.
  • the distillation residue is sprayed into the fluidized bed with the aid of at least one spray nozzle shielded from thermal insulation.
  • the insulation here advantageously consists of a layer of porcelain applied to the spray nozzle.
  • distillation residue is introduced into that region of the fluidized bed in which the fluidizing gas required for the formation of the fluidized bed is introduced into the pyrolysis reactor.
  • the process according to the invention is very preferably used to utilize the distillation residue which arises in the processing of waste oil or waste oil containing chlorine compounds, the chlorine compounds being converted into sodium chloride by metallic sodium before the fractional distillation of the waste oil or waste oil.
  • the pyrolysis plant has a standing, circular-cylindrical pyrolysis reactor 10.
  • a horizontally extending nozzle base 12 is arranged, which has a plurality of uniformly distributed openings 14.
  • the distance between the nozzle base 12 and the lower end of the pyrolysis reactor is approximately 10 to 20% of its clear height.
  • the fluidized bed 16 forms above the nozzle base 12, a free space 18 remaining above the fluidized bed in which the pyrolysis gas collects.
  • the clear height of the free space 18 is approximately 15 to 25% of the clear height of the pyrolysis reactor 10.
  • the feed tube 20 for the flowable distillation residue opens into the fluidized bed 16.
  • the feed pipe runs approximately in the vertical longitudinal axis 22 of the pyrolysis reactor 10 and is guided from the outer space through the fluidizing gas space 24 arranged below the nozzle base 12 and through the nozzle base 12 into the fluidized bed 16.
  • the feed tube 20 protrudes into the fluidized bed 16 approximately to a length which corresponds to two to five times its diameter. Further explanations of the feed tube 20 are given in the explanation of FIG. It is advisable to provide several feed pipes evenly distributed over the bottom of the nozzle.
  • a pipeline 26 is connected to the lower end of the feed pipe 20 in the drawing and is connected to a standing, closed container 32 by inserting a throttling and shut-off valve 28 and a pump 30.
  • the container 32 is provided with thermal insulation 33 and is used to hold the distillation residue.
  • the container 32 is provided with a heater 34, which is expediently designed as a coil.
  • An electrical or gas-heated pipe coil is likewise expedient, pyrolysis gas being used as the heating gas.
  • the pyrolysis plant shown in FIG. 1 is operated in connection with a processing plant, the distillation residue is transported from the processing plant into the container 32. This is indicated by the dashed line 40 provided with an arrow, which connects the processing plant 42 shown schematically to the container 32.
  • the processing plant works according to a process which is described in the article "Cleaning with metallic sodium” in issue 21, page 184 of the "Chemische Rundschau" year 1986. Reference is expressly made here to the disclosure of this article.
  • the pyrolysis indicated in the circuit diagram of the article is carried out with the present inventive method. In this known method, the waste oil or waste oil is processed with finely divided metallic sodium. This makes it possible to separate organic chlorine compounds and other contaminants from the waste oil or waste oil.
  • a jacket radiant tube 44 is provided in the fluidized bed for heating the fluidized bed 16 to operating temperature.
  • This straight jacket radiant tube is inserted horizontally into the fluidized bed 16 from the outside and runs approximately halfway up the fluidized bed 16.
  • a plurality of jacket radiant tubes 44 are expediently provided. Since the jacket jet heating tube is fired with heating gas, a heating gas line 46 with an inserted throttle and shut-off element 48 is provided. The air required for the combustion is supplied through the air line 50. Further information on the jacket radiant tube is given in connection with the explanation of FIG. 6.
  • an overflow channel 54 running with a slope is connected, which opens into the upper area of a residue container 56.
  • the lower area of this residue container is provided with a discharge device 58, indicated in FIG. 1, which expediently has the shape of a discharge lock.
  • a line 60 is connected to the free space 18 of the pyrolysis reactor and, with the interposition of a throttle and shut-off element 62, is connected to a container 64 which serves to hold powdery additives.
  • the free space 18 is connected by a gas line 66 to the inlet of a cooler 68.
  • a cyclone separator 70 is inserted, the bottom with a line 72 including shut-off device 74 for the Removal of the separated solids is provided.
  • a line leads from the outlet of the cooler 68 to a separating container 76, which is provided for the separation of gaseous and liquid substances. While the liquid substances are drawn off through line 78 with the shut-off element 80 inserted, the separated gas is fed through line 82 to a second cooler 84, which is constructed similarly to cooler 68 a second separator tank 88, the structure and function of which is identical to that of the separator tank 76.
  • the gas separated in the second separating tank 88 is discharged into the pyrolysis gas line 90, into which a compressor 92 is inserted. Downstream of the compressor 92, the heating gas line 46 is connected to the pyrolysis gas line 90. Likewise, the fluidizing gas chamber 24 is connected to the pyrolysis gas line 90 downstream of the compressor 92 through the fluidizing gas line 94 with an inserted throttle and shut-off element 96.
  • a gas storage device 104 is connected to the pyrolysis gas line 90 upstream of the compressor 92 through a pipeline 106 with an inserted second compressor 108.
  • FIG 2 shows the area II, ie the area of the feed pipe 20 of Figure 1 as a detail and in a larger representation. Accordingly, the feed pipe 20 is guided from the outer space 110 through the fluidized gas space 24 and through an opening 112 of the nozzle base 12 into the fluidized bed 16 and opens there.
  • the feed tube 20 is concentrically surrounded by a protective tube 114.
  • the protective tube has a clear width that is approximately five to ten times the outer diameter of the feed tube 20.
  • the protective tube 114 is closed at its upper end with a circular disk 116 which abuts the nozzle base 12.
  • the feed tube 20 penetrates the circular disc 116.
  • the other end of the straight protective tube 114 is provided with a flange 118 which is fastened to the outside of the bottom 120 of the fluidizing gas space and carries the protective tube 114.
  • the protective tube is not closed in the region of the flange 118, so that its interior has a full cross section with the exterior 110.
  • the upper end of the feed pipe 20 is provided with a spray nozzle 122 which is surrounded by an insulating layer 124.
  • the spray nozzle is welded or screwed to the supply pipe.
  • the insulating layer reduces heat transfer from the fluidized bed 16 to the spray nozzle and is preferably made of porcelain.
  • Parts of the feed tube 20 which protrude into the fluidized bed are likewise provided with the insulating layer.
  • the entire feed tube 20 is expediently insulated from external heat in the region of the fluidizing gas space 24 with a further insulating layer 123.
  • the thickness of the porcelain insulation layers is approximately 2 to 4 cm.
  • Hard porcelain which contains a high proportion of feldspar or quartz and which is stable up to a temperature of approximately 800 ° C. is expediently used as the porcelain.
  • a porcelain such as is used in spark plugs of gasoline engines is advantageously used.
  • Figure 6 shows the jacket jet pipe 44 of Figure 1 in the central vertical section as a detail and in a larger representation.
  • the region of the casing tube 126 which projects into the fluidized bed 16 has a length which is approximately the same, five to four Twenty times its outside diameter.
  • the wall 128 itself is double-shelled and filled with an insulating material 132, expediently in the form of glass or rock wool. On the inside, the wall 128 is still insulated with a ceramic layer 129.
  • a guide tube 134 is arranged concentrically in the jacket tube 126 and runs at a distance from the jacket tube, so that a first annular channel 136 is formed.
  • the gas supply tube 138 runs concentrically and at a distance from the guide tube 134, so that a second annular channel 140 is formed.
  • the ring channels and the gas supply line end in the outer space 110.
  • the gas supply pipe 138 is connected to the heating gas line 46 for heating gas supply (cf. FIG. 1), the second ring channel 140 is connected to the air line 50 and the first ring channel 136 is connected to the exhaust gas line 142. All connections are in the outer space 110.
  • the guide tube 134 ends in front of the closed end 144 of the jacket tube 126 at a distance which is two to four times the inside width of the jacket tube 126.
  • the gas supply pipe 138 ends in front of the open end 146 of the guide pipe at a distance which is approximately two to four times the clear width of the guide pipe 134.
  • the end of the gas supply pipe 138 is provided with a gas nozzle 148.
  • the operation of the jacket radiant tube 44 proceeds as follows. Heating gas is passed through the heating gas line 46 and the gas supply pipe 138 to the gas nozzle 148 and enters the guide pipe 134 there. At the same time, air is introduced through the air line 50 into the second ring channel 140, where it flows to the open end 146.
  • the heating gas emerging from the gas nozzle 148 mixes with the supplied air, so that after ignition of the gas-air mixture, combustion takes place in the end region of the guide tube 134.
  • the hot flue gases pass from the guide tube 134 into the end region of the casing tube 126, are deflected there in the opposite direction and flow through the first ring channel 136 to the exhaust gas line 142, which conducts the exhaust gases into the outside space.
  • the jacket tube 126 is heated to a temperature of approximately 900 to 1100 ° C. by the combustion of the heating gas. Due to this high temperature, the heat transfer to the fluidized bed 16 is considerable. The heat transfer is approximately ten to twenty times that of heating pipes which are obtained from a heat transfer medium, e.g. hot gases that are heated.
  • a heat transfer medium e.g. hot gases that are heated.
  • the distillation residue which is preferably obtained in the waste oil treatment plant 42, is introduced into the container 32.
  • the distillation residue is usually semi-solid or viscous at ambient temperature.
  • the distillation residue is heated by the heater 34.
  • a hot heat transfer medium expediently steam, is guided through the coil of the heater 34 with the aid of the lines 36 and 38. The heating is carried out so far that the distillation residue becomes pumpable and flowable. It should be noted, however, that the coking temperature is not exceeded. Because at higher temperatures, the distillation residue tends to crack and excrete tar coke-like substances, which would lead to blockages in the pipes and to system malfunctions.
  • the distillation residue is preferably reduced to at most one Limit temperature heated, which is approximately 50 ° C below the coking temperature. This safety distance ensures that the coking temperature is not reached anywhere in the system.
  • the flowable distillation residue is expediently heated to the limit temperature if possible. This preheating facilitates and accelerates further heating to the pyrolysis temperature in the fluidized bed.
  • the flowable and pumpable distillation residue is then fed to the feed pipe 20 by means of the pump 30 and sprayed into the fluidized bed 16 through the spray nozzle 122.
  • the mass flow of the flowable distillation residue is adjusted to the required level by the throttle and shut-off device 28.
  • the pipeline 26 and the throttle and shut-off element 28 are first of all provided with heat-insulating insulation 150, which is indicated in FIG. 1. As a result, heating of the pipeline 26 by external heat sources, for example the pyrolysis reactor, is avoided. However, the introduction of the flowable distillation residue into the pyrolysis reactor requires special attention.
  • the feed tube 20 is surrounded by the protective tube 114 in the region of the pyrolysis reactor, as shown in FIG. 2. This avoids shielding against the effects of heat from the hot pyrolysis reactor.
  • the intermediate space 113 between the protective tube 114 and the feed tube 20 is connected to the outer space 110 only at its lower end, a resting, warm air layer is formed in the intermediate space 113, which has a heat-insulating effect. It is also expedient to provide the feed tube 20 with a heat-insulating porcelain layer in the area of the protective tube 114.
  • the spray nozzle 122 Since the spray nozzle 122 is directly exposed to the hot pyrolysis layer, the temperature of which is preferably 400 to 800 ° C., the spray nozzle 122 must also be protected against heating above the limit temperature.
  • the spray nozzle is provided with the insulating layer 124 made of ceramic, preferably porcelain (see FIG. 2). Parts of the feed pipe 20 which lead to the spray nozzle 122 and run in the fluidized bed must also be provided with the same insulating layer.
  • the flowable distillation residue is thus introduced into the pyrolysis reactor with shielding against external heat and sprayed there into the fluidized bed 16.
  • the fluidized bed 16 consists of swirled, small-grain fluidized material, in particular sand.
  • a fluidizing gas is fed through the fluidizing gas line 94 to the fluidizing gas space 24. From this fluidizing gas space 24, the fluidizing gas flows through the openings 14 of the nozzle base 12 into the pyrolysis reactor and swirls the fluidizing material present there, so that the fluidizing bed 16 is formed.
  • Pyrolysis gas which is fed through the pyrolysis gas line 90 and the compressor 92 to the fluidization gas line 94 is expediently used as the fluidizing gas.
  • the pyrolysis gas is taken directly from the second separating tank 88 or, in particular for starting up the system, from the gas storage device 104.
  • the throttle and shut-off device 154 which is arranged in line 152, must be opened.
  • the fluidized bed 16 is preferably heated by a plurality of jacket radiant tubes, of which one jacket jet tube 44 is shown in FIG. 1.
  • the heating gas required for firing the jacket radiant tube is taken from the pyrolysis gas line 90 through the heating gas line 46.
  • the gas pressure required for the flow of the pyrolysis gas and for the formation of the fluidized bed is brought about by the compressor 92. Since the jacket jet heating tube is fired directly with heating gas, it reaches a surface temperature between 1000 and 1100 ° C.
  • the heating power of the jacket radiant tube is therefore correspondingly high.
  • the heat transfer takes place here on the one hand by heat radiation on the sand serving as a fluidizing medium and on the other hand by convection.
  • the fluidized bed is therefore heated intensively, so that the flowable distillation residue sprayed into the fluidized bed is heated very quickly to the required pyrolysis temperature.
  • the preheating of the distillation residue to the limit temperature also contributes significantly to this.
  • the pyrolysis gas which is obtained in fluidizing bed 16 in a reducing atmosphere with exclusion of air, collects in free space 18.
  • the pyrolysis residue is drawn off through the overflow channel 54 and passed into the residue container 56.
  • a discharge device 58 is connected to this for the removal of the pyrolysis residue, which is preferably fed to a landfill.
  • additive material 64 is introduced into the pyrolysis reactor from the container. Fine-grained lime, calcium oxide or dolomite are used as additives.
  • the pyrolysis gas is fed from the free space 18 through the gas line 66 to the cooler 68.
  • the pyrolysis gas flows through the cyclone separator 70, in which dust-like components are separated. These components are then removed from the cyclone separator through line 72.
  • the pyrolysis gas is cooled to a temperature between 100 ° C and 250 ° C.
  • part of the pyrolysis gas condenses and a pyrolysis oil is formed which is separated from the pyrolysis gas in the separating tank 76.
  • the pyrolysis oil collects in the bottom region of the separating container and is removed and processed further through line 78. Cooling water is expediently used for the indirect cooling of the pyrolysis gas in the cooler 68.
  • the cooled pyrolysis gas which collects in the upper region of the separating container 76, flows through the line 82 to the second cooler 84, in which it is cooled to a temperature of approximately 20 to 40 ° C.
  • the pyrolysis oil resulting from partial condensation of the pyrolysis gas is separated from the pyrolysis gas in the second separating tank 88.
  • the pyrolysis oil is drawn off through a pipeline and reused. Cooling water is expediently used for the indirect cooling of the pyrolysis gas in the second cooler 84.
  • the pyrolysis gas separated from the pyrolysis oil in the second separation tank 88 is fed to the pyrolysis gas line 90.
  • the pyrolysis gas it is expedient for the pyrolysis gas to be introduced into the pyrolysis gas line 90 subject to further cooling and / or to pass through a gas scrubber.
  • pyrolysis gas is removed from the pyrolysis gas line 90 and fed to the fluidizing gas space 24 and the jacket radiant tube 44.
  • the remaining pyrolysis gas is conveyed through the second compressor 108 and the line 106 into the gas storage 104. From here it is removed and reused, e.g. for heating rooms.
  • the gas storage device 104 is also connected by a line 152 to the pyrolysis gas line 90, the throttle and control element 154 being inserted into the connection. This is only open while the system is starting up as long as no pyrolysis gas is generated. In this case, previously stored pyrolysis gas is removed from the gas storage device 104 and fed to the pyrolysis gas line 90 for supplying the fluidized bed 16 and the jacket radiant tube 44.
  • the pyrolysis residue which is obtained in the residue container 56 is approximately 10 to 15% by weight of the distillation residue supplied, and accordingly around 90% of the distillation residue is converted into valuable raw materials.
  • a characteristic mass balance is given in Table 1 (see Appendix).
  • the pyrolysis oils obtained in the separation tanks 76 and 88 consist predominantly of valuable aromatic hydrocarbon compounds. About 70% by weight of these compounds consist of benzene, toluene, ethylbenzene, xylene, styrene, indane and indene.
  • the composition of the pyrolysis gas that is delivered to the pyrolysis gas line 90 is given, for example, in Table 2 (see Appendix).
  • the great advantage of the present process lies in the high quality of the pyrolysis products and the low proportion of pyrolysis residue.
  • the advantage is increased by the fact that the sulfur originating from the waste oils or waste oils, which collects in the distillation residue, is bound during the pyrolysis by basic additives such as lime, calcium oxide or dolomite.
  • the pyrolysis products are then almost free of hydrogen sulfide.
  • the shielding of the feed tube 20 against external heat radiation according to FIG. 2 will be selected if the distillation residue is only heated to a temperature which is far below the limit temperature, preferably by at least 50 ° C. However, if it is necessary to heat the distillation residue to a temperature close to the limit temperature or to the limit temperature in order to generate the flowability and to preheat it largely, additional measures must be taken to further heat the flowable distillation residue, in particular in the area of its introduction into the pyrolysis. Prevent reactor with the aim of avoiding coking. In this case, an introduction according to FIG. 3 is chosen. Thereafter, the feed pipe 320 is additionally cooled in the region of the pyrolysis reactor by cooling water which is fed in through the line 322 and discharged through the line 324.
  • the feed pipe 320 is surrounded by a first annular space 326.
  • the first annular space 326 is connected to a second annular space 328, which coaxially surrounds the first annular space 326.
  • the second annular space 328 runs at a distance from the protective tube 314, so that a third annular space 330 is formed which is in contact with the outer space 110 Connection is so that outside air for cooling can enter this annulus.
  • the line 322 which supplies cooling water, is connected to the second annular space 328.
  • the cooling water then flows in the second annular space 328 in the direction of the spray nozzle 122 and passes into the first annular space 326 at the upper end region of the second annular space.
  • the cooling water flows to the lower end of the supply pipe 320 and is discharged through the line 324.
  • the combination of protective tube 314 and liquid cooling will surely prevent additional heating of the flowable distillation residue due to external heat.
  • the distillation residue can therefore be heated in the container 32 up to the limit temperature without the risk that the coking temperature is reached by external heat.
  • the nozzle 122 is protected against heating in the same way as was described in connection with FIG. 2.
  • the cooling of the feed pipe 320 is carried out in the region of the fluidizing gas space 24.
  • FIG. 4 shows an embodiment variant of the pyrolysis reactor 10 from FIG. 1, the other parts of the system according to FIG. 1 connected to the pyrolysis reactor are unchanged and are therefore not shown.
  • the standing pyrolysis reactor 410 has a circular-cylindrical region 412, which is followed by a circular-conical region 414 at the bottom.
  • a vertical discharge channel 415 is connected to the lower end of the circular-conical area 414 and opens into a discharge device 417.
  • This discharge device has a screw conveyor 421 which is driven by a motor 423.
  • a plurality of, preferably eight to sixteen, tubes 424 which are evenly distributed around the circumference and which are introduced from the outer space 110 approximately at right angles through the wall of the pyrolysis reactor into the pyrolysis reactor 410 and end there in the vicinity of the inner wall .
  • These tubes 424 have openings 426 in the pyrolysis reactor which point downwards to the connection point of the discharge channel 415.
  • the other end of the tubes 424 is connected in the outer space to a ring line 428 which surrounds the pyrolysis reactor.
  • the ring line 428 is in turn connected to the fluidizing gas line 94 (cf. also FIG. 1).
  • the horizontally extending jacket radiant tubes 44 are provided, of which only a piece is shown in FIG. 4.
  • the heating gas line 46, the air line 50 and the exhaust line 142 are provided.
  • the feed pipe 420 provided for the feed of the flowable distillation residue is arranged below the pipes 424 on the circular conical region 414 of the pyrolysis reactor. If necessary, a plurality of feed pipes 420 are provided and are evenly distributed around the circumference.
  • the feed pipe 420 penetrates the wall of the pyrolysis reactor approximately at a right angle and has at its upper end a spray nozzle 422 which is directed vertically upwards and accordingly sprays upwards into the fluidized bed 416. If there is only one spray nozzle, then this is arranged centrally. If several spray nozzles are provided, they are arranged evenly distributed over the cross section of the pyrolysis reactor.
  • FIG. 5 shows the area of the feed pipe 420 as a detail and on a larger scale.
  • the feed pipe 420 is cooled here in the same way as the feed pipe 320 according to FIG. 3, so that reference is made to the description of FIG. 3 regarding the structure.
  • the only difference is that a bend 430 is provided at the end of the feed pipe 420, which connects the vertically arranged spray nozzle 422 to the inclined feed pipe 420.
  • the spray nozzle 422 is provided with an insulating layer 124 which, in the present case, additionally extends over the bend 430 which connects the inclined feed pipe to the spray nozzle 422.
  • the wall 432 of the pyrolysis reactor is designed exactly as it was explained in connection with FIG. 6.
  • the insulation consists of the same material and has the same dimensions as in the example according to FIG. 1 or 3.
  • pyrolysis gas is supplied to the ring line 428 as a fluidizing gas through the fluidizing gas line 94.
  • the fluidizing gas flows from the ring line 428 through the tubes 424 into the pyrolysis reactor 410 and exits from the openings 426 at an angle downwards.
  • the fluidizing material present in the pyrolysis reactor preferably sand, is whirled up and the fluidized bed 416 is formed.
  • the fluidized bed is heated by the jacket jet heating tube 44, which is operated in the same manner as described above.
  • the flowable distillation residue is fed through the insulated pipe 26 from the container 32 to the feed pipe 420 and through the spray nozzle 422 into the fluidized bed 416 sprayed (see also Figure 1).
  • the supply pipe 420 is cooled by cooling water.
  • the sprayed-in distillation residue as described in connection with FIG. 1, is thermally decomposed with the exclusion of air and the pyrolysis gas is fed through the gas line 66 to the coolers.
  • additives which have been removed from the container 64 are added to bind the pollutants.
  • the pyrolysis residue is discharged from the pyrolysis reactor through the discharge channel 415 and conveyed into the external space 110 with the aid of the screw conveyor 421.
  • the pyrolysis residue is then fed to a landfill, just as in the exemplary embodiment according to FIG.
  • the delivery capacity of the screw conveyor 421 is regulated in such a way that the fluidized bed 416 has the desired height or thickness.
  • waste oil and "waste oil” in the sense of the present invention include, in addition to the actual oils of this type, in particular also those oils which are mentioned in the present description on page 6, below, and on page 7, above.
  • FIG. 7 shows the upper end region of the spray nozzle 122, 422 as a detail and in a representation which is enlarged compared to the representations of FIGS. 2, 4 and 5.
  • the metallic spray nozzle 122 or 422 which tapers and has an outlet opening 156.
  • the spray nozzle is surrounded by an insulating layer 124, but the outlet opening 156 remains free.
  • the insulating layer 124 preferably consists of the substances mentioned above.
  • the outlet opening 156 is preferably provided with a swirl body which atomization of the spray nozzle is improved. Such swirl bodies for spray nozzles are known, in the present case the swirl body is therefore not shown in the drawing.
  • the diameter of the outlet opening 156 is small compared to the diameter of the feed pipes 20, 320, 420.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (11)

1. Procédé de mise en valeur par pyrolyse de résidu de distillation, qui s'accumule lors du traitement thermique d'huile usée et/ou d'huile résiduaire, caractérisé en ce que le résidu de distillation est introduit dans un réacteur de pyrolyse (10; 410) à l'état fluide, mais au maximum à une température limite qui est située en dessous de la température de cokéfaction du résidu de distillation et qui présente un écart de sécurité par rapport à la température de cokéfaction, et sous une protection vis-à-vis d'un chauffage supplémentaire dépassant la température limite et en ce qu'il est soumis à une pyrolyse dans un lit fluidisé (16; 416) chauffé indirectement à 400 jusqu'à 900°C.
2. Procédé suivant la revendication 1, caractérisé en ce que le lit fluidisé (16; 416) est chauffé par au moins un tube de chauffage radiant (44).
3. Procédé suivant l'une des revendications 1 et 2, caractérisé en ce que le résidu de distillation est pulvérisé dans le lit fluidisé (16, 416) à l'aide d'au moins une tuyère de pulvérisation (122; 422) qui est protégée contre un chauffage par une couche isolante (124).
4. Procédé suivant l'une des revendications 1 à 3, caractérisé en ce que le résidu de distillation est introduit dans la zone inférieure du lit fluidisé (16, 416).
5. Procédé suivant l'une des revendications 1 à 4, caractérisé en ce que le résidu de distillation est introduit dans la zone du lit fluidisé (16; 416) dans laquelle le gaz de tourbillonnement nécessaire à la formation du lit fluidisé est introduit dans le réacteur de pyrolyse (10; 410).
6. Procédé suivant l'une des revendications 1 à 5, caractérisé en ce que, dans la zone du réacteur de pyrolyse, le résidu de distillation est introduit dans le réacteur de pyrolyse (10; 410) par un tube d'amenée (20; 320; 420) protégé de l'extérieur vis-à-vis d'une pénétration de chaleur.
7. Procédé suivant l'une des revendications 1 à 6, caractérisé en ce que le lit fluidisé (16; 416) est produit à l'aide de gaz de pyrolyse qui est libéré d'éléments liquides.
8. Procédé suivant l'une des revendications 1 à 7, caractérisé en ce que le résidu de pyrolyse est évacué du réacteur de pyrolyse par un canal de trop-plein (54) ou par une vis transporteuse (421).
9. Procédé suivant l'une des revendications 1 à 8, caractérisé en ce que de la chaux, de l'oxyde de calcium ou de la dolomie finement moulu est introduit dans le lit fluidisé (16; 416) pour la fixation du soufre.
10. Procédé suivant l'une des revendications 1 à 9, caractérisé en ce que le résidu de distillation est introduit dans le réacteur de pyrolyse en étant chauffé à la température limite.
11. Application du procédé suivant l'une des revendications 1 à 10 pour la mise en valeur de résidu de distillation qui s'accumule lors de la distillation fractionnée d'huile usée et/ou d'huile résiduaire qui contient des composés chlorés et dont les composés chlorés ont été, avant la distillation fractionnée de l'huile usée ou de l'huile résiduaire, convertis en chlorure de sodium par du sodium métallique.
EP88113623A 1987-08-29 1988-08-20 Procédé pour l'utilisation pyrolytique d'un résidu de distillation Expired - Lifetime EP0305847B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88113623T ATE64407T1 (de) 1987-08-29 1988-08-20 Verfahren zum pyrolytischen verwerten von destillations-rueckstand.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3728871A DE3728871C1 (de) 1987-08-29 1987-08-29 Verfahren zum pyrolytischen Verwerten von Destillationsrueckstand und Anwendung des Verfahrens
DE3728871 1987-08-29

Publications (2)

Publication Number Publication Date
EP0305847A1 EP0305847A1 (fr) 1989-03-08
EP0305847B1 true EP0305847B1 (fr) 1991-06-12

Family

ID=6334752

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Application Number Title Priority Date Filing Date
EP88113623A Expired - Lifetime EP0305847B1 (fr) 1987-08-29 1988-08-20 Procédé pour l'utilisation pyrolytique d'un résidu de distillation

Country Status (5)

Country Link
EP (1) EP0305847B1 (fr)
JP (1) JPS6470591A (fr)
CN (1) CN1013202B (fr)
AT (1) ATE64407T1 (fr)
DE (2) DE3728871C1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5707592A (en) * 1991-07-18 1998-01-13 Someus; Edward Method and apparatus for treatment of waste materials including nuclear contaminated materials
DE102007051373B4 (de) * 2007-10-26 2010-11-11 Hii-Gmbh - Industrianlagen - Bau Und Beratung Verfahren und Vorrichtung zur Gewinnung von Diesel oder Heizöl aus kohlenwasserstoffhaltigen Rückständen
CN103044736B (zh) * 2012-12-21 2014-11-05 焦作市弘瑞橡胶有限责任公司 一种橡胶助剂的生产方法
CN107686740B (zh) * 2017-09-05 2019-09-06 柳州淦源环保科技有限公司 一种高温热解反应器及加氢热解处理油泥或废油的系统和方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMISCHE RUNDSCHAU, Nr. 21, 39. Jahrgang, 23.05.86, Solothurn, " Aufbereitung von Altöl; Reinigen mit metallischem Natrium." Seite 184 *

Also Published As

Publication number Publication date
ATE64407T1 (de) 1991-06-15
JPS6470591A (en) 1989-03-16
DE3728871C1 (de) 1989-01-19
DE3863253D1 (de) 1991-07-18
EP0305847A1 (fr) 1989-03-08
CN1031710A (zh) 1989-03-15
CN1013202B (zh) 1991-07-17

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