EP4227382A1 - Procédé et installation de production d'énergie électrique et d'hydrogène à partir de rba - Google Patents

Procédé et installation de production d'énergie électrique et d'hydrogène à partir de rba Download PDF

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Publication number
EP4227382A1
EP4227382A1 EP23156163.0A EP23156163A EP4227382A1 EP 4227382 A1 EP4227382 A1 EP 4227382A1 EP 23156163 A EP23156163 A EP 23156163A EP 4227382 A1 EP4227382 A1 EP 4227382A1
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EP
European Patent Office
Prior art keywords
hydrogen
pyrolysis
steam
oxygen
gas
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EP23156163.0A
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German (de)
English (en)
Inventor
Peter Wiederkehr
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Wiederkehr Engineering Gmb
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Wiederkehr Engineering Gmb
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Publication of EP4227382A1 publication Critical patent/EP4227382A1/fr
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    • 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
    • C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
    • C10B57/12—Applying additives during coking
    • 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
    • C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation

Definitions

  • the present invention relates to a method and a plant for generating energy from RESH (RE from residues and SH from shredder ), and generally from contaminated hydrocarbon-containing organic and inorganic materials as substitute fuels, in particular from residues from shredder systems for disused vehicles.
  • RESH RE from residues and SH from shredder
  • the end product is hydrogen, which can be used for any purpose, but specifically for internal combustion engines in vehicles.
  • the containment of CO 2 emissions is a primary goal, which is extremely successful when operating a vehicle with a combustion engine on the basis of hydrogen.
  • the seats are removed, the dashboards including the steering wheels are removed, as are door panels and interior panels , that means the floor carpets, also in the trunk, the Headliner and all electronic components and wiring harnesses and everything combustible is dismantled, including the tires. In principle, everything is dismantled that is not steel or metal, including glass. As already mentioned, this combustible residual waste is called RESH in technical jargon.
  • the interior fittings with seats, insulation and dashboard make up the main part of the ASR. Metal parts such as the body, engine and chassis are not counted as ASR.
  • ASR consists of the following components, with approximate weight percentages that can vary: plastics, rubber 62% car glass, sand 16% Paint dust, rust 16% Textiles, leather, fibers 6% wood fiber, cardboard 4% metals 1%
  • plastics plastics
  • rubber 62% car glass
  • Paint dust Paint dust
  • rust 16% Textiles leather
  • fibers 6% wood fiber
  • cardboard 4% metals 1%
  • the steel body remaining from the vehicle is mechanically shredded and pressed into a compact package, which then goes into a furnace to recover the various metals it contains.
  • ASR could be thermally disposed of in waste incineration plants (WIP) from 1996 onwards.
  • the Swiss Federal Office for the Environment (FOEN) set the mixing ratio for household waste at 5% by weight. This does not change the emission behavior during combustion, the organic substances are burned and the slag can be disposed of in managed landfills without endangering the environment. This reduces the volume of the ASR by 70 percent and the mass by 50 percent.
  • the high calorific value of ASR is used as valuable energy for electricity production and district heating.
  • this step represents a major ecological advance.
  • the Swiss Auto Recycling Foundation pays disposal contributions to the Swiss shredder works.
  • the shredder plants must submit the canceled vehicle registration documents for the shredded vehicles.
  • the object of the present invention is to provide a method and a plant with which it is possible to use all kinds of contaminated hydrocarbon-containing waste and in particular RESH, such as is produced in large quantities, above all when disused vehicles are demolished, as an energy source for the simplest and most direct and efficient production of hydrogen can be used.
  • a Hydrogen produced could then primarily be used to operate vehicles with internal combustion engines, for driving without CO 2 emissions.
  • the ASR is converted into oil and gas using pyrolysis.
  • a burner is fed with this oil-gas mixture, which burns this fuel at 2200 degrees Celsius within 2 seconds.
  • pressurized steam is generated in a steam boiler.
  • the steam is used to be expanded through a steam turbine, with the output shaft of the steam turbine driving an AC generator.
  • the electricity produced in this way is rectified in a rectifier system and is used to feed an electrolysis system for splitting water H 2 O into hydrogen H 2 and oxygen O 2 .
  • Part of the hydrogen generated keeps the pyrolysis going, which is otherwise usually operated with natural gas.
  • the excess hydrogen is preferably stored in a metal hydride MeHy storage.
  • the metal concentrate can be used for copper processing, and the exhaust air from the burner is converted into fuel or other substances via a Co 2 /NO x reduction. Excess steam on the downstream side of the turbine can be removed via a District heating network can be used as a source of heat, or used to dry metals or sewage sludge.
  • the thermal splitting of the hydrocarbon-containing waste, residues and/or substitute fuels with subsequent cleaning opens up the possibility of using these four existing pyrolysis products energetically for the operation of steam generation by separating unwanted contaminants in the four products mentioned above. Some undesired contaminants can also be removed from the subsequent thermal utilization by not using the pyrolysis coke and can be removed separately and utilized elsewhere.
  • ASR ASR
  • process gas is generated at 550°C, i.e. a synthesis gas. Residual energy is gasified at 600°C and reaches a downstream burner at 450°C, while only inert slag remains from the pyrolysis of the ASR.
  • the pyrolysis plant is used for the thermal conversion of carbon-containing starting materials, eg biomass or waste materials, into liquid pyrolysis oil, pyrolysis gas and pyrolysis coke and takes place in the absence of oxygen or at least essentially without the presence of oxygen.
  • Pyrolysis is an endothermic process, although individual sub-processes can be exothermic.
  • the pyrolysis must be maintained with an energy supplier. A small proportion of the hydrogen produced using the process presented here is sufficient for this.
  • the percentages of the pyrolysis products mentioned can be influenced by the input material, its residual moisture content and the process conditions such as temperature, residence time, pressure and the rate of heating and cooling.
  • This pyrolysis of ASR results in gas, oil and coke, which can be used as alternative fuels for steam generation and can partially or completely replace other energy sources.
  • a pyrolysis reactor R is fed with ASR pellets, which can be delivered by train, ship or truck, depending on the location. They contain what is left over from the recycling of old cars after all metal parts have been removed.
  • the ASR pellets themselves are temporarily stored in a bunker B with a volume of 250 cubic meters, for example, and from there they are continuously fed to the pyrolysis reactor R after pre-treatment.
  • the ASR is pyrolyzed in the absence of air at temperatures between 350°C and 800°C.
  • the ASR Before it gets into the reactor R, the ASR first goes through a pretreatment PT (pre-treatment) and is processed in this process step with the supply of steam. A portion is then fed to the pyrolysis reactor R, while the remainder is fed directly to the burner for generating pressurized steam via a delivery line D1 (delivery line 1).
  • pretreatment PT pre-treatment
  • D1 delivery line 1
  • the pyrolysis reactor R for example an EREKA bioreactor from M.E.E. Schwerin GmbH in Germany, breaks down waste containing hydrocarbons, residues and/or alternative fuels into the four typical pyrolysis products.
  • This reactor R is a horizontal, closed steel pipe, inside which at least one heatable rotating screw conveyor slowly conveys the input material fed in on one side to the other side. Depending on the design, several such heatable screw conveyors can also be arranged inside the reactor tube.
  • the pyrolysis of the input material takes place in the absence of oxygen at a temperature of 350°C to 800°C.
  • the essential post-treatment of the pyrolysis products oil, gas and coke follows in order to remove unwanted contaminants from these pyrolysis products. With the system presented here, after the thermal splitting of the starting material by means of pyrolysis in the reactor R, this is done by processing in a central technical-chemical processing facility downstream of the reactor R.
  • the pyrolysis products resulting from the pyrolysis process are treated differently depending on the type.
  • the pyrolysis gas is fed to a gas purification GP (Gas Purification), for which water is also required, as can be seen from the water supply drawn in.
  • the gas cleaning device includes a quencher and an electrostatic filter. The gases are thus washed, cooled and solid particles are separated by means of an electrostatic field.
  • the permanent gas fraction exiting the reactor R and the short-chain hydrocarbons contain NOx, SOx, mercury, CI, HCl, various other halogens and their compounds.
  • the decontamination takes place in the gas cleaning unit GP using acid and a basic wash in a quench device Q.
  • aerosols, dust particles, which can also be contaminated can be separated in this gas cleaning unit GP. This is done using the downstream electrostatic precipitator. After cleaning, this pyrolysis gas can be used for energy in accordance with the regulations and is fed directly to the burner and boiler via the supply line D2.
  • the delivery line D2 must not be longer than 50 meters in order to avoid resin precipitation that would otherwise occur.
  • the pyrolysis oil produced in the reactor R by the pyrolysis of the ASR contains heavy metals such as Cd, Se, Ba, etc. It is decontaminated in a quencher Q, in which it is washed.
  • the oil/water mixture then flows into the water treatment WT, in which water is separated and the oil is finely filtered.
  • the residual water from the water treatment is drawn off and fed to a separate wastewater treatment system via the supply line D5, while the oil is fed directly to the burner via the supply line D3 after this cleaning. After this cleaning, this pyrolysis oil can be fed directly to the burner and boiler as an energy source.
  • Pyrolysis coke is largely free of hydrocarbons, but is still slightly contaminated with organic substances such as mineral oil hydrocarbons MKW, polyaromatic hydrocarbons PAH, and mixtures of all kinds of aromatic hydrocarbons BTX, as well as heavy metals such as copper, Cd, Fe, Ni, Co, Zn, Sn, Al, and inorganic components such as Si0 2 and the like.
  • Decontamination is carried out by magnetic iron removal in a separate coke post-treatment CT (Coke Treatment). There they are sorted, the pollutants are washed out chemically, or they are separated electrolytically, or a part is sent directly to a smelter via the delivery line D6. The separated metals and all separated non-ferrous materials are thus reused.
  • Metal concentrate can be delivered to a copper processor, for example.
  • the energetic utilization of the carbon content takes place after this cleaning of the previously contaminated coke, in which it is fed directly to a downstream burner of a boiler via the delivery line D7, or can be stored temporarily for later use.
  • Pyrolysis water contains contaminants CI, HCl, other halogens and their compounds, various salts and an organic load (BTX, phenols, PAH, etc.). Its decontamination is done by neutralization, precipitation and filtering. After cleaning, further use can take place via the delivery line D5.
  • the substitute fuels obtained after this treatment and now in compliance with the regulations are fed directly into the burner of a steam generation plant via a maximum 50 meter long line D1 to D4. In this way, a precipitation of resins in the gas line D2 can be avoided.
  • the oil is sprayed in together with the pyrolysis water via line D3, and the coke via a separate feed line D4.
  • These substitute fuels are supplied either directly from the after-treatment units PT, GP, WT or CT, or from appropriate storage tanks in which the oil is kept at at least 150°C and the gas at >1 bar, i.e. at the same pressure above atmospheric pressure to allow it to flow of its own accord to the downstream burner.
  • oils and gases from pyrolysis can be used without restriction and are even less polluting than coal.
  • Alternative fuels include tires, plastic chips, waste oil, sterilized meat meal, sewage sludge and solvents. All of this can be processed with the pyrolysis process presented.
  • the untreated coke resulting from the pyrolysis process as a waste product has a calorific value of 10-20 MJ/kg.
  • this coke contains heavy metals in quantities which, for example, exceed the requirements of the "cement directive" and are not even allowed to be used in cement kilns in Switzerland.
  • This dirty coke is therefore separated via line D7 and collected in containers and transported away for further processing without direct use for incineration and steam generation.
  • the environmental impact assessment has shown that the overall environmental impact is low if heat generation is switched from hard coal to coke, which is obtained from ASR pyrolysis. Overall, even CO 2 is saved because the ASR pellets would have to be burned anyway. Instead of being used in a waste incineration plant, they are used according to the process presented here for steam generation, with downstream electricity generation, electrolysis of water and oxygen/hydrogen storage.
  • Another advantage of this process and the heating of a boiler with the pyrolysis products for steam generation is that the masses of ASR that would otherwise have to be landfilled are reduced to around 50% compared to the mass of the starting material. It is also advantageous that the pyrolysis products gas and oil can be stored, which is conducive to the continuous operation of a boiler and the generation of steam and electricity. In this way, more or less gas and/or oil can be metered into the combustion system at any time with fine control.
  • the technologies for obtaining pressurized steam from a fuel are known in many forms in the prior art, and the expansion of pressurized steam via a turbine to drive an electrical generator is also well known.
  • the basic scheme for this is in figure 2 shown.
  • the heat supply 1 comes from the supply lines D1 to D4 of the pyrolysis plant. Steam is generated in boiler 2, which is heated by the burner. The hot pressurized steam is fed via the steam line 3 to a turbine 4 and expanded via this.
  • the output shaft 5 of this turbine 4 drives a generator 6, which generates electrical AC voltage, which is intended to supply approximately 10 megawatts of electricity for the power generation downstream of an ASR pyrolysis plant.
  • the turbine 4 is followed by a condenser 7 whose waste heat 8 is supplied for further use, for example for heating apartments, commercial and office space and greenhouses. For this purpose, it can be fed into any existing district heating network in the vicinity.
  • the condensed and expanded steam, ie the water, is conveyed into the boiler 2 via a feed pump 10 via the feed line 9 .
  • the figure 3 shows the system components based on an example electrolysis system, which is the generator 6 downstream.
  • the alternating current generated is transformed down in the transformer 11 to a suitable voltage for the electrolysis.
  • the energetic efficiency of the electrolysis of water is around 70%.
  • Several system manufacturers e.g. Electrolyser Corp., Brown Boweri, Lurgi, De Nora
  • Electrolyser Corp., Brown Boweri, Lurgi, De Nora offer large electrolysers with an even higher efficiency - of almost 100%. Since the electrolyte concentration and the temperature of an electrolyte solution have a major influence on the cell resistance and thus on the energy costs, a 25-30% KOH solution is used in modern systems, and the temperature is around 70-90°C.
  • the current density is around 0.15 A/cm 2 and the voltage around 1.90 V, with overvoltage around 2.06 V.
  • Liquid hydrogen H 2 passes through a filter 16 into a lye container and this lye is pumped to the alkaline electrostack 13 via a motor 18 to promote the electrolysis.
  • the gaseous hydrogen H 2 arrives after the purifier 15 in an intermediate tank 30. From this, liquid hydrogen H 2 is branched off at the bottom and flows through a compressor and is returned by a pump 32 via a line to an upper region of the intermediate tank 30 and expanded there via the valve 33 with cooling.
  • the gaseous hydrogen H 2 above the liquid level is removed via line 34 and buffered in a gas tank 21 . From there it is fed via a liquid gas compressor into a deoxidizer 23 and then discharged via the two dryers 24 and a control valve 25 into a storage tank.
  • the resulting substances hydrogen H 2 and oxygen O 2 are collected and the hydrogen is preferably stored in metal hydride storage tanks for use as required.
  • a part of the hydrogen H 2 produced, about a third, is used to maintain the pyrolysis of the ASR and can replace the natural gas otherwise required for this.
  • the exhaust air from the burner is converted into fuel or other substances via a Co 2 /NO X reduction.
  • the excess steam can be fed into a district heating network or used to dry metals or sewage sludge.
  • the volumetric energy density of hydrogen even at high pressures is relatively low, the density is relatively low.
  • the density at 700 bar is only approx. 40kg/m 3 .
  • a volume of approx. 25 liters is required even at 700 bar.
  • a volumetric energy density of 4.8 MJ/I (megajoules per liter) is obtained. That is about 6 times less than petrol with 31 MJ/I offers.
  • a 40-ton truck for example, can only transport around 400 kg of compressed hydrogen. For a supply of hydrogen filling stations, for example, this would be a rather unsatisfactory value. The transport costs would be far higher than those for liquid fuels.
  • a higher storage density with a simultaneously greatly reduced pressure is possible by storing liquefied hydrogen at a very low temperature of -253°C. But then you get the difficulties of scale with such low temperatures.
  • the energy density of liquid hydrogen at 8.5 MJ/l, is less than a third of the value for petrol.
  • the energy consumption for the liquefaction of the hydrogen is also considerable. Depending on the technology selected, it corresponds to at least about a fifth of the calorific value, but often even more than a quarter.
  • evaporation is a major problem for vehicle applications.
  • Liquid hydrogen carriers another variant, have the advantage that they can be easily stored in tanks or transported through pipelines. In principle, various substances can be used for this purpose.
  • ammonia AHs
  • LOHC liquid organic hydrogen carriers
  • toluene which is converted to methylcyclohexane by hydrogenation, was investigated, as well as N-ethylcarbazole and dibenzyltoluene. In all these cases, CC double bonds are converted into single bonds during hydrogenation.
  • a catalyst is usually used for injection and withdrawal.
  • Dibenzyltoluene has particularly interesting properties for use as a liquid hydrogen carrier. It has been used as a heat transfer oil for decades and has proven to be superior to other carrier substances in several respects. After all, dibenzyltoluene can absorb several percent of its weight in hydrogen. One liter can store approx. 660 liters of hydrogen gas at normal pressure, which, however, only results in an energy density of 7.1 MJ/I in relation to the calorific value, i.e. a good four times less than for petrol. Due to the low vapor pressure, only very little of the carrier substance gets into the dissolved hydrogen during the discharge - despite the relatively high discharge temperatures of e.g. B. between 250 °C and 320 °C. This substance is also favorable in terms of safety, for example far better than diesel oil: practically no hydrogen escapes at moderate temperatures, which means that the substance is practically incombustible even when loaded.
  • Liquid hydrogen carriers could thus in principle be used like conventional liquid fuels to power fuel cells in vehicles, although unfortunately the energy density would be around 4 to 5 times lower than that of conventional fuels.
  • part of this disadvantage is compensated for by the fact that the efficiency of the electricity generation of the Hydrogen using fuel cells is significant and better than direct combustion of fuels in internal combustion engines.
  • the quantities of liquid to be transported and stored are "only" increased by a factor of 2 to 3 compared to petrol or diesel.
  • high-temperature fuel cells are used, the waste heat of which is sufficient to enable the storage tank to be discharged.
  • the discharged hydrogen carrier is sucked off during refueling in order to be reloaded with hydrogen elsewhere.
  • the "state of charge" of such LOHC storage devices can be checked relatively easily using measurements, for example optically via the refractive index.
  • the figure 4 shows the entire plant in an overview, from pyrolysis, power generation, electrolysis and hydrogen storage in one scheme.
  • typical matching sizes for this system are given below, assuming an annual operating time of 7,000 hours.
  • the ASR is fed to a shredder and the light fraction from it is fed to the pyrolysis. If, for example, 14,000 tons of ASR are generated per year, this results in 2 tons of ASR per hour, which is fed to pyrolysis.
  • the pyrolysis is operated at a temperature of at least 450°C, in further stages up to 600°C.
  • the waste products are CO 2 , carbon and metal concentrates at a rate of approximately 1,400 tons per year, or 0.1 to 0.2 tons per hour.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Processing Of Solid Wastes (AREA)
EP23156163.0A 2022-02-14 2023-02-10 Procédé et installation de production d'énergie électrique et d'hydrogène à partir de rba Pending EP4227382A1 (fr)

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CH1342022 2022-02-14

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100077711A1 (en) 2008-09-29 2010-04-01 Horst Weigelt Thermochemical reactor for a self-propelled harvesting vehicle
DE202011110102U1 (de) * 2011-11-16 2012-11-19 New Power Pack GmbH Vorrichtung zur Energiegewinnung aus Biomasse
WO2020239716A1 (fr) 2019-05-27 2020-12-03 Covestro Intellectual Property Gmbh & Co. Kg Procédé de valorisation de déchets de matériau de polyuréthane pour produire des matières premières chimiques destinées à produire des isocyanates et des polyuréthanes

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100077711A1 (en) 2008-09-29 2010-04-01 Horst Weigelt Thermochemical reactor for a self-propelled harvesting vehicle
DE202011110102U1 (de) * 2011-11-16 2012-11-19 New Power Pack GmbH Vorrichtung zur Energiegewinnung aus Biomasse
WO2020239716A1 (fr) 2019-05-27 2020-12-03 Covestro Intellectual Property Gmbh & Co. Kg Procédé de valorisation de déchets de matériau de polyuréthane pour produire des matières premières chimiques destinées à produire des isocyanates et des polyuréthanes

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