EP2536495B1 - Procédé et dispositif pour l'obtention de carburants et gaz combustibles à partir de substances organiques - Google Patents
Procédé et dispositif pour l'obtention de carburants et gaz combustibles à partir de substances organiques Download PDFInfo
- Publication number
- EP2536495B1 EP2536495B1 EP10705328.2A EP10705328A EP2536495B1 EP 2536495 B1 EP2536495 B1 EP 2536495B1 EP 10705328 A EP10705328 A EP 10705328A EP 2536495 B1 EP2536495 B1 EP 2536495B1
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- EP
- European Patent Office
- Prior art keywords
- reactor
- thermal decomposition
- carbon
- organic materials
- decomposition
- Prior art date
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- 239000007789 gas Substances 0.000 title claims description 75
- 238000000034 method Methods 0.000 title claims description 69
- 239000011368 organic material Substances 0.000 title claims description 31
- 239000000446 fuel Substances 0.000 title claims description 24
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 63
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 59
- 230000008569 process Effects 0.000 claims description 57
- 229910052799 carbon Inorganic materials 0.000 claims description 54
- 230000015572 biosynthetic process Effects 0.000 claims description 43
- 238000003786 synthesis reaction Methods 0.000 claims description 39
- 238000000354 decomposition reaction Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 229910010272 inorganic material Inorganic materials 0.000 claims description 11
- 239000011147 inorganic material Substances 0.000 claims description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 238000001149 thermolysis Methods 0.000 claims description 6
- 241000196324 Embryophyta Species 0.000 claims description 5
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000005201 scrubbing Methods 0.000 claims description 5
- 239000002699 waste material Substances 0.000 claims description 5
- 239000002023 wood Substances 0.000 claims description 5
- 238000001722 flash pyrolysis Methods 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000002028 Biomass Substances 0.000 claims description 3
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 3
- 239000003575 carbonaceous material Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000013538 functional additive Substances 0.000 claims description 3
- 238000002485 combustion reaction Methods 0.000 claims description 2
- 239000002361 compost Substances 0.000 claims description 2
- 239000010791 domestic waste Substances 0.000 claims description 2
- 238000012432 intermediate storage Methods 0.000 claims description 2
- 235000013372 meat Nutrition 0.000 claims description 2
- 239000003921 oil Substances 0.000 claims description 2
- 235000019198 oils Nutrition 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 2
- 239000008158 vegetable oil Substances 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims 1
- 229920000642 polymer Polymers 0.000 claims 1
- 238000005096 rolling process Methods 0.000 claims 1
- 239000010865 sewage Substances 0.000 claims 1
- 239000007858 starting material Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 description 44
- 238000002309 gasification Methods 0.000 description 13
- 238000000197 pyrolysis Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 8
- 239000002956 ash Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000005416 organic matter Substances 0.000 description 6
- 239000003245 coal Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000001335 aliphatic alkanes Chemical group 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000011269 tar Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000013502 plastic waste Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical class [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000010883 coal ash Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 239000010801 sewage sludge Substances 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/58—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels combined with pre-distillation of the fuel
- C10J3/60—Processes
- C10J3/64—Processes with decomposition of the distillation products
- C10J3/66—Processes with decomposition of the distillation products by introducing them into the gasification zone
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/007—Screw type gasifiers
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/02—Fixed-bed gasification of lump fuel
- C10J3/06—Continuous processes
- C10J3/10—Continuous processes using external heating
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2200/00—Details of gasification apparatus
- C10J2200/15—Details of feeding means
- C10J2200/156—Sluices, e.g. mechanical sluices for preventing escape of gas through the feed inlet
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0903—Feed preparation
- C10J2300/0909—Drying
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0953—Gasifying agents
- C10J2300/0973—Water
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/12—Heating the gasifier
- C10J2300/1246—Heating the gasifier by external or indirect heating
Definitions
- the invention relates to a process for the recovery of combustible fuels and gases from organic matter, wherein the organic substances are thermally decomposed to form the combustible fuels and gases and to form carbon.
- the invention relates to an apparatus for carrying out such a method, with a reactor for the thermal decomposition of organic substances to form combustible fuels and gases and to form carbon.
- Processes and apparatuses for extracting combustible fuels and gases from organic matter are well known, for example, as systems for the conversion of biomaterials into biogas which have been in operation for some years, but at the same time they are also the enormous problems that surround the entire industry.
- a certain proportion of organic materials is also thermally decomposed, especially in pyrolysis plants, with the formation of combustible fuels and gases and the formation of carbon, but here too the efficiency left much to be desired and this also always requires not inconsiderable investments.
- the quality of the gases produced in this way is often very inconsistent - on the one hand due to the diversity of the thermally decomposable organic materials, and, on the other hand, depending on the nature of the respectively selected settings in the process control.
- the method known to be mixed usually with inorganic material such. As with metals or salts, resulting carbon must be disposed of as unusable ashes.
- Exemplary of this are the methods and devices in the following documents. This is how the document describes US 2008/0149471 A2 a pyrolysis furnace and a one-step process running in it.
- the document EP 1865 045 A1 describes a steam reformer and also a one-step process.
- the document US 5,151,159 A describes a pyrolysis process in which coal is produced, which is then burned.
- the document US 2003/0010266 A1 describes a two-stage pyrolysis process with subsequent oxidation.
- the document EP 1 160 307 A2 describes a one-step carbonization process.
- the document EP 1 447 438 A1 describes a four-pass gasification with two pyrolysis steps: pre-gasification and re-gasification.
- the document EP 1 323 810 A1 describes a double-tube gasifier with recycling of the non-gasified residual material.
- the document DE 196 14 689 A1 describes a multivalent usable plant for the thermal treatment of starting substances a single reactor.
- the document US 1,538,796 describes a "multiple unit retort" for separating volatile gases from carbonaceous material with a number of horizontal retort segments.
- a method of the type mentioned is the WO 01/68789 A1 refer to.
- This document discloses a pyrolysis unit which is disclosed in there in Fig. 2 illustrated execution in the form of a heated indirectly via a heating jacket screw conveyor and to which a gasification unit connects with an oxidation zone.
- Moist raw material such as biomass or wood chips
- a so-called dryer unit in which steam is also supplied, where it is pyrolyzed, ie thermally decomposed to form a gaseous and a solid fraction. Both fractions arrive from the pyrolysis unit in the gasification unit, in particular in a gasification reactor, which is traversed from top to bottom by a gasification agent.
- This gasification agent is described as preheated air and / or water vapor and is intended to cause a partial oxidation of the volatile constituents in the sense of further thermal decomposition .
- the so-called gasification unit is essentially another pyrolysis unit.
- solids from the pyrolysis unit are gasified and the tar content of the introduced volatile components is lowered.
- the occurring reactions are not described and do not open up from the specified reaction temperatures, especially not because the respective compositions of the gasification agent and the incoming gas-solid mixture are indefinite.
- the invention has for its object to provide a method and a device of the type mentioned in a technologically less expensive way, with which the degree of utilization of the organic substances used in the production of combustible fuels and gases can be increased.
- this is achieved in that the carbon generated in the thermal decomposition is converted in a decomposition spatially and temporally downstream synthesis process in water vapor atmosphere to carbon monoxide and hydrogen, wherein the thermal decomposition and the synthesis process in two separate technologically connected in series Reactors, a decomposition reactor for the thermal decomposition of organic substances and a synthesis reactor for the formation of carbon monoxide and hydrogen takes place, and wherein the inventive method has the features of claim 1.
- the reactor for thermal decomposition is technologically followed by a synthesis reactor for the formation of carbon monoxide and hydrogen from water vapor and carbon formed in the reactor for thermal decomposition, the reactors gas-tight separate furnace sections or ovens are connected to each other via a gas-tight lock for supplying the carbon from the reactor for thermal decomposition in the synthesis reactor, wherein the reactor for thermal decomposition has a gas outlet for decoupling of the gases formed in it with connected gas cooler, and wherein the inventive device having the features of claim 13.
- the thermal decomposition of organic substances can be carried out as so-called flash pyrolysis in a temperature range of 300 ° C to 600 ° C, based on 100% dry matter of organic substances about 75% to 85% combustible fuels and gases and about 15% to 25% carbon arise.
- Important for full utilization of the energy of the organic substances used according to the invention is the conversion of the carbon. If you take z.
- wood as decomposing organic substance or as an energy supplier which has a calorific value of about 18 MJ / kg of dry matter, then make 20% residual carbon with a calorific value of about 34 MJ / kg at least about 38% of the wood immanent energy which can be used more according to the invention in comparison with a process without a synthesis step.
- Another possibility - if a high hydrogen yield is desired - is to carry out the thermal decomposition of the organic substances as so-called monocarbon thermolysis in a temperature range of 650 ° C to 800 ° C, based on 100% dry matter of the organic substances more than 20 % Carbon - together with CO, H 2 , CH 4 - is formed, which is then available for the synthesis reaction, the composition depending on the nature of the input material and its moisture.
- the amount of carbon formed during thermal decomposition depends on the temperature; the higher this is, the more carbon is liberated because, as will be shown in detail below, it is formed at the thermolytic interfaces of the polymeric organic molecules.
- the thermally decomposable organic substances contain components from which arise in the thermal decomposition of inorganic ash products. Also during the thermal decomposition of the organic substances the process especially in water dissolved functional additives, such as salts and salt formers, such as phosphoric acid or potassium hydroxide, are supplied - so to order z.
- water dissolved functional additives such as salts and salt formers, such as phosphoric acid or potassium hydroxide, are supplied - so to order z.
- the invention is based on the finding that a combination of thermal decomposition and synthesis in a single reactor space leads to problems. For example, while a thermolysis takes place, expanding gas clouds are formed around the decomposing particles of the organic substances, which would effectively force away the steam required for conversion to hydrogen and carbon monoxide from the reaction site, so that no water molecule reaches the carbon. In addition, remains at a thermolysis - as known from the production of activated carbon - always a stable carbon skeleton in the resulting carbon, so that here the surface, although theoretically large, but the water molecules is accessible only to a limited extent, so that no complete implementation can take place.
- An important step towards the full utilization of the energy contained in the organic matter to be decomposed is also the division of the hybrid device into the stage of decomposition with the o. G. middle or with the o. g. higher, but compared to the temperature of the synthesis stage, which - is carried out as a high-temperature process in the temperature range of 850 ° C to 1000 ° C - because of the high purity of the coal and also because of the presence of chemically inactive inorganic substances, comparatively lower temperature range.
- the CO / H 2 production can be followed in a further reactor, a water gas shift reaction, which at temperatures between 250 ° C and 450 ° C on a ferric oxide catalyst, the carbon monoxide in an exothermic process in water vapor. Atmosphere is converted to carbon dioxide, with the amount of hydrogen approximately doubled.
- the method according to the invention with the decomposition and the synthesis process although anaerobic and in each case as an endothermic reaction - that is not autothermic - led to be realized in the overall balance with high energy efficiency, since on the one hand the energy required for decomposition and synthesis at least more than 80% , Preferably more than 95%, by combustion of the combustible fuels and gases obtained from the organic substances and / or by recuperation of the heat generated in the water gas shift process can be provided, only for a first or possibly after downtime repeated commissioning of the device according to the invention is a one-time energy input, for example, with externally supplied combusting fuel gas, necessary. In the stationary state, the heat can be provided 100% process-immanent.
- the carbon from the stage of decomposition of the organic substances preferably passes directly into the synthesis reactor, ie without cooling and intermediate storage, ie already at the reaction temperature prevailing in the decomposition stage, so that in the synthesis stage only nor the difference amount of energy to reach the relevant temperature is spent.
- the reactors of the device according to the invention in particular in the reactor for thermal decomposition, it may preferably be carried out by means of screw conveyors.
- spatula and / or roller units integrated into the screws can very finely distribute the organic material over the bottom of the oven, so that all particles can be brought directly to an optimum flash temperature, for example about 475 ° C., via contact heat from the reactor wall.
- Scraper units mounted behind can then free the floor or reactor wall wall of buildup and make it free for subsequent direct contact with the organics.
- the resulting carbon agglomerates are broken, so that only pulverized coal, usually mixed with inorganic material, the point of discharge is fed from the reactor.
- an organic moisture-containing substance 1 or else a mixture of substances is set in a heated funnel 2 to a desired dry matter content.
- Plant substances such as wood or compost, biomass, household waste, plastic waste, sewage sludge, meat waste, old car tires and the like can be used more as organic substances 1.
- the organic substances used to form the combustible fuels and gases may contain 5% to 50%, preferably 15% to 20%, moisture, which is preferably adjusted by the drying preceding the thermal decomposition.
- the thermally decomposable organic substances 1 can also contain constituents from which arise during thermal decomposition inorganic ash products.
- the organic substance 1 used to form the combustible fuels and gases or the organic substances 1 are comminuted before decomposition and drying, in particular comminuted to mean particle sizes in the range from 2 mm to 5 mm, preferably one Dimension in a spatial dimension of the particles (length, width, height) should be smaller than 100 microns.
- the particles have an optimum surface-to-volume ratio for the decomposition reaction and, for the purpose of heat transfer, the thermal attack.
- the organic substance 1 falls into a sluice 3, which is shown as an example in the drawing as a rotary valve, and passes through the opening 4 in the interior of the reactor 5 for decomposition.
- the lock 3 closes the reactor also airtight from the material supply point down.
- the thermal decomposition of the organic substance 1 is performed as an anaerobic process, wherein the organic material 1 can also be introduced into the reactor 5, in particular under protective gas.
- an axially extending screw conveyor 6 moves the material continuously up to the discharge opening 8, which in turn opens into a gas-tight lock 9, in particular a rotary valve.
- the decomposition reactor 5 also has a feed 7, via which water, optionally with functional additives dissolved therein, can be supplied.
- the screw conveyor 6 always has transverse bars, which extend longitudinally to the housing of the decomposition reactor 5.
- transverse bars which extend longitudinally to the housing of the decomposition reactor 5.
- simple scratch and turning seals are enough - like the one in Fig. 5 with the reference numeral 62 designated latch - but also bars can be added with other functions, as well as those described below Fig. 5 to 10 can be seen.
- the organic material in the reactor 5 is then thermally decomposed, in particular subjected to a thermolysis.
- the described configuration of the screw conveyor 6 allows not only Hochtemperaturthermolysen and the implementation of the aforementioned flash pyrolysis.
- the organic material 1 is heated very quickly in the absence of oxygen in a medium-temperature process, preferably at about 475 ° C.
- small particles are decomposed at very high heating and heat transfer rates, whereby usually about 60% to 70% (then at room temperature) liquid products are produced as combustible fuels, and additionally each still about 10% to 20% combustible gas and about 15% to 25% residual carbon, based on 100% dry substance of the organics (organic substance 1).
- the carbon mixes with any inorganic material which may be present or formed, such as e.g. As metals or salts.
- the thermal decomposition of the organic substances 1 can also be carried out as so-called monocarbon thermolysis in a temperature range of 650 ° C to 800 ° C, based on 100% dry matter of organic substances 1 only CO, H2, CH4 and carbon arise.
- the resulting gas is decoupled from the gas outlet 11 and passes into a gas cooler 12, where it is cooled down in a cooling coil 13, for example to a temperature of 50 ° C. suitable for later use of the gas for power generation.
- Liquid fractions condense and are collected in the container 14. From this, the liquid fuels and residual water can be withdrawn via an outlet 15.
- oils in particular vegetable oils, preferably rapeseed oil
- Rapeseed oil has a particularly good ability to bind tars.
- the scrubbing liquid laden with solids, in particular with carbon, is sucked off via an outlet 19 and can be supplied as input material to the process of thermal decomposition of the organic substances 1. This can happen, in particular, if so much pulverized coal has formed in the reactor that the viscosity has increased so much that the gas can only pass through the washing liquid to a limited extent.
- the purified gas is sucked by means of a pump 17 and pressed into a gas supply system 18, wherein gas sensors and flow meters are located.
- the mixture of pure carbon and inorganic material passes through the aforementioned gas-tight lock 9 directly into a synthesis reactor 10.
- the carbon generated in the decomposition in a spatially and temporally decomposition downstream synthesis process in steam atmosphere reacted at temperatures in the range of 850 ° C to 1000 ° C to carbon monoxide and hydrogen.
- the water vapor necessary for the synthesis is sprayed via a feed line 20.
- the carbon is continuously conveyed, swirled in the chamber and fed to an outlet 22 in the inorganic material remaining in the synthesis reaction.
- this is then passed as ash or residual waste via a further rotary valve 23 in an ash pan 24.
- the resulting CO / H 2 gas mixture is decoupled at the gas outlet 25 and then tempered down in a cooler 26. Any existing residual water from unreacted water vapor is separated and removed via a water outlet 27.
- the gas flows into a gas scrubber 28 and is freed from residual dust there.
- a sump 29 of the scrubber 28 is then sucked in an overload with dust on the Sumpfabsaugung 30, wherein the liquid can also be fed back to the reactor 5 for thermal decomposition.
- the gas mixture is sucked off via a pump 31, controlled in the gas stream by means of sensors 32 and then pressed into a gas line 33.
- this can then - regardless of the gas composition which has the gas exiting from the decomposition reactor 5 - advantageously always identical gas mixture via a shift reactor 34 for the water gas further treated by in the shift reactor 34 when supplying steam to iron (III) oxide catalysts 35 at temperatures in the range of 250 ° C to 450 ° C, the carbon monoxide is converted into carbon dioxide, wherein additionally hydrogen arises: Complete conversion of CO into CO 2 doubles the production of hydrogen.
- the carbon dioxide contained in the gas mixture can in a further optional refrigeration unit 38, which z. B. is filled with liquid nitrogen as a coolant, are liquefied by passing it through a cooling coil 39 and thereby cooled to below - 60 ° C.
- the liquid CO 2 then flows at a pressure of over 6 bar into the collecting vessel 41 and can be removed from there via the outlet 42.
- the pure hydrogen gas is then available in the gas line 40.
- Fig. 2 It is shown how water vapor 45 is prevented from a thermally decomposing organic particles 43, since permanent decomposition gas 44 flows out of the particle 43.
- the figure thus illustrates that, as already stated above, it is technologically unfavorable to carry out thermal decomposition and synthesis in a single reactor because complete conversion of the organic substances 1 can not take place. Instead, with the hybrid system according to the invention, organic material can advantageously be converted 100% into combustible fuels and gases.
- FIG. 5 to 10 some constructive details of the device according to the invention are illustrated, to which also independent inventive importance is attributed and take into account the fact that the thermal decomposition of the organic substances and the synthesis process run as endothermic processes, the energy required is supplied allothermic process, ie that it is coupled in particular indirectly via walls of the reactors 5, 10 or alternatively or additionally also via a heat transfer medium guided through, for example, heating coils in each case through the reaction space.
- the reactors 5, 10 of the device according to the invention may preferably be tube furnaces in which conveyor screws 6, 21 are arranged.
- reactors 5, 10 but also rotary kilns can be used, wherein during the thermal decomposition and the synthesis process, the organic matter 1 and the carbon are continuously conveyed by kiln rotation.
- an improvement in terms of intensifying the reaction of thermal decomposition by a change in the inside of the decomposition reactor 5 (in Fig. 5 designated by the reference numeral 62) screw conveyor (in Fig. 5 designated by reference numeral 60).
- this screw conveyor 60 initially has scraping and turning bars 62. These are at least partially longitudinally to a housing of the reactor 5 extending, in particular approximately in cross-section approximately trapezoidal, transverse bar, which are shaped and arranged so that they the organic matter 1, the inorganic substances and / or the carbon in a Turn over movement through the reactor 5, if appropriate, also vortex and / or scrape off from a wall 59 of the reactor 5.
- Fig. 5 to 8 shows - additionally attached to the worm 60 Aufpressriegel 61, which in their various possible working positions in Fig. 6 to 8 Also designated by the reference numerals 64, 66 and 69 are. It is preferred, as the drawing illustrates, to longitudinally to a housing of the reactor 5 extending, in particular wing-like, in cross-section approximately crescent-shaped, obliquely to radial rays R through the reactor 5 arranged longitudinal bars which are shaped and arranged such that they distribute the organic substances 1, the inorganic substances and / or the carbon in a movement through the reactor 5 in a few millimeters thick layer on the wall of the reactor 5 and press against the wall 59 of the reactor 5.
- the sequence of figures 6 to 8 shows that the material (in Fig. 6 with the reference numeral 65 and in Fig. 7 denoted by 68) of the organic substance 1, which is located on a lower inner wall 63 of the reactor 5, taken up by the Aufpressriegel 64 and is brought in the rotational movement of the screw conveyor 60 as a thin layer 67 in direct contact with the hot housing surface 63. If the pressure bar then reaches position 69 ( Fig. 8 ), the entire material 71 is pressed in a thin layer on the hot surface 70 and evaporates or decomposes in direct contact with the wall very spontaneously and in a few seconds.
- FIGS. 9 and 10 can show on the worm (here denoted by reference numeral 73) in addition to scraping and Wenderiegeln (here by the reference numeral 74) and pressure rollers 75 may be attached.
- These are preferably longitudinal bars extending longitudinally of the housing of the reactor 5, which are designed as rollers which are freely movable in the radial direction and are fastened and designed on the conveyor screw 73 in such a way that they hold the organic, Inorganic substances and / or press the carbon in a few millimeters thick layer to the wall 72 of the reactor 5 and comminute by a Zerwalzen on the wall of the reactor 5.
- Such pressure rollers 75 can react more easily to strongly cohesively shaped fittings of inorganic material and thus also avoid jamming. Furthermore, these rollers 75 roll the resulting carbon small.
- the roles in Fig. 10 denoted by the reference numeral 77 have a self-gravity and be mounted in a guide bar 76 on the worm, that the axis 78 of the roller can move freely in a recess (slot 79) of the guide bar 76.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
- Treatment Of Sludge (AREA)
Claims (15)
- Procédé d'obtention de carburants et gaz combustibles à partir de substances organiques (1), les substances organiques (1) étant décomposées thermiquement avec formation des carburants et gaz combustibles et avec formation de carbone,
le carbone formé dans l'espace intérieur d'un réacteur de décomposition (5) lors de la décomposition thermique étant transformé en monoxyde de carbone et hydrogène par un procédé de synthèse en aval de la décomposition dans un réacteur de synthèse (10) dans une atmosphère de vapeur d'eau, la décomposition thermique étant réalisée sous la forme d'un procédé anaérobie, un mélange de carbone pur et de matière inorganique formé lors de la décomposition thermique des substances organiques (1) passant depuis le réacteur de décomposition directement, sans refroidissement ni stockage intermédiaire, dans le réacteur de synthèse (10), et un gaz formé lors de la décomposition dans le réacteur de décomposition (5) étant découplé du réacteur de décomposition (5) par une sortie de gaz (11) et traité séparément, le carbone formé lors de la décomposition thermique des substances organiques (1) dans le réacteur de décomposition (5) étant mis en réaction de manière anaérobie dans le réacteur de synthèse (10) dans le procédé de synthèse en aval de la décomposition dans l'espace et dans le temps dans l'atmosphère de vapeur d'eau dans une plage de température allant de 850 °C à 1 000 °C, la décomposition thermique des substances organiques et le procédé de synthèse se déroulant sous la forme de procédés endothermiques, et l'énergie nécessaire pour cela étant introduite dans le procédé de manière allothermique, par couplage de celle-ci indirectement par des parois des réacteurs (5, 10) et/ou par un caloporteur mis en circulation dans des serpentins de chauffage dans la chambre de réaction respective, et des sections de four ou des fours séparés l'un de l'autre de manière étanche aux gaz étant utilisés en tant que réacteurs (5, 10). - Procédé selon la revendication 1, caractérisé en ce que des fours tubulaires sont utilisés en tant que réacteurs (5, 10).
- Procédé selon la revendication 1 ou 2, caractérisé en ce que les substances organiques (1) et le carbone sont transportés en continu, notamment à l'aide de vis de transport (6, 21, 60, 73) et/ou par rotation du four, pendant la décomposition thermique et le procédé de synthèse.
- Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que des résidus végétaux, tels que du bois ou du compost, une biomasse, des ordures ménagères, des déchets de plastique, des boues d'épuration, des déchets de viande, des pneus automobiles usagés et analogues sont utilisés en tant que substances organiques (1) pour la formation des carburants et gaz combustibles, les substances organiques (1) utilisées pour la formation des carburants et gaz combustibles contenant notamment 5 % à 50 %, de préférence 15 % à 20 %, d'humidité, qui est de préférence ajustée par un séchage en amont de la décomposition thermique, et les substances organiques (1) utilisées pour la formation des carburants et gaz combustibles étant notamment broyées en particules avant la décomposition, notamment d'une taille de particule moyenne dans la plage allant de 2 mm à 5 mm, une dimension des particules dans une dimension de l'espace des particules étant de préférence inférieure à 100 µm.
- Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que des additifs fonctionnels sont introduits dans le procédé pendant la décomposition thermique des substances organiques (1).
- Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que la totalité du carbone formé lors de la décomposition thermique est mis en réaction dans le procédé de synthèse, seuls les produits de cendre inorganiques formés lors de la décomposition étant notamment déchargés en tant que matières résiduelles.
- Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que les carburants et gaz combustibles formés par la décomposition thermique et le mélange gazeux de monoxyde de carbone et d'hydrogène formé lors du procédé de synthèse sont traités séparément, par condensation de ceux-ci et/ou soumission de ceux-ci à une épuration des gaz (16, 28), des huiles, notamment des huiles végétales, de préférence de l'huile de colza, étant notamment utilisées lors d'une épuration (16) des gaz formés par la décomposition thermique en tant que liquides de lavage, et, après une épuration (16) des gaz formés par la décomposition thermique et/ou du mélange de monoxyde de carbone et d'hydrogène, un liquide de lavage chargé avec un solide, notamment avec du carbone, étant notamment introduit dans le procédé de décomposition thermique des substances organiques (1) en tant que matériau de départ, notamment pour augmenter sa fluidité.
- Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce que le monoxyde de carbone formé lors du procédé de synthèse est transformé catalytiquement en dioxyde de carbone et hydrogène supplémentaire par un procédé de conversion du gaz à l'eau dans une plage de température allant de 250 °C à 450 °C avec de la vapeur d'eau supplémentaire, le dioxyde de carbone formé dans le procédé de conversion du gaz à l'eau étant notamment séparé de l'hydrogène, notamment par refroidissement en dessous de -60 °C.
- Procédé selon l'une quelconque des revendications 1 à 8, caractérisé en ce que les substances organiques (1) sont introduites dans le procédé de décomposition thermique sous un gaz protecteur.
- Procédé selon l'une quelconque des revendications 1 à 9, caractérisé en ce que la décomposition thermique des substances organiques (1) a lieu sous la forme d'une pyrolyse rapide dans une plage de température allant de 300 °C à 600 °C, notamment à environ 475 °C, environ 75 % à 85 % de carburants et gaz combustibles et environ 15 % à 25 % de carbone se formant par rapport à 100 % de masse sèche des substances organiques.
- Procédé selon l'une quelconque des revendications 1 à 9, caractérisé en ce que la décomposition thermique des substances organiques (1) a lieu sous la forme d'une thermolyse de monocarbone dans une plage de température allant de 650 °C à 800 °C, essentiellement du CO, de l'H2, du CH4 et du carbone se formant par rapport à 100 % de masse sèche des substances organiques.
- Procédé selon l'une quelconque des revendications 1 à 11, caractérisé en ce que l'énergie nécessaire pour la décomposition thermique des substances organiques (1) et pour le procédé de synthèse est mise à disposition au moins à hauteur de plus de 80 %, de préférence de plus de 95 %, par combustion des carburants et gaz combustibles obtenus à partir des substances organiques (1) et/ou par la chaleur formée dans un procédé de conversion du gaz à l'eau.
- Dispositif pour la réalisation d'un procédé selon l'une quelconque des revendications 1 à 12, comprenant un réacteur (5) pour la décomposition thermique de substances organiques (1) avec formation de carburants et gaz combustibles et avec formation de carbone, un réacteur de synthèse (10) pour la formation de monoxyde de carbone et d'hydrogène à partir de vapeur d'eau et à partir du carbone formé dans le réacteur (5) pour la décomposition thermique étant raccordé techniquement en aval du réacteur (5) pour la décomposition thermique, les réacteurs (5, 10) étant des sections de four ou des fours séparés l'un de l'autre de manière étanche aux gaz, qui sont reliés l'un avec l'autre par une écluse étanche aux gaz (9) pour l'introduction du carbone issu du réacteur (5) pour la décomposition thermique dans le réacteur de synthèse (10), le réacteur (5) pour la décomposition thermique comprenant une sortie de gaz (11) pour le découplage des gaz formés dans celui-ci, avec un refroidisseur de gaz raccordé (12), les réacteurs (5, 10) pouvant être chauffés indirectement par leurs parois et/ou par un caloporteur mis en circulation dans des serpentins de chauffage dans la chambre de réaction respective.
- Dispositif selon la revendication 13, caractérisé en ce que les réacteurs (5, 10) sont agencés l'un sur l'autre, de telle sorte que le carbone puisse s'écouler depuis le réacteur (5) pour la décomposition thermique dans le réacteur de synthèse (10) sous l'effet de son propre poids.
- Dispositif selon la revendication 13 ou 14, caractérisé en ce qu'au moins une vis de transport s'étendant axialement (6, 21, 60, 73) est agencée au moins dans un réacteur (5, 10), qui d'une part déplace les substances organiques (1), les substances inorganiques et/ou le carbone dans le réacteur (5, 10) et d'autre part racle et lamine les parois (59) du réacteur (5, 10), ladite au moins une vis de transport (6, 21, 60, 73), de préférence dans le réacteur (5) pour la décomposition thermique, comprenant notamment des traverses (62), notamment de forme approximativement trapézoïdale dans la section transversale, qui s'étendent au moins en zones longitudinalement par rapport à un boîtier du réacteur (5), qui sont dimensionnées et agencées de manière à retourner, faire tourbillonner et/ou racler sur une paroi (59) du réacteur (5) les substances organiques (1), les substances inorganiques et/ou le carbone lors d'un déplacement dans le réacteur (5), et/ou ladite au moins une vis de transport (6, 21, 60, 73), de préférence dans le réacteur (5) pour la décomposition thermique, comprenant des traverses longitudinales (61, 64, 66, 69) agencées en biais par rapport aux rayons dans le réacteur, approximativement sous la forme de faucille dans la section transversale, notamment à la manière d'une ailette, qui s'étendent longitudinalement par rapport à un boîtier du réacteur (5), qui sont dimensionnées et agencées de manière à répartir les substances organiques (1), les substances inorganiques et/ou le carbone lors d'un déplacement dans le réacteur (5) en une couche (67) d'une épaisseur de quelques millimètres sur la paroi du réacteur, et à les presser sur la paroi (59, 63) du réacteur (5), et/ou ladite au moins une vis de transport (6, 21, 60, 73), de préférence dans le réacteur (5) pour la décomposition thermique, comprenant des traverses longitudinales qui s'étendent longitudinalement par rapport à un boîtier du réacteur (5), qui sont configurées sous la forme de rouleaux presseurs (75) librement mobiles dans la direction radiale, et qui sont fixés sur la vis de transport (6, 21, 60, 73) et réalisés de manière à presser les substances organiques (1), les substances inorganiques et/ou le carbone en une couche d'une épaisseur de quelques millimètres sur la paroi (72) du réacteur (5), et à les broyer par laminage sur la paroi (72) du réacteur (5).
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PCT/EP2010/051938 WO2011101020A1 (fr) | 2010-02-16 | 2010-02-16 | Procédé et dispositif pour l'obtention de carburants et gaz combustibles à partir de substances organiques |
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DK (1) | DK2536495T3 (fr) |
ES (1) | ES2734519T3 (fr) |
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DE102023102586A1 (de) * | 2023-02-02 | 2024-08-08 | GSE Green Synthetic Energy GmbH | Verfahren und Vorrichtungen zur Erzeugung eines wasserstoffhaltigen Synthesegases |
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US1538796A (en) * | 1921-11-22 | 1925-05-19 | American By Products Corp | Multiple-unit retort |
US5151159A (en) * | 1990-11-15 | 1992-09-29 | Coal Technology Corporation | Method and apparatus for converting coal into liquid fuel and metallurgical coke |
DE19614689C2 (de) * | 1996-04-13 | 1999-11-04 | Maximilian Bauknecht | Multivalent einsetzbare Anlage zur thermischen Behandlung von Ausgangssubstanzen |
DK200000417A (da) * | 2000-03-15 | 2001-09-16 | Cowi Radgivende Ingeniorer As | Fremgangsmåde og anlæg til dekomposition, forgasning og/eller forbrænding af fugtigt brændsel. |
ATE372370T1 (de) * | 2000-05-26 | 2007-09-15 | Kunststoff Und Umwelttechnik G | Verfahren und vorrichtung zur thermischen behandlung und chemischen umsetzung von natur- und synthesestoffen unter zeugen eines produktgases zur weiteren verwendung |
US6758150B2 (en) * | 2001-07-16 | 2004-07-06 | Energy Associates International, Llc | System and method for thermally reducing solid and liquid waste and for recovering waste heat |
EP1323810A1 (fr) * | 2001-12-12 | 2003-07-02 | von Görtz & Finger Techn. Entwicklungs Ges.m.b.H. | Installation de gazéification à tubes doubles |
EP1447438B1 (fr) * | 2003-02-12 | 2015-07-08 | von Görtz & Finger Techn. Entwicklungs Ges.m.b.H. | Gazéification avec pré-pyrolyse de biomasse et gazéification additionnelle des gaz |
ATE551414T1 (de) * | 2006-06-07 | 2012-04-15 | Ilw Ingeneurbuero | Verfahren und vorrichtung zur dampfvergasung von biomasse |
BRPI0720677A2 (pt) * | 2006-12-26 | 2014-03-18 | Nucor Corp | Aparelho e método para produzir carvão. |
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