EP4530331A1 - System und verfahren zur pyrolyse von schwerem heizöl - Google Patents

System und verfahren zur pyrolyse von schwerem heizöl Download PDF

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Publication number
EP4530331A1
EP4530331A1 EP23200708.8A EP23200708A EP4530331A1 EP 4530331 A1 EP4530331 A1 EP 4530331A1 EP 23200708 A EP23200708 A EP 23200708A EP 4530331 A1 EP4530331 A1 EP 4530331A1
Authority
EP
European Patent Office
Prior art keywords
rotating reactor
reactor
auger
coke
base frame
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.)
Pending
Application number
EP23200708.8A
Other languages
English (en)
French (fr)
Inventor
Philipp RÖSSCHEN
Bernd Drechsel
Harry Hennig
Holger Hörig
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.)
Puraglobe Holding GmbH
Original Assignee
Puraglobe Holding GmbH
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 Puraglobe Holding GmbH filed Critical Puraglobe Holding GmbH
Priority to EP23200708.8A priority Critical patent/EP4530331A1/de
Priority to PCT/EP2024/077316 priority patent/WO2025068531A1/en
Publication of EP4530331A1 publication Critical patent/EP4530331A1/de
Pending legal-status Critical Current

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Classifications

    • 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
    • C10G9/02—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils in retorts
    • C10G9/04—Retorts
    • 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
    • C10B43/00—Preventing or removing incrustations
    • C10B43/02—Removing incrustations
    • C10B43/04—Removing incrustations by mechanical means
    • 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
    • C10B47/00—Destructive distillation of solid carbonaceous materials with indirect heating, e.g. by external combustion
    • C10B47/28—Other processes
    • C10B47/32—Other processes in ovens with mechanical conveying means
    • C10B47/34—Other processes in ovens with mechanical conveying means with rotary scraping devices
    • 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
    • C10B55/00—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material
    • 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
    • C10B7/00—Coke ovens with mechanical conveying means for the raw material inside the oven
    • C10B7/02—Coke ovens with mechanical conveying means for the raw material inside the oven with rotary scraping devices
    • 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
    • C10G9/06—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by pressure distillation
    • C10G9/08—Apparatus therefor
    • C10G9/12—Removing incrustation
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27B—FURNACES, KILNS, OVENS OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
    • F27B7/00—Rotary-drum furnaces, i.e. horizontal or slightly inclined
    • F27B7/20—Details, accessories or equipment specially adapted for rotary-drum furnaces
    • F27B7/2075—Removing incrustations
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D25/00—Devices or methods for removing incrustations, e.g. slag, metal deposits, dust; Devices or methods for preventing the adherence of slag
    • F27D25/001—Devices or methods for removing incrustations, e.g. slag, metal deposits, dust; Devices or methods for preventing the adherence of slag comprising breaking tools, e.g. hammers, drills, scrapers

Definitions

  • the invention provides an abrasion device (300) for continuously removing coke from the inner wall of a rotating reactor (110) comprising a cylindrical part (114) and comprising a base frame (310) with suspensions (311) for mounting auger scrapers (320), wherein said suspensions (311) are mounted at the base frame (310) and connect an upper part (312) and a lower part (313) of the base frame (310); said lower part (313) of the base frame (310) comprises at least one auger scraper (320), wherein said at least one auger scraper (320) comprises a central roller (321) with an outer auger helix (322), said at least one auger scraper (320) being rotatably mounted at cross members (314) at the lower part (313) of the base frame (310) at the ends of the suspensions (311) that are protruding in direction of the bottom of the cylindrical part (114) of the rotating reactor (110).
  • the invention further provides a system (100) for continuous processing of heavy fuel oil from recycling waste oil and the processing residues of crude oil into useful products comprising means for feeding waste oil; at least one hot-gas filter, at least one condenser, at least one rotating kiln comprising an outer stationary jacket (120) which forms a heating channel (121), and an inner rotating reactor (110), and the abrasion device (300) for removing solid coke from the rotating reactor (110).
  • a system (100) for continuous processing of heavy fuel oil from recycling waste oil and the processing residues of crude oil into useful products comprising means for feeding waste oil; at least one hot-gas filter, at least one condenser, at least one rotating kiln comprising an outer stationary jacket (120) which forms a heating channel (121), and an inner rotating reactor (110), and the abrasion device (300) for removing solid coke from the rotating reactor (110).
  • the invention further relates to a process for continuous processing of heavy fuel oil from recycling waste oil and the processing residues of crude oil into useful products, preferably with the system of the invention.
  • the heavy oil (residual oil) produced during oil distillation accounts for about 70 percent of the fuel used in shipping worldwide. From 2020 onwards, ships on the high seas will only be allowed to burn fuel with a Sulphur content of 0.5 percent or below instead of 3.5 percent allowed so far, or will alternatively have to remove the Sulphur from the exhaust gases. As a result of the new regulation, which will be set in force in 2020, environmentally harmful heavy fuel oil cannot be used as a fuel anymore and a large number of international shipping companies will have to replace heavy fuel by more environmentally friendly ship diesel. This in turn has a direct influence on the refineries. There will no longer be a market for their residual heavy oil products in the future.
  • Heavy fuel oil essentially consists of long-chain saturated hydrocarbon compounds (heavy boilers).
  • processes are needed to degrade these long chain hydrocarbons into shorter chains.
  • One suitable method is pyrolysis, i.e. the so-called “cracking process”.
  • the pyrolysis is forced by high temperatures under exclusion of oxygen. Gases, liquids and solids are produced as pyrolysis products.
  • pyrolysis is performed in systems comprising a rotating kiln as reactor, in which the cracking of the long chain hydrocarbons of the heavy oil takes place.
  • the heavy oil In the rotating kiln, the heavy oil must be finely atomized and evenly distributed on the inner wall of the rotating kiln.
  • the necessary reaction temperature is usually produced by external heating the rotating kiln and the cracking reaction takes place at the inner wall of the kiln.
  • the rotating kiln can be purged with a protective medium such as nitrogen.
  • the cracking reaction takes place, the long chain hydrocarbons are converted into gaseous products and coke is produced as a major byproduct.
  • the coke occurs as a soft coke, which is distributed in the gaseous phase and which has to be eliminated from the gaseous products before their condensation. Coke further occurs as solid coke adhering to the inner wall of the rotating kiln.
  • a growing coke layer at the inner wall of the rotating kiln is disadvantageous, because it forms a heat insulating layer, which disturbs the cracking reaction. As a result, the heavy fuel oil cannot reach the reactor wall and the temperature for initiating the cracking reaction cannot be reached effectively.
  • CA 2926434 concerns a rotary kiln for the treatment of waste oil and other organic waste.
  • the rotary kiln here is equipped with loosely mounted plates which shall prevent the deposition of coke in the bottom area of the rotary kiln, or shall lead to the scraping off deposited coke.
  • the loosely mounted plates are distributed randomly within the rotary kiln and after short time of operation, the bottom of the rotary kiln is blocked by a mixture of plates and coke debris.
  • the material flow in the reactor is hindered and the coke cannot be discharged quickly enough, which further increases the size of the bed. This means that the required temperatures cannot be maintained and the heavy fuel oil is sprayed onto the material on the bottom of the reactor and the cracking reaction is thereby disturbed. Therefore, a continuous operation of the rotary kiln as described in CA 2926434 is not possible.
  • the German utility model DE 29704044 U1 deals with the problem of the formation of solid layers on the inner wall of rotary kilns resulting from the smoldering of materials containing hydrocarbons, such as residues from heavy oil and coal hydrogenation.
  • rolling elements are used to clean the inner wall of the drum. These rolling elements, however, are themselves covered with the solid material during operation of the rotary kiln, wherein their effectivity in cleaning the inner wall of rotary kilns is decreased and the maintenance efforts of the entire system is increased.
  • the invention relates to a device for removing contaminants from used oil, in which device the oil is subjected to evaporation and pyrolysis to form coke. Contaminants such as heavy metals remain in the coke, which can then be separated from the oil.
  • the device comprises a rotating kiln, which is indirectly heated.
  • the problem has to be solved that coke deposited on the reactor walls has to be removed.
  • the reaction chamber is equipped with granular, crude solids (such as metal chips), which act to chafe and crush coke from the reactor wall.
  • Such system can only be operated discontinuously, because the granular, crude solids are mixed with the coke crushed from the reactor wall during operation. This mixture accumulates in the reactor and needs to be removed regularly from the reactor.
  • WO 2020187754 A1 concerns a system for continuous processing of heavy fuel oil from recycling waste oil and the processing residues of crude oil into useful products, said system comprising scraper means that are mounted in a rotating kiln, wherein the distance between the scraper means and the reactor wall is in the range of 0.5 to 2.0 mm. This leads to the fact the coke still accumulates at the reactor wall as a layer with a thickness between 0.5 to 2.0 mm.
  • Said abrasion device comprises a base frame with suspensions for mounting auger scrapers.
  • the suspensions are mounted at the base frame, connect an upper part and a lower part of the base frame and are preferably designed to be telescopic and allow a vertical movement of the lower part of the base frame, which comprises the auger scrapers.
  • the auger scrapers comprise a central roller with an outer auger helix, which is preferably made of steel.
  • the auger scrapers are rotatably mounted at cross members at the lower part of the base frame at the ends of the suspensions that are protruding in direction of the bottom of the rotating reactor.
  • each abrasion device comprises one, two or three, preferably two, most preferably three auger scrapers.
  • the rotating reactor of the invention comprises two abrasion devices comprising two to six auger scrapers, preferably four, most preferably six auger scrapers.
  • the auger scraper means are aligned with the reactor wall.
  • the auger scrapers are arranged over the entire length of the bottom of the cylindrical part of the rotating reactor.
  • the auger scrapers are arranged alternately on the left and right side of the base frame with the telescopic suspensions, when seen from the top view. This ensures an even load on the telescopic suspensions by the auger scrapers.
  • the abrasion device of the invention comprises at least one, preferably some, most preferably all of the following further special embodiments:
  • the invention further provides a system for continuous processing of heavy fuel from the recycling of waste oil and the processing of residues from crude oil into useful products comprising
  • Said system is preferably configured to operate at a process temperature in the range of 600 to 650 °C, measured at the inner wall of the rotating reactor.
  • the continuous cleaning of the inner wall of the rotating reactor is one of the crucial points in the construction of the system according to the invention since the heat transfer is hindered by the layer structure of the coke and thus the cracking process of the heavy fuel oil on the reactor wall and within the volume of the rotating reactor is disturbed. It is a great advantage of the abrasion device and system of the invention comprising said abrasion device that substantially all accumulated coke is removed from the inner wall of the rotating reactor. Compared to prior art technologies, e.g. to the technology disclosed in WO 2020187754 A1 , no coke layer is formed the inner wall of the rotating reactor during operation. So, the heat transfer and energy efficiency of the abrasion device and system of the invention is greatly improved compared to technologies known in the prior art.
  • the rotating reactor is equipped at the lower end of the inclined reactor with a funnel, wherein said funnel comprises auger plates to discharge the material from the rotating reactor.
  • the funnel and the auger plates are preferably made of a suitable material, such as iron or steel or stainless steel.
  • the rotating reactor comprises a cylindrical part and a funnel with the auger plates.
  • the cylindrical part has usually a length of 4.50 to 6.00 m.
  • the cylindrical part has a length of 5.00 to 5.50 m.
  • the cylindrical part has a length of 5.23 m.
  • the funnel has usually a length of 1.50 to 2.50 m.
  • the funnel has a length of 1.80 m to 2.20 m.
  • the funnel has a length of 2.02 m.
  • the cylindrical part and the funnel together usually have a length of 6.00 m to 8.50 m.
  • the cylindrical part and the funnel together have a length between 6.50 and 8.00 m.
  • the cylindrical part and the funnel together have a length of 7.25 m.
  • the cylindrical part has usually a diameter in the range of 2.40 m to 3.20 m, preferably in the range of 2.60 m to 3.00 m. Most preferably, the cylindrical part has a diameter of 2.80 m.
  • the rotating reactor has two barrel rings, i.e. one barrel ring on each end of the reactor. Each of the barrel rings interacts with a bearing of a frame construction. When the cylindrical part and the funnel together have a length of 7.25 m, the two barrel rings have a distance of 7,00 m.
  • Ovality is the degree of deviation from perfect circularity of the cross section of the reactor.
  • the ovality i.e. the deviation from perfect circularity of the cross section of the reactor is in the range of ⁇ 3 mm at the barrel rings.
  • a further problem is the so-called deflection over the longitudinal axis of the reactor.
  • the value of the deflection may increase with the length of the reactor.
  • the length of the reactor is relatively short and a value of 1 to 2 mm was calculated for the deflection.
  • the rotating reactor of the present invention comprises at the outer wall of its cylindrical part, means that ensure that the heating gas is evenly distributed in the heating tunnel (discussed below).
  • Such means are preferably plates, such as ribbed plates, which are welded on the outer wall of the cylindrical part. These welded ribbed plates on the outer wall of the reactor have a further stabilizing effect, which further decreases the deflection below the value of 1 to 2 mm.
  • the ovality and deflection of the reactor play a minor role. Deviations from the "roundness" of the reactor are advantageously compensated by the abrasion device of the invention, which allows vertical movements of the lower part of the base frame, which comprises the auger scrapers of the abrasion device, through the telescopic suspensions.
  • the advantage of this construction in particular the combination of the abrasion device of the invention with the funnel comprising auger plates is that the scraped coke is discharged from the rotating reactor continuously in an easy way and without the need of further constructural means, simply by gravity.
  • the discharge of the scraped coke by gravity is further supported by the arrangement of the rotating reactor, which is inclined in direction of the lower end, i.e. towards the funnel comprising auger plates.
  • the rotating reactor is inclined at an angle between 2 und 8°, preferably 3 to 6°, most preferably 4 to 5°.
  • the system of the invention comprises downstream components such as a diverter, double pendulum dampers and screws for discharging the scraped coke.
  • Preferred downstream elements comprise a diverter, a mill or a grinder, rotary valves or double sluice gates, a hot-rolling screw conveyor and a cooling screw conveyor. The solids are conveyed from the rotating reactor into the diverter.
  • the coke In the subsequent downstream elements, the coke must be cooled from the process temperature down to a temperature of e.g. 60 °C in the cooling screw. After passing the cooling screw, the scraped coke may be filled in big bags or other types of containers for storage and further handling.
  • the system of the invention comprises in a further embodiment downstream means for filling the scraped coke into containers, such as Big Bags.
  • the rotating reactor In order to promote the cracking reaction, the rotating reactor must be heated to reach and maintain the process temperature, which is suitably in the range of 400 to 700°C, preferably between 550 and 700°C, more preferably between 600 and 650°C.
  • the rotating reactor is heated indirectly. This has the advantage that the occurrence of hotspots or punctual heat in the reactor wall is prevented, which could occur with direct heating. Indirect heating is realized preferably by an outer jacket, which forms a housing and heating channel around the rotating reactor. External burners, such as external gas burners, that are placed outside of the rotating reactor and outside of the housing, are used to produce heat that is blown into the heating channel (the space between the rotating reactor and the outer jacket) of the system of the invention.
  • a further challenge is to apply the required heat evenly over the whole body of the rotating reactor.
  • This problem is solved in the preferred embodiment of the invention in that and number of burners, such as gas burners are arranged to apply indirect heat along the entire length of the rotating reactor.
  • 2 to 6 gas burners are used for indirect heating, more preferably 3 to 5 gas burners most preferably 4 gas burners.
  • the number of gas burners may be adopted in accordance with the dimensions of the rotating reactor.
  • the gas burners must have an output sufficient to support the cracking reaction in the rotating reactor.
  • the total output of the gas burners is preferably between 500 and 2,000 kW, more preferably between 750 and 1,500 kW, most preferably between 950 and 1.250 kW.
  • the burners are mounted to the heating tunnel via a pre-combustion chamber. In order to prevent heat loss, the pre-combustion chamber and the heating tunnel are insulated.
  • means are provided on the outer wall of the rotating reactor.
  • Such means are preferably plates, such as ribbed plates, which are made from a suitable material, such as iron, steel or stainless steel. These means increase the surface of the reactor wall and ensure a turbulent flow of the heating gas as well as a more efficient heat transfer into the rotating reactor.
  • the system of the invention therefore comprises in a further embodiment ribbed plates for supporting the distribution of the heated air, wherein said ribbed plates are mounted on the outer wall of the rotating reactor.
  • the number and the dimensions of these ribbed plates are configured in accordance with the dimensions of the system of the invention, i.e. of the rotating reactor.
  • the system of the invention further comprise holes in the jacket for directing the heating gas into the space between housing and reactor wall of the rotating reactor.
  • a further challenge, which has been solved by the system of the invention, is the even distribution of the heavy fuel oil over the entire length of the rotating reactor. For this reason, the heavy fuel oil is not distributed into the rotating reactor with one spray lance only.
  • the number of spray lances has been rather increased in accordance with the length of the rotating reactor, especially in accordance with the length of the cylindric part of it.
  • the system of the invention comprises more than one, e.g. 2 to 8, preferably 3 to 5, most preferably 4, evenly most preferred 3 spray lances, which guarantee even distribution of the sprayed heavy fuel oil with in the rotating reactor.
  • the spray lances have different lengths in order to distribute the heavy fuel oil with defined parts or areas of the rotating reactor, whereby it is advantageous that the length of the spray lances is selected in order to prevent overlapping spray pattern.
  • the design of the nozzles, which are mounted at the end of the spray lances in the rotating reactor, has also been optimized.
  • the nozzle used are as fine as possible and do not have a too large spray cone.
  • This construction has the advantage that an overlapping spray pattern is prevented.
  • the use of a flat spray nozzles is not recommended, as these are only to be used for coarse spray patterns.
  • the nozzles used at the end of the spray lances have a spray cone with a spray angle at the outlet of the nozzle of approx. 45°. This construction ensures that not too much material is sprayed onto a too small area, because this would deteriorate the heat transfer within the rotating reactor and therefore disturb the cracking reaction.
  • Solids such as coke
  • Solids are continuously scraped from the rotating reactor wall during its operation, forming a bed of debris in the certain area on the bottom of the rotating reactor.
  • This bed of debris detonates the heat transfer on the reactor wall and into the rotating reactor at least locally.
  • Spraying the heavy fuel oil on the bed of the breeze would lead to an incomplete cracking reaction.
  • the direct action of the nozzles is therefore arranged to spray the heavy fuel oil on areas of the wall of the rotating reactor, which is free of debris of solids and coke.
  • the system of the invention therefore comprises in a further embodiment means for removal of the remaining solids from the gas stream.
  • Suitable means for the removal of the remaining solids from the gas stream are for example cyclones or hot gas filtration systems.
  • Most preferred in accordance with the invention are hot gas filtration systems.
  • a suitable hot gas filtration system comprises e.g. fibre-ceramic filter cartridges.
  • Such a hot gas filter may comprise rigid filter elements, which are suspended in an insulated container with a conical dust collection chamber, wherein the filter cartridges made of robust ceramic fibes are resistant to temperatures up to 850 °C and chemicals.
  • the hot gas filter is equipped with means for cleaning the filter cartridges.
  • Such means are e.g. selected from jet valves, which are opened in short intervals (fractions of a second), whereby the filter cartridges are purged with an inert purge gas, such as nitrogen gas at high pressure.
  • the system of the invention comprises seals between the rotating reactor and the inlet and outlet housings, and a seal between the heating channel and the reactor.
  • the seals between the rotating reactor and the inlet and outlet housings are important for operating the process of the invention and a reliable manner.
  • the system of the invention is in further embodiment equipped with heat exchanger.
  • This has the advantage that the pyrolysis and flue gases can be used for heat recovery, i.e. the thermal energy of the flue gases is used to preheat the combustion air required for the gas burners in order to ultimately save natural energy, i.e. natural gas, and also to reduce the output size of the burners as far as possible.
  • the pyrolysis gas is fed via a heat exchanger for residual heat utilization, heat energy can be obtained between 120 and 170 MJ/h at efficiencies between 0.5 and 0.7 with the system of the invention. Accordingly, the system of the invention can be operated in an environmental-friendly manner.
  • the system of the invention comprises a condenser for separating the heavy boiling hydrocarbons, aqueous phase and inert gas fraction from the dust-free pyrolysis gas.
  • the condenser is suitably arranged in the system after the hot gas filter.
  • the system is operated under slight overpressure in an oxygen free atmosphere.
  • the system of the invention is configured to prevent any cold bridges and to keep the temperature of and in the rotating reactor including parts that are connected to the rotating reactor, in the range of the process temperature as described above.
  • the invention provides a process for continuous processing of heavy fuel oil from the recycling of waste oil and the processing of crude oil, into useful products comprising the steps of
  • the process of the invention can be described in a general manner as follows:
  • the thermal cracking (pyrolysis) takes place in the rotating reactor of the invention.
  • Feed pumps convey the starting product (heavy fuel oil) from the storage tank to the subsequent subsystems.
  • the oil is mixed with steam on the input side, preferably under ratio control, and injected into the rotating reactor.
  • the pyrolysis takes place in a temperature range between 400 to 700°C, preferably between 450 and 600°C, more preferably between 600 and 650°C, measured at the inner wall of the rotating reactor.
  • the temperature in the inner volume of the reactor is preferably between 450°C and 500°C, most preferably 450°C.
  • the long-chain hydrocarbon compounds are degraded and pyrolysis coke and pyrolysis gas are produced.
  • the coke adheres to a great extent to the reactor wall and forms solid coke, which disturbs thermal flow from the heating channel of the system of the invention into the rotating reactor.
  • the solid coke is therefore removed by auger scrapers and discharging means and conveyed out of the rotating reactor by gravity.
  • the pyrolysis gas produced contains a not inconsiderable proportion of solids. These are to be removed directly from the hot gas stream, preferably by means of a hot gas filter, which in a more preferred embodiment of the invention comprises fiber-ceramic filter cartridges.
  • the quality of the purified gas is decisive for the stability of the further process.
  • the solids-free pyrolysis gas is a mixture of heavy boiling hydrocarbons, low boiling hydrocarbons and water in the presence of inert gas components which are separated by condensation.
  • the resulting hydrocarbon liquids from heavy boiling hydrocarbons and water are discharged from the system of the invention via defined service lines in a storage tank for further use.
  • the remaining non-condensed gases (low boilers) serve as fuel for the gas heaters of the system of the invention.
  • the separated solids are fed to a Big Bag filling system via a hot-rolling screw conveyor and a cooling screw conveyor.
  • the Big Bags are e.g. temporarily stored in a small warehouse before they are shipped for recycling by truck. Recycling of the separated solids may e.g. be done by use as fuel for blast furnaces.
  • the invention relates to the use of the gas oil / naphta produced with the system and/or the process of the invention for manufacturing useful products, such as fuel, base oil and base oils products.
  • the invention relates to the use of the powdery coke produced with the system and/or the process of the invention as fuel in blast furnaces.
  • the advantage of this aspect of the invention is that almost any products as well as waste products resulting from the process of the invention are re-usable or recyclable.
  • FIG. 1 shows a cross-sectional view of the system 100 of the invention.
  • the system 100 comprises a rotating reactor 110, which is equipped with an abrasion device 300 in the cylindrical part 114 of the rotating reactor.
  • Said abrasion device 300 comprises a base frame 310 with suspensions 311 for mounting auger scrapers 320.
  • the suspensions 311 are mounted at the base frame 310, connect an upper part 312 and a lower part 313 of the base frame 310 and are telescopic thereby allowing a vertical movement of the lower part 313 of the base frame 310, which comprises the auger scrapers 320.
  • the auger scrapers 320 comprise a central roller 321 with an outer auger helix 322, which is made of steel.
  • the auger scrapers 320 are rotatably mounted at cross members 314 at the lower part 313 of the base frame 310 at the ends of the suspensions 311 that are protruding in direction of the bottom of the cylindrical part 114 of the rotating reactor 110.
  • the embodiment shown in Figure 1 comprises two abrasion devices 300, wherein each abrasion device 300 comprises three auger scrapers 320.
  • the auger scrapers 320 are aligned with the inner wall of the rotating reactor 110 and are arranged over the entire length of the bottom of the cylindrical part 114 of the rotating reactor 110.
  • the auger scrapers 320 are arranged alternately on the left and right side of the base frame 310 with the telescopic suspensions 311, when seen from the top view. This ensures an even load on the telescopic suspensions 311 by the auger scrapers 320.
  • the abrasion device 300 of the system 100 shown in Figure 1 is characterized by the following further special embodiments:
  • the rotating reactor 110 shown in this embodiment comprises a cylindrical part 114 and a funnel 115 with the auger plates 116.
  • the cylindrical part 114 has a length of 5.23 m and diameter of 2.80 m.
  • the cylindrical part 114 and the funnel 115 together have a length of 7.25 m.
  • the ovality, i.e. the deviation from perfect circularity of the cross section of the rotating reactor 110 is in the range of ⁇ 3 mm.
  • the value of the deflection over the length of the rotating reactor 110 was calculated with 1 to 2 mm, which is further decreased by the ribbed plates 122, which are welded on the outer wall of the cylindrical part 114.
  • the rotating reactor 110 is inclined at an angle of 4°, which further supports the transport of the scraped solids by gravity into the direction of the funnel 115.
  • the funnel 115 is located at the lower end of the inclined reactor 110 and comprises auger plates 116.
  • the funnel 115 with the auger plates 116 supports the transport of the scraped solids out of the reactor 110 into a diverter (not shown), from which the solids are removed from the system 100 via an outlet 172 through a mill 175 and a doble sluice gate 176.
  • Figure 2 shows cross-sectional view of the funnel 115 of the rotating reactor 110, which is equipped with auger plates 116 supports the transport of the scraped solids out of the reactor 110 into a diverter (not shown).
  • the reactor comprises in the central axis 113 spray lances 150 with nozzles 151.
  • FIGS 3 and 4 show embodiments of a side-view on and into the system 100 of the invention.
  • the system 100 comprises an outer jacket 120 which forms a housing of the system 100. Between the housing 120 and rotating reactor 110, a heating channel 121 is formed.
  • Four gas burners 130 are mounted in a pre-combustion chamber 140 outside the rotating reactor and outside the housing and are connected to the heating channel 121 via connecting pipes 123.
  • an indirect heating of the reactor 110 is achieved.
  • the indirect heating prevents the formation of punctual heat or hot spots, which otherwise may occur upon direct heating.
  • the rotating reactor 110 is equipped with ribbed plates 122, which are fixed on the outer wall of the reactor 110.
  • the system 100 comprises four spray lances 150 with nozzles 151.
  • the spray cones 152 of the nozzles 151 are indicated. It can be seen from figures 3 and 4 that the spray cones 152 show non-overlapping pattern in order to support an even distribution of the heavy fuel oil sprayed into the reactor 110 and to prevent local overdosing of heavy fuel oil in the reactor 110.
  • the system 100 further comprises the abrasion device 300 of the invention (not shown in Figures 3 and 4 ).
  • FIG. 5 it is shown that the funnel 115 of the rotating reactor 110 protrudes into the diverter 170.
  • Figure 5 shows a cross-sectional view of an embodiment of the diverter 170.
  • the diverter 170 comprises at the lower end a funnel 171 with an outlet 172 for the solids, which fall through a mill (not shown) into a double sluice gate (not shown) by gravity and are discharged thereby from the system 100.
  • the diverter 170 On the upper end, the diverter 170 comprises an outlet for the pyrolysis gas, which is connected to the hot gas filter (not shown).
  • the diverter 170 further comprises a maintenance opening 174.
  • Figure 6 illustrates the principle, how the direction of rotation (indicated by the arrow) and the spraying is coordinated in the reactor 110.
  • a debris of scraped solids 153 is formed, which accumulates at a certain position in the reactor 110 due to the rotation of the reactor 110.
  • the nozzles 152 are oriented such that spraying of the heavy fuel oil into the direction of the accumulated debris 153 is prevented, i.e. the heavy fuel oil is sprayed on areas of the inner wall 114 of the reactor 110, which are free from debris 153 of solids.
  • This construction ensures that the heavy fuel oil sprayed into the reactor 110 contacts the inner wall 114 of the reactor 110 directly, wherein the reactor wall 114 has the required reaction temperature of 600 to 650 °C.
  • Figures 7 and 8 show embodiments of the housing 120 of the system 100, which forms the heating chamber 121.
  • Four gas burners 130 are connected via connector pipes 123 to the heating chamber 121.
  • the heating pipes 123 are part of a pre-combustion chamber 140.
  • Further shown in Figure 8 is the seal 160 of the central axis 113 and a bearing 190 of the rotating reactor 110.
  • the housing further comprises an opening 160 for exhaust gas.
  • FIG. 9 shows the hot gas filter 180 comprising a filter housing 181 and pressure lines 182 for introducing purge gas into the hot gas filter 180 via purge gas inlet 186.
  • the cleaning of the filter cartridges 184 with purge gas, such as nitrogen, is controlled by jet valves 182.
  • the pyrolysis gas is introduced into the hot gas filter via inlet 185.
  • the hot gas filter 180 comprises at the lower end a conical form, which ends with an outlet 188 for the solids that are removed from the pyrolysis gas. The solids fall into the diverter 170 by gravity.
  • the hot gas filter 180 further comprises an outlet 189 for the solids-free pyrolysis gas into direction of the condenser (not shown).
  • the hot gas filter 180 comprises a backflush tank 187.
  • Figure 10 shows an embodiment of the abrasion device 300 of the invention with the features as detailed in Fig. 1 , wherein Fig. 10A is a top view, Fig. 10B is a front view and Fig. 10C is a side view of the abrasion device 300.
  • Fig. 10A is a top view
  • Fig. 10B is a front view
  • Fig. 10C is a side view of the abrasion device 300.
  • the weights 330 are covered by a roof 340, which prevents the accumulation of off-scraped coke powder on the weights of the abrasion device 300, which supports the maintenance of the contact pressure of 120 N/mm 2 on the inner side of the wall of the cylindrical part 114 of the rotating reactor 110 exerted by the lower part 313 of the base frame 310 with the auger scrapers 320, which comprise a central roller 321 and an auger helix 322.
  • the lower part 313 of the base frame 310 comprises a further frame 315 to increase the stability of the lower part 313 of the base frame 310.
  • Figure 11 represents a flowsheet of the process of the invention.
  • the process according to Figure 10 can be described as follows: 200
  • the system 100 of the invention is fed with the heavy fuel oil from storage tanks via a pump and a pressure line.
  • a second pump may be kept in reserve.
  • the pressure line to the rotating reactor 110 is electrically heated with an operation temperature in the range of 50 to 80 °C, preferably 60 to 70 °C, most preferably of 65 °C, because a lower temperature results in an increase in viscosity of the heavy fuel oil and thus in increased pressure losses.
  • the heavy oil must be finely atomized, coated with a protective medium and evenly distributed on the inner wall 114 of the rotating reactor 110. In the rotating reactor 110 the cracking reaction takes place.
  • the heavy fuel oil is fed into the rotating reactor 110 via a number of spray lances 150 comprising nozzles 151 in order to achieve a uniform spray pattern but to also to prevent an overlapping spray pattern of the individual nozzles 151.
  • a number of spray lances 150 comprising nozzles 151 in order to achieve a uniform spray pattern but to also to prevent an overlapping spray pattern of the individual nozzles 151.
  • four nozzles 151 are used to meet the prerequisites of the spray pattern.
  • they are fed individually into the reactor 110 via separate spray lances 150 of different length.
  • the input feed is thus divided into four identical partial feeds.
  • the required protective film is achieved by dosing steam in a ratio of approx. 1: 10 with controlled quantities.
  • Static mixers are used to achieve a largely homogeneous mixture of oil and steam.
  • the required operating temperature of 500 to 600°C at the inner wall 114 of the rotating reactor 110 is achieved by four gas burners 130 with a 250 kW output, operated with natural gas or recycled pyrolysis gas.
  • the combustion air is preheated with the hot flue gases according to the counterflow principle.
  • Coke adhering to the rotating reactor wall 114 is removed by scraping and conveyed due to the inclined position rotating reactor 110 towards the outlet of the reactor 110 into the diverter.
  • the solid material accumulates at the lower end of the diverter and is discharged by a separating system via a mill and double sluice gate.
  • the gas flow is discharged at the upper outlet of the diverter.
  • the diverter as well as the downstream system components between reactor 110 and condenser are electrically heated at a holding temperature of 550°C.
  • the temperature of the diverter is determined by the temperature of the reactor 110. The high temperatures are important to prevent condensation in the system components before the condensation stage in order to prevent sticking and clogging of the system components. 220
  • Solid particles contained in the gas stream are filtered in the downstream hot gas filter 180.
  • Rigid filter elements 184 are suspended in an insulated container 181 with a conical dust collection chamber at the lower end, which comprises filter cartridges 184 made of robust ceramic fibers resistant to temperatures up to 850 °C and chemicals.
  • the pyrolysis gas is introduced laterally in the lower part of the filter via inlet 185, where the dust containing gas is deflected in such a way that larger particles are already separated here as a result of gravity forces.
  • the pyrolysis gas which is still loaded with fine dust, now flows through the filter elements 184 suspended in the filter container from the outside to the inside, whereby the dust is separated on the surface of the filter cartridges 184.
  • the now dust-free pyrolysis gas reaches the gas outlet 189 via the filter head and is still at a temperature level sufficient for the subsequent condensation.
  • the filter elements 184 located in the hot gas filter 180 are grouped into several filter groups, which can be shut off separately towards the outlet. Differential pressure and/or time-controlled, one chamber at a time is decoupled from the gas cleaning process, while the gas filtration continues to run normally via the filter elements 184 of the remaining chambers. To clean the filter elements, jet valves 182 of the shut-off chamber are opened one after the other for fractions of a second, whereby purge gas (N 2 / 300°C) flows into the interior of the filter cartridges 184 at high pressure via pressure lines 183. This short rinsing impulse is sufficient to blow off the filter cake.
  • purge gas N 2 / 300°C
  • the "offline" cleaning process means that the dust is not immediately drawn back onto the filter elements 184, but falls downwards into a dust collection chamber. Since only small quantities of purge gas are used for pulse cleaning, there is no temperature reduction in the gas and dust collection chamber of the filter 180, which is also sufficiently heat-insulated and electrically heated (500 °C). The dust falls into the diverter 170 and is discharged by the operation of the mill and the double sluice gate, which is also used for discharging the scraped coke from the lower end of the rotating reactor 110. 520
  • the dust-free pyrolysis gas is fed to the condensation stage via the shortest possible route at 550°C process temperature.
  • the condenser heavy boiling hydrocarbons, aqueous phase and inert gas fraction are separated.
  • the essential condensation products are gas oil/naphtha and water. These are collected in a storage container and, after a certain dwell time, separated in a level-controlled manner and transported to downstream plants or storage tanks for further use.
  • the non-condensable residual gas flow is fed into an exhaust system. 240
  • the low-boiling hydrocarbons (methane, ethane, propane, butane, pentane) comprised in the produced gas, are fed as fuel to the gas burners 130 to heat the rotating rector 110. 250
  • the coke produced exits the diverter 170 and the hot gas filter 180 at 550 °C process temperature.
  • the coke With a mill and a double sluice gate, the coke is discharged under gas-tight conditions to the downstream equipment.
  • a hot-rolling screw conveyor collects the material flow and conveys it to a cooling screw conveyor.
  • the coke is cooled down to a temperature of 60 °C in the cooling screw. Subsequently it is filled into Big Bags.
  • the Big Bags are inflated with nitrogen prior to filling, which in turn inertises the conveying and cooling screws in counterflow to the coke.
  • the Big Bags are preferably dustproof and conductive.
  • the system and process of the invention have several advantages compared to the conventional systems and processes.
  • One main problem associated with cracking of heavy fuel oil is the formation of coke which adheres at the reactor wall at one hand and which is partly distributed in the gaseous reaction products as soft coke and dust.
  • the system and process of the invention it is possible for the first time to operate a pyrolysis reactor in a reliable and continuous manner over long time periods, because means and methods are provided to effectively remove the coke from the reactor wall as well as from the gaseous reaction products continuously.
  • the system further solves problems like the prevention of hot spots in the reactor by indirect heating of the rotating reactor with a hot gas stream produced by external gas burners outside the pyrolysis reactor.
  • the entire system is temperature controlled to prevent cold points and undesired condensation in the reactor and associated assemblies.
  • the system of the invention further fulfills today's environmental requirements. Almost any products resulting from the process of the invention are further used or recycled, such as gas oil /naphta for the production of fuel and recycling oils, such as base oil and base oil products.
  • gas oil /naphta for the production of fuel and recycling oils, such as base oil and base oil products.
  • the combustion air is preheated with the hot flue gases according to the counterflow principle.
  • the pyrolysis gas produced with the method of the invention is re-used for producing the required process heat with the gas burners of the system.
  • the scraped coke is further used as fuel for blast furnaces.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • General Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
EP23200708.8A 2023-09-29 2023-09-29 System und verfahren zur pyrolyse von schwerem heizöl Pending EP4530331A1 (de)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP23200708.8A EP4530331A1 (de) 2023-09-29 2023-09-29 System und verfahren zur pyrolyse von schwerem heizöl
PCT/EP2024/077316 WO2025068531A1 (en) 2023-09-29 2024-09-27 System and process for heavy fuel oil pyrolysis

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EP23200708.8A EP4530331A1 (de) 2023-09-29 2023-09-29 System und verfahren zur pyrolyse von schwerem heizöl

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US1403980A (en) * 1919-09-13 1922-01-17 Arthur D Smith Apparatus for effecting circulation and maintaining clean surfaces in stills
DE29704044U1 (de) 1997-03-06 1998-07-09 VEBA OEL Technologie und Automatisierung GmbH, 45879 Gelsenkirchen Walzkörper für eine Drehtrommel sowie einen Walzkörper aufweisende Drehtrommel
DE69732164T2 (de) 1996-09-27 2005-12-15 Alberta Oil Sands Technology And Research Authority, Calgary Thermisches Gerät und Verfahren zum Entfernen von Verunreinigungen aus Öl
CN102764749A (zh) * 2011-05-04 2012-11-07 中国有色（沈阳）冶金机械有限公司 一种无动力螺旋刮料装置
CN106091674A (zh) * 2016-08-16 2016-11-09 新疆中金科瑞新能源发展股份有限公司 一种回转窑结焦清除装置和清除方法
CA2926434A1 (en) 2016-04-07 2017-10-07 Louis Bertrand Rotating kiln and apparatus for thermal conversion of organic wastes, method for converting organic wastes into useful products, manufacturing of rotating kilns and apparatus and uses thereof
CN209662731U (zh) * 2018-12-13 2019-11-22 湖南万通科技股份有限公司 一种脱水仓
WO2020187754A1 (en) 2019-03-15 2020-09-24 Puraglobe Holding Gmbh System and process for heavy fuel oil pyrolysis
CN211871768U (zh) * 2020-02-24 2020-11-06 清华珠三角研究院 一种油泥热解旋转窑的窑内刮刀结构
US20230167367A1 (en) * 2020-04-07 2023-06-01 Vance E. McClure Reaction Vessel for Liquid Phase Catalytic Pyrolysis of Polymers

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1403980A (en) * 1919-09-13 1922-01-17 Arthur D Smith Apparatus for effecting circulation and maintaining clean surfaces in stills
DE69732164T2 (de) 1996-09-27 2005-12-15 Alberta Oil Sands Technology And Research Authority, Calgary Thermisches Gerät und Verfahren zum Entfernen von Verunreinigungen aus Öl
DE29704044U1 (de) 1997-03-06 1998-07-09 VEBA OEL Technologie und Automatisierung GmbH, 45879 Gelsenkirchen Walzkörper für eine Drehtrommel sowie einen Walzkörper aufweisende Drehtrommel
CN102764749A (zh) * 2011-05-04 2012-11-07 中国有色（沈阳）冶金机械有限公司 一种无动力螺旋刮料装置
CA2926434A1 (en) 2016-04-07 2017-10-07 Louis Bertrand Rotating kiln and apparatus for thermal conversion of organic wastes, method for converting organic wastes into useful products, manufacturing of rotating kilns and apparatus and uses thereof
CN106091674A (zh) * 2016-08-16 2016-11-09 新疆中金科瑞新能源发展股份有限公司 一种回转窑结焦清除装置和清除方法
CN209662731U (zh) * 2018-12-13 2019-11-22 湖南万通科技股份有限公司 一种脱水仓
WO2020187754A1 (en) 2019-03-15 2020-09-24 Puraglobe Holding Gmbh System and process for heavy fuel oil pyrolysis
US20220145191A1 (en) * 2019-03-15 2022-05-12 Puraglobe Holding Gmbh System and Process for Heavy Fuel Oil Pyrolysis
CN211871768U (zh) * 2020-02-24 2020-11-06 清华珠三角研究院 一种油泥热解旋转窑的窑内刮刀结构
US20230167367A1 (en) * 2020-04-07 2023-06-01 Vance E. McClure Reaction Vessel for Liquid Phase Catalytic Pyrolysis of Polymers

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