WO2017115019A1 - Arrangement and method for preparing a gas - Google Patents
Arrangement and method for preparing a gas Download PDFInfo
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- WO2017115019A1 WO2017115019A1 PCT/FI2016/050939 FI2016050939W WO2017115019A1 WO 2017115019 A1 WO2017115019 A1 WO 2017115019A1 FI 2016050939 W FI2016050939 W FI 2016050939W WO 2017115019 A1 WO2017115019 A1 WO 2017115019A1
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- reactor
- gasification
- water
- gas
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- 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
- C10J3/72—Other features
- C10J3/78—High-pressure apparatus
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0405—Apparatus
- C07C1/041—Reactors
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0485—Set-up of reactors or accessories; Multi-step processes
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- 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
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- 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
- C10J3/20—Apparatus; Plants
- C10J3/30—Fuel charging devices
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- 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
- C10J3/72—Other features
- C10J3/723—Controlling or regulating the gasification process
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/08—Production of synthetic natural gas
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/755—Nickel
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- 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
- C10J2200/09—Mechanical details of gasifiers not otherwise provided for, e.g. sealing means
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- 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
- C10J2200/154—Pushing devices, e.g. pistons
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- 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
- C10J2300/0913—Carbonaceous raw material
- C10J2300/0916—Biomass
- C10J2300/092—Wood, cellulose
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- 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
- C10J2300/0913—Carbonaceous raw material
- C10J2300/0946—Waste, e.g. MSW, tires, glass, tar sand, peat, paper, lignite, oil shale
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- 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
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- 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
- C10J2300/0979—Water as supercritical steam
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- 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
- C10J2300/1269—Heating the gasifier by radiating device, e.g. radiant tubes
- C10J2300/1276—Heating the gasifier by radiating device, e.g. radiant tubes by electricity, e.g. resistor heating
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- 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
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/1603—Integration of gasification processes with another plant or parts within the plant with gas treatment
- C10J2300/1621—Compression of synthesis gas
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- 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
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
- C10J2300/1656—Conversion of synthesis gas to chemicals
- C10J2300/1662—Conversion of synthesis gas to chemicals to methane (SNG)
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Definitions
- the invention relates to an arrangement according to the preamble of claim 1 for preparing a gas in a closable reactor by supplying said reactor with biomass or chopped wood material, especially chips, in substantially oxygen-free conditions, by allowing the biomass or chopped wood material to gasify at a high temperature, and by recovering a (gasification) gas generated in the gasification reaction.
- the invention relates also to an arrangement according to the preamble of claim 2 for preparing a gas in a closable reactor by supplying said reactor with plastic material or plastic-based material in substantially oxygen-free conditions, by allowing the plastic material or plastic-based material to gasify at a high temperature, and by recovering a gas generated in gasification reaction.
- wood gas particularly from wood material, and even more specifically from chips
- wood gas can be produced wood gas by introducing excess air into a fuel and air mixing chamber or mixer head.
- the resulting gas contains a fairly large amount of unburned inert nitrogen gases and the combustion value of generated wood gas per unit of supplied wood material remains low.
- the production costs will rise dramatically because of the price of oxygen feed.
- Both foregoing problems are at least partially avertable in so-called pyrolysis, wherein wood material, such as chips, is heated while attempting at the same time to avoid the passage of air or oxygen into the mixer head or gasification space.
- wood material such as chips
- the pyrolysis of wood material, such as chips provides a solution to the foregoing problems relating to the produced gas having a low combustion value per unit of supplied wood material
- one major problem in pyrolysis results from impurities which migrate from wood material to gas fraction and hamper further processing of the product for example with a well-known Fischer-Tropsch process, and from impurities, most notably tars, which are left in so-called pyrolysis oil as a result of incomplete combustion.
- the elimination of impurities contained in pyrolysis oil and in gas fraction entails normally a considerable increase in pyrolysis costs.
- the pyrolysis-generated impurities can be reduced with a so-called ablative pyrolysis in which wood material, such as chips, is gasified at a high tempera- ture and at a relatively high pressure, but the problem here turns out to be a low conversion of wood material, resulting in 30-35% of unburned carbon residue per kilogram of supplied dry wood material.
- a further objective of the invention was to provide an arrangement that would also enable the gasification of plastics or a plastic-based material.
- the invention relates to an arrangement for preparing a gas in a closable reactor by supplying said reactor with carbon-based biomass or chopped wood material, especially chips, in substantially oxygen-free condi- tions, by allowing the chips to gasify at a high temperature, and by recovering the gas (G) generated in a gasification reaction.
- the arrangement for preparing a gas in a closable reactor by supplying said reactor with carbon-based biomass or chopped wood material, especially chips, in substantially oxygen-free condi- tions, by allowing the chips to gasify at a high temperature, and by recovering the gas (G) generated in a gasification reaction.
- a reactor's interior is defined by a feed pipe whose inlet is closable with a shut-off valve, especially with a ball valve, and whose outlet end adjoins a heatable gasification dome,
- the reactor's interior is supplied with free water/water vapor (V), preferably in its supercritical state, which is optionally prepared catalytically by splitting the water/water vapor (V),
- the biomass or wood material is conveyed into the reactor interior's gasification space, which is in connection with the heated gasification dome and which is adapted to have existing conditions selected in a manner such that the water (V) present in said gasification space is present in its supercritical state, - the gas (G) generated in the gasification reaction is recovered.
- the reactor is elongated.
- the invention relates also to an arrangement of claim 2, which differs from that of claim 1 in the sense that the biomass or wood-based material is here replaced by using a plastic material or a plastic-based material.
- the invention relates also to a method for preparing a gas in a closable reactor by supplying said reactor with carbon-based biomass or chopped wood material, especially chips (H), in substantially oxygen-free conditions, by allowing the biomass or wood material to gasify at a high temperature and by recovering a resulting gas (G).
- the method comprises:
- the supercritical water refers to a state of water in which the separate vapor and liquid phases of water are no longer distinguishable but, instead, water is present in the form of a supercritical fluid in which the liquid and gaseous forms of water are in equilibrium. Water is present in the form of a supercritical fluid when it is above a certain supercritical point at which it has a pressure of 22.064 Mpa (about 217 bar) and a temperature of 647 K (374 )
- the carbon-based biomass refers in this disclosure to so-called energy waste or combustible wood, logging waste, as well as plants with a content of sugar and starch.
- the gasification space is adapted to have an existing pressure of not less than 220 bar and a temperature of 374 .
- the principal components of a gasification gas G generated in a chips gasification reaction of the invention are H 2 , CO, CO 2 , CH 4 and possibly some higher hydrocarbons, depending on a temperature of the gasification space. However, by a higher partial pressure of water in a gasification reaction (R)
- the reaction is controlled in such a way that a majority of the gasification gas (G) consists of hydrogen gas, nor is there present hardly any higher hydrocarbons.
- a significant benefit attained with a method and arrangement of the invention is a capability of controlling the gasification process effectively so as to efficiently minimize the amount of impurities in a gasification gas or in a product gas obtained from methanation of the gasification gas.
- Supplementing the reactor's interior, preferably the gasification chamber, with free water/steam /V), preferably in its supercritical state, provides an ability to improve the process considerably in terms of its manageability and control as compared to the situation in which the water/steam would all be delivered along with a material, such as biomass or chips, to be supplied into the process.
- the process can, among others, be supplied with precisely measured additives e.g. for reducing the amount of tar and for optimizing energy production on the basis of the composition, water content of the material to be supplied into the process.
- biomass or chopped wood material is supplied from an inlet end of the feed pipe into the reactor's interior.
- the water content held by supplied biomass or chopped wood material and/or the amount and type of impurities contained in biomass or chopped wood material will be measured or assessed.
- the measured or assessed water content of supplied biomass or chopped wood material is used as a basis for regulating the amount of free water/steam supplied into the reactor's interior, preferably into the gasification space.
- the water content of biomass or chopped wood material can be assessed or measured before or after its delivery into the reactor's interior.
- the process control provides a capability of controlling the process in a manner that is faster, more precise, and more versatile than in methods known from the prior art: publications WO2013030028, WO9630464 and JPH06299169, among others, have proposed methods for the gasification of chips and biomass, wherein the entire amount of water/steam to be introduced into the process arrives along with the chips/biomass supply.
- Such a process is considerably more inconvenient to regulate than the one provided by the invention, because, for example, the feedback control is awkward and less precise.
- additives which enable the binding of materials possibly contained in the feed and detrimental to further process, or materials whose bonding to ash is desirable.
- additives include for example various calcium compounds, which may enable alkali metals to be bonded to ash, such as potassium, contained in wood, thereby improving the fertilizer value of ash.
- the use of calcium compounds provides a capability of binding as calcium sulfate for exam- pie the sulfur S present in wood, which may otherwise cause problems as the process continues.
- a major benefit attained by the use of high pressure is that the amount of produced tars is very small, i.e. the produced gasification gas G is very pure in and of itself.
- the gas can be purified further by converting impurities left in the gas into a form soluble in water or in an aqueous solvent.
- the reactor is supplied, along with supercritical water, with an oxygen-binding sub- stance such as carbon or sodium.
- a gasification dome's discharge opening by which the gasification gas G generated in the gasification space and the ash are able to exit into the reaction chamber's discharge space in such a way that the gasification gas G passes through the ash.
- the method and arrangement of the invention enable a minimization of the amount of carbon in the ash discharging from the gasification space.
- water is present in the gasification space in its supercritical state. This provides a considerable benefit in the sense that the complete gasification of wood is accomplished at a temperature as low as about 374 ⁇ C, preferably at a tern perature higher than 700 ⁇ C, thereby enabling a minimization of the carbo n content of ash.
- the carbon content is extremely low, less than 1 %, preferably less than 0,5% - as a result of a high pressure used in the gasification reaction and the presence of supercritical water in the reaction.
- the reactor's interior has its gasification space 30; 31 supplied with water V; V2 in supercritical state for increasing the amount of carbon dioxide and hydrogen in what takes place in the gasification space 30, 31 as a gasification reaction R:
- the gasification gas G (or subsequently also simply the gas), generated in the reaction R, has a ratio H 2 /CO > 2.
- the gas can be synthesized for example with Fischer-Tropsch synthesis.
- Fig. 1 shows in a schematic presentation the steps of a method according to the invention.
- Fig. 2 shows, in a lengthwise sectional view, the chips supply means, a reactor, as well as a reactor chamber for an apparatus used in an arrangement of the invention.
- Fig. 3 shows, in a lengthwise sectional view, a heat exchanger and a gas scrubber for an apparatus used in an arrangement of the invention.
- the method comprises a supply 300 of chopped wood material, particularly chips, into a reactor 3 of chips feeding means 2, and a subsequently occurring gasification 100 of the chips in a gasification space 31 of the reactor 3.
- the chips supply 300 includes chopping 310 the chips with a chip container's crusher 232, packing 320 the chips in a densification cylinder 21 through the use of a feeding cylinder 22.
- an optional carbon dioxide supply 500 for displacing oxygen from chips H This is followed by the chips H being preheated 330 and delivered by means of the feeding cylinder 22 into the reactor 3.
- a gasification gas G proceeds into a pipe heat exchanger 6 opening into the upper part of a reaction chamber 4, wherein the gasification gas G has its thermal energy used for heating water to be supplied into the reactor 3 and, at the same time, the gasification gas G is methanated 610 in catalytic Sapatier reaction into a product gas G1 .
- Water V; V2 to be supplied into the reactor's gasification space 31 is first heated by means of a heat exchange with the gasification gas G while being simultaneously conveyed through a catalytic zone 66 for bringing the water V to a supercritical state prior to its introduction into the gasification space 31 .
- Fig. 2 shows the upstream end of an apparatus 1 used for the gasification 100 of chips employed in an arrangement of the invention, said upstream end extending from the supply 300 of chips to the supply of gasification gas into the pipe heat exchanger 6.
- fig. 3 shows parts of the apparatus 1 , which are used for the methanation of gasification gas into a product gas G1 and for the simultaneous heating 410 of water V; V1 into supercritical water V; V2, and for the scrubbing 600 of the product gas G1 .
- the apparatus 1 used in an arrangement of the invention comprises the following principal components: chips supply means 1 , a reactor 3, a reaction cham- ber 4, a cooling liquid tank 5, a catalytic pipe heat exchanger 6, an ash removal device 7, a gas scrubber, a methane separator.
- the wood shavings H are delivered 3 with the supply means 2 into the reactor 3.
- These chips supply means 2 include a chips feeder 23, which is visible in fig. 2 and which is intended for bringing the crushed chips first into a chips densification cylinder 21 .
- the chips are compressed for removing excess water and air.
- a feeding cylinder 22 In connection with the densification cylinder 21 is a feeding cylinder 22 by means of which the compressed and crushed chips are intended to be delivered into an interior 30 of the reactor 3 by way of a shut-off valve 24 and a compaction plate 25.
- the reactor 3 is surrounded by a reaction chamber 4, into which the gasification gas G and the ash discharge from the reactor 3 as subsequently described.
- the reaction chamber 4 is surrounded by a cooling liquid tank 5 and the gasification gas G is recovered and methanated in a catalytic heat exchanger 6 which is located in conjunction with the reaction chamber 4, commencing from its upper part, extending by way of the reaction chamber 4 and the cooling liquid tank surrounding the same, the catalytic heat exchanger 6 being also provided with means for bringing the water to be supplied into the reactor to a supercritical state by means of a heat exchange with a hot product gas traveling in the heat exchanger 6.
- the reaction chamber has its bottom part provided with an ash removal device 7, comprising a base plate, an ash removal conduit, and a two-piece valve assembly 73 present in the ash removal conduit for regulating the removal of ash.
- the methanated product gas discharging from the catalytic heat exchanger is cleaned by liquefaction in a gas purifier 8, which operates on the Fischer Trop- sch method.
- a gas purifier 8 In functional communication with the purifier 8 is a water scrubbing unit or scrubber 10 for impurities as well as a methane separator 9,
- the chips supply means 2 have the chips feeder thereof provided with a storage conveyor 233, such as a screw or chain conveyor, which extends from chips storages (not shown in the figures) to the chips container 231 fitted with a crusher 232.
- the chips container's 231 crusher 232 is intended for crushing the wood shavings for crushed wood as "pulpy" as possible and consistent in quality, preferably without leaving any splinters, bark slivers or the like.
- the chips container 231 must be tight as it has connected thereto an optional carbon dioxide supply 237.
- the purpose of carbon dioxide is to displace air from the crushed chips H so as not to generate too much carbon monoxide in subsequent gasification of the chips H. If necessary, the chips can be heated in the chips container 231 with appropriate heating elements coupled to the chips container.
- a bottom portion of the chips container is provided with a feed conveyor 234 such as a screw conveyor 234.
- the feed conveyor 235 has its bottom end located in connection with the chips container 231 while its top end extends to a vertical densification cylinder 21. Between a longitudinal direction of the feed conveyor and a longitudinal direction of the densification cylinder 21 must exist an angle of at least 45 degrees.
- the densification cylinder 21 comprises an upper cylinder 21 1 and a tubular compaction piston 212 intended for compressing the chips to a condition as dense as possible for the removal of excess oxygen and air.
- the feeding cylinder 22 comprises a lower cylinder 221 and a feeding piston 222.
- the feeding cylinder 22 is intended for delivering the chips into a reactor and for further packing the chips in the densification cylinder 21 by pressing the chips at a top end of the densification cylinder 21 into the reactor 3 through a shut-off valve 24, especially a ball valve, and a compaction plate 25 located downstream thereof in the feeding direction.
- the densification cylinder 21 has a filling capacity of about 3,5 liters, into which densification cylinder 21 is squashed about 5-6 liters of crushed chips by the feed conveyor 235.
- the piston of the feeding cylinder 22 is a hydraulic cylinder piston rod, for example 100 mm in diameter and for example 400 mm + 230 mm in stroke length.
- the densification cylinder 21 is provided with a tubular compaction cylinder/piston 212 with a tubular piston rod which has a material thickness of about 2 mm and is made of a highly durable material.
- the tubular compaction piston 212 is machined for a tight tolerance with the feeding piston 222.
- the lower cylinder 221 has such a tolerance that gaseous substances, such as "excess" water and possible air contained in the chips, will be able to depart from the system upon pre-pressing the chips against said shut-off valve, especially the ball valve 24, with a force of about 20-30 tn.
- the shut-off valve 24 is preferably a ball valve 24, which is designed for a pressure of about 350 bar.
- the compaction plate 25 is a conically tapering throttle plate which opens into a bottom part of the reactor's 3 feed pipe 35. The compaction plate 25 packs the chips H to a "final" density, as well as prevents the chips from "trickling" back towards the feeding cylinder 22.
- the reactor 3 becomes closed by a feed pipe 35 capable of being provided from the bottom end, by a gasification dome 36 delimiting it from the top end, and by heating devices 42 for the gasification dome 36.
- the feed pipe 35 comprises a conically expanding tubular reactor, which has a bottom part 200 mm in diameter and which is delimited at the top end by the gasification dome 36. It is the feed pipe 35 and the gasification dome 36 adjacent thereto which define an interior 30 for the feed pipe or reactor, wherein gasification of the crushed and packed chips H takes place.
- the gasification dome 36, delimiting the feed pipe 35 at the top end, is preferably a hemispherical conduction parabola capable of being heated electrically with the gasification dome heating devices 42.
- the gasification dome 36 is preferably insulated from outside for example with an aerogel or alumina wool insulation of about 20 mm in thickness.
- the conduction parabola 36 must be made of a material capable of withstanding the temperature of at least +1700 ⁇ C as it is heated to about 1500 ⁇ C with an electric current generated by the heating devices 42.
- the reactor 3 has its interior 30 defined by a reactor cooling space 33 located at a bottom part of the feed pipe downstream of the supply means 2 in the chips feeding direction, as well by a reactor preheating space 32 and by a reactor gasification space 31 located in the proximity of the gasification dome 36.
- the gasification space 31 is capable of being supplied with supercritical water by way of a supercritical water inlet pipe 61 with nozzles at its end opening into said gasification space 31 .
- the supercritical water is produced, as subsequently described, with a heat transfer taking place between gasification gas generated in the gasification space 31 and water in a pipe heat exchanger 6.
- the temperature of chips in the chips feeding direction rises in the feed pipe 35 rapidly to about 240 ⁇ C over a distance of 10 cm.
- the formation of tars begins in the interior 30 of the reactor 3 near the compaction plate 25 opening into a bottom end of the feed pipe 35 (at a distance of about 15-20 cm from the compaction plate in the chips advancing direction).
- the pressure existing in the interior 30 pushes the tars downward to fill all cell tissues of the chips arriving in the interior.
- the further down tars are able to penetrate in the feed pipe 35, counterclockwise with respect to the chips feeding direction or chips advancing direction, the colder are the chips present in the reactor's cooling space 33.
- the tars coagulate to build a plug which contributes to prohibiting the escape of pressure.
- the temperature of chips H exceeds +700 and the water , possibly contained in the chips, has turned into a supercritical state, promoting effectively the de- composition of tars into gases.
- the actual gasification reaction R of chips takes place in a gasification space, which is at a top end of the feed pipe 35, near the gasification dome 36, and in which a pile is built up by chips H and ash.
- the chips H present in the gasification space is heated to the temperature of +1000 ⁇ C - +1200 with a hemi- spherical conduction parabola of the gasification dome 36.
- the infrared rays generated by the conduction parabola 36 are focused in the middle of a gasification space in the reactor's interior 39, wherein the gasification reaction of chips takes place and into which the catalytically split supercritical water is also pumped by way of a nozzle in the water inlet pipe 61 .
- Water is present in the form of a supercritical fluid above a certain supercritical point at which it has a pressure of 22.064 Mpa (about 217 bar) and a temperature of 647 K (374*C).
- the principal components of a gasifying reaction-generated gasification gas G are H 2 , CO, CO 2 , CH 4 and possibly some higher hydrocarbons, depending on temperature in the gasification space.
- said reac- tion is controlled by a high partial pressure of water in the reaction (R) in such a way the chips gasification gas G consists for the most part of hydrogen gas, nor is there present hardly any higher hydrocarbons.
- the gasification space 31 should have an existing pressure of at least 220 bar and a temperature of 374 .
- Under the gasification dome are gasification dome discharge openings 41 , leading to a reaction chamber 4 that surrounds the reactor 3.
- the gasification gases of about 145 kg/100 kg of chips, generated in the reaction (R), as well as ash, shall exit by way of the discussed discharge openings 41 into the reactor-surrounding reaction chamber 4, such that the gasification gases G discharge through the ash layer as in a traditional co-current downdraft gasifi- er, whereby a major portion of the gas impurities shall remain in possibly molten ash, the amount of which is about 0,5-1 kg per 100 kg of chips.
- the reaction chamber 4 is built up of two pressure vessel hemispheres cou- pled to each other by welding, bolts or otherwise to form a pressure vessel.
- Walls 49; 49b defining a middle section of the reaction chamber's 4 interior are half-heart shaped in the reaction chamber shown in the figure, and walls 49; 49c of the reaction chamber's 4 bottom end have attached thereto the reactor's feed pipe 35, as well as an ash removal conduit 72 and a base plate 71 of the ash removal device 7.
- the reaction chamber has its bottom part provided with a water point 45 wherefrom it is conducted to the pipe heat exchanger 6 along a cooling water conduit 64 in which it is converted into supercritical water.
- the reaction chamber 4 has its top end fitted with a safety valve 47, which releases the gas pressure in case the pressure in the reaction chamber 4 rises too much, e.g. to higher than 230 bar.
- the reaction chamber 4 has an ash channel 44, which surrounds the reactor preheating space 32 and cooling space 33 present in a bottom part of the feed pipe 35.
- the reaction chamber 4 has its bottom part provided with an ash removal device 7, which is in communication with the ash channel 44.
- the hot ash falls from the gas discharge openings downward into the ash channel and towards the ash removal device 7.
- the gasification gases G discharge by way of a discharge opening 41 about 20 mm wide into a spherical gas discharge space 40 of the reaction chamber 4, wherein the flow rate of gases G becomes slower.
- the reaction chamber 4 has its upper part, i.e.
- the reaction chamber which is defined by the walls 49; 49a, provided with a gas removal space 43 which is in communication with the gas discharge space 40.
- the pipe heat exchanger 6 which in this case is a catalytic pipe heat exchanger with the supercritical water inlet pipe 61 extending therein. It is an objective that the heat of hot ash migrating downward along the ash channel 44 be transferred as effectively as possible to the chips H moving upward in the reactor's interior 30. This is why the ash channel 44 includes heat transfer flanges 46 at a point of the feed pipe 35 in alignment with the reactor preheating space 32 at a bottom part of the feed pipe 35 (approximately halfway along the feed pipe 35).
- the reactor 3 has its internal surface insulated with a high temperature resistant insulation material, for example alumina or aerogel.
- the insulation layer is required to prevent the temperature as high as +1200 of the reactor 3 from penetrating into the reaction chamber's pressure vessel structure.
- To a bottom part of the reactor 3 is welded a sturdy plate, upon which the entire apparatus has been erected and to which is fastened with bolts a cooling liquid tank 5 insulated with PU insulation and surrounding the reaction chamber 4.
- the ash removal device includes a chilled base plate 71 , which is inclined quite a lot and bent into a curved shape, the ash cooling rapidly.
- the ash trickles from the base plate into an ash removal conduit 72.
- An upper part 72a of the ash removal conduit 72 includes an upper valve assembly 73; 73a and a lower part 72b of the ash removal conduit includes a lower valve assembly 73; 73b.
- Each of the valve assemblies 73; 73a, 73b is provided with a sleeve valve and a ball valve (shut-off valve). The sleeve valves are manipulated with a 221 bar pressure from side to side.
- the catalytic pipe heat exchanger 6 is shown in figs. 2 and 3.
- the pipe heat exchanger 6 consists of three concentric tubes.
- the outermost tube is a pressurized water pipe 63 in which water V; V1 arrives at a pressure of about 225 bar and at a temperature of about 90 from a cooli ng water pipe 64 which comes from the water point 45 (fig. 2).
- the pressurized water pipe 63 must have its walls 63a capable of withstanding a pressure of at least 350 bar.
- the next inner tube is a gas pipe 62 about 54-55 mm in diameter. The difference between a water pressure existing in the pressurized water pipe 63 and a gas pressure of the gas pipe 62 is about 5 bar.
- the gasification gas G discharging from the reaction chamber 4 into the gas pipe 62 has a temperature of about 1000 ⁇ C at the re action chamber end of the gas pipe 62, and moreover, the gas pipe 62 must also be capable of withstanding acids present in the gasification gas G.
- Around the gas pipe 62 is wound a wire of less than 2 mm for a spring that retains the gas pipe 62 and the pressurized water pipe 63 apart from each other and compels the water to travel a longer distance for an effective transfer of heat from the gasification gas G to the water V; V1 flowing in the pressurized water pipe 63.
- the water temperature rises about 400 ⁇ C in the pressurized wa ter pipe.
- a supercritical water inlet pipe 61 which includes a catalyst zone 66 for the decomposition of water V; V1 passing therethrough into supercritical water V; V2 before the water V; V2 arrives in the reactor's gasification space 31 .
- Possible catalysts include, among others, cobalt Co, manganese dioxide (MnO 2 ) or nickel borate.
- V2 can be pumped into the reactor's gasi- fication space 31 also substances which facilitate the bonding of impurities to ash.
- V2 can also be pumped other chemicals into the reaction for providing a desired gas composition.
- the supercritical water pipe 61 and the pressurized water pipe 63 remains a space of about 5 mm, in which the gasification gas G flows at a speed sufficient for possible particles to keep up with the flow.
- a spiral spring On a surface 62a of the supercritical water pipe 61 is wound a spiral spring.
- An external surface 63a of the pressurized water pipe 63, an internal surface 66a of the gas pipe 62, as well as the spiral spring can be coated with a catalyst material, e.g. nickel (Ni), for generating a so-called Sapatier reaction in which the gasification gas is methanated.
- a catalyst material e.g. nickel (Ni)
- the gas recovery 600 water is removed from the product gases G1 and impurities are water washed from the gases in a gas scrubber 10.
- the gases are cooled to below a dew point temperature for the densification and removal of water.
- the gases are conducted in a conventional manner into water, in which are retained those impurities which have not bonded to ash in the reactor 3 and discharged, such as acids, ammonia, sulfuric acid, hydrogen chloride, alkali metals.
- the gases are conducted to a gas purifier/liquefier 8, in which the product gas G1 is liquefied for example with a catalytic Fischer- Tropsch process by raising temperature of the gases by +250 - +300 ⁇ C with the heat of through-flowing gases.
- the product gas obtained from the catalytic gas purifier 8 should be as follows: hydrogen (H 2 ) about 50%, carbon monoxide (CO) about 25%, and methane (CH 4 ) about 25%.
- the non-liquefiable gases such as methane
- the non-liquefiable gases are conveyed by way of a refrigerator and a pressure reducing valve into a pressure container 9 to a maximum pressure of about 200 bar, wherefrom the methane gas is collected either to a gas engine or a fuel cell to produce electricity.
- Fischer-Tropsch synthesis and catalysts such as Fe, Co, Ru can be used for the liquefaction of hydrogen gas H 2 e.g. into biodiesel or some other desirable chemical compound (ethanol, methanol, DME, etc.).
- the process control can be upgraded in such a way that, when biomass or chopped wood material is introduced from an inlet end of the feed pipe 35 into an interior of the reactor 3, the supplied biomass or chopped wood material is measured or assessed for its water content.
- the measured or assessed water content of biomass or chopped wood material delivered into the reactor is used as a basis for regulating the amount of free supplementary wa- ter/supplementary steam to be introduced into the reactor.
- the water content of biomass or chopped wood material can be assessed or measured before or after its delivery into the interior of the reactor 3.
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- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
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Abstract
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Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
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JP2018553317A JP6999571B2 (en) | 2015-12-30 | 2016-12-30 | Equipment and methods for preparing gas |
CN201680077683.8A CN108431181B (en) | 2015-12-30 | 2016-12-30 | Apparatus and method for producing gas |
CA3009581A CA3009581A1 (en) | 2015-12-30 | 2016-12-30 | Method of preparing a gas from biomass in a reactor |
EP16881331.9A EP3397733B1 (en) | 2015-12-30 | 2016-12-30 | Arrangement and method for preparing a gas |
ES16881331T ES2928946T3 (en) | 2015-12-30 | 2016-12-30 | Arrangement and method for preparing a gas |
DK16881331.9T DK3397733T3 (en) | 2015-12-30 | 2016-12-30 | DEVICE AND METHOD FOR MANUFACTURING A GAS |
PL16881331.9T PL3397733T3 (en) | 2015-12-30 | 2016-12-30 | Arrangement and method for preparing a gas |
US16/066,505 US10752851B2 (en) | 2015-12-30 | 2016-12-30 | Arrangement and method for preparing a gas |
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FI20156029 | 2015-12-30 |
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PCT/FI2016/050939 WO2017115019A1 (en) | 2015-12-30 | 2016-12-30 | Arrangement and method for preparing a gas |
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US (1) | US10752851B2 (en) |
EP (1) | EP3397733B1 (en) |
JP (1) | JP6999571B2 (en) |
CN (1) | CN108431181B (en) |
CA (1) | CA3009581A1 (en) |
DK (1) | DK3397733T3 (en) |
ES (1) | ES2928946T3 (en) |
PL (1) | PL3397733T3 (en) |
WO (1) | WO2017115019A1 (en) |
Cited By (3)
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US11286436B2 (en) | 2019-02-04 | 2022-03-29 | Eastman Chemical Company | Feed location for gasification of plastics and solid fossil fuels |
US11447576B2 (en) | 2019-02-04 | 2022-09-20 | Eastman Chemical Company | Cellulose ester compositions derived from recycled plastic content syngas |
US11939406B2 (en) | 2019-03-29 | 2024-03-26 | Eastman Chemical Company | Polymers, articles, and chemicals made from densified textile derived syngas |
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- 2016-12-30 JP JP2018553317A patent/JP6999571B2/en active Active
- 2016-12-30 EP EP16881331.9A patent/EP3397733B1/en active Active
- 2016-12-30 CN CN201680077683.8A patent/CN108431181B/en active Active
- 2016-12-30 US US16/066,505 patent/US10752851B2/en active Active
- 2016-12-30 DK DK16881331.9T patent/DK3397733T3/en active
- 2016-12-30 CA CA3009581A patent/CA3009581A1/en active Pending
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US11447576B2 (en) | 2019-02-04 | 2022-09-20 | Eastman Chemical Company | Cellulose ester compositions derived from recycled plastic content syngas |
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Also Published As
Publication number | Publication date |
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PL3397733T3 (en) | 2022-12-05 |
EP3397733A1 (en) | 2018-11-07 |
EP3397733A4 (en) | 2019-08-14 |
US20190002777A1 (en) | 2019-01-03 |
US10752851B2 (en) | 2020-08-25 |
EP3397733B1 (en) | 2022-08-24 |
CN108431181A (en) | 2018-08-21 |
DK3397733T3 (en) | 2022-11-07 |
JP6999571B2 (en) | 2022-01-18 |
JP2019505654A (en) | 2019-02-28 |
ES2928946T3 (en) | 2022-11-23 |
CN108431181B (en) | 2021-10-01 |
CA3009581A1 (en) | 2017-07-06 |
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