Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
  • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
  • C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
  • C10G3/40—Thermal non-catalytic treatment
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
  • C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
  • C10B57/005—After-treatment of coke, e.g. calcination desulfurization
• • 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
  • C10J3/46—Gasification of granular or pulverulent flues in suspension
  • C10J3/48—Apparatus; Plants
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
  • C10K1/00—Purifying combustible gases containing carbon monoxide
  • C10K1/002—Removal of contaminants
  • C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
  • C10K1/004—Sulfur containing contaminants, e.g. hydrogen sulfide
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1011—Biomass
  • C10G2300/1014—Biomass of vegetal origin
• • 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
  • C10J2300/0966—Hydrogen
• • 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
  • C10J2300/0976—Water as steam
• • 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
  • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
  • C10L2290/04—Gasification
• • 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
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E50/00—Technologies for the production of fuel of non-fossil origin
  • Y02E50/10—Biofuels, e.g. bio-diesel
• • 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
  • Y02P30/00—Technologies relating to oil refining and petrochemical industry
  • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

• the subject of the present invention is a method for the manufacture of bio-methane and eco-methane by hydrogasification of bio-carbon and fossil carbon where bio-hydrogen is the gasification agent.
• Bio-hydrogen is a product formed from biomass through reaction of bio-methane with water vapour.
• Bio-methane is a product of hydrogasification of bio-carbon using bio-hydrogen.
• the product of hydrogasification of coal or lignite using bio-hydrogen is eco-methane.
• Bio-carbon is a product of pyrolysis of dry biomass preferably with high content of cellulose, hemicellulose and lignin.
• Another favourable pyrolysis product is flammable vapours and gases - hereinafter referred to as the pyrolytic gas.
• the product of incomplete pyrolysis of biomass at 170°C-270°C is semi- carbon which contains approximately 60%-65% elemental carbon C with chemical properties similar to those of lignite.
• the product of a complete pyrolysis of biomass at temperature above 270°C, preferably at 300°C is bio-carbon which contains approximately 65%-80% elemental carbon C with chemical properties similar to those of coal or coke.
• the HYGAS method is a high pressure process of hydrogasification of coal combined with gasification of fine coke, which makes it possible to obtain a high thermal value gas (substitute for natural gas).
• Hydrogen is obtained either by oxygen-steam coal gasification or electrothermal gasification or as a result of oxidation-reduction of iron oxides with gas obtained from gasification of fine coke (steam-iron system).
• the Hydrane method consists in obtaining a high thermal value gas by direct reaction of coal with hydrogen.
• Coal feedstock any grade
• the gasification process occurs at 815°C.
• Coal gasification occurs in a co-current, falling and thinned bed suspended in an internal reactor. Fine coke thus produced precipitates to a fluidized bed in an external reactor, to undergo further reaction with hydrogen.
• the internal and external reactors form a single device.
• Hydrogen for the process is obtained in a separate reactor by steam-oxygen gasification of a part of fine coke.
• All these methane manufacturing processes feature large consumption of elemental carbon C - to produce two molecules of CH4 at least 5 elemental carbon atoms C are consumed. This limits the efficiency of the carbon hydrogasification processes. It is characterized by high CO2 emissions to atmosphere and an increased emission of solid waste to the environment.
• the present invention solves the issue of application of plant-based raw materials from cultivated crops and organic waste and full utilisation of biomass having high content of cellulose, hemicellulose and lignin to produce bio-carbon and bio-methane, and, subsequently, bio-hydrogen for hydrogasification of bio-carbon to bio-methane and fossil carbon to eco-methane and high- efficiency conversion, exceeding 60% of the chemical energy of the resulting fuel to electricity.
• the method for the manufacture of bio-methane and eco-methane as well as electricity and thermal energy using a process of pyrolysing biomass to biocarbon mixed with comminuted and, possibly, appropriately prepared fossil carbon and using a process of hydrogasification of the carbon mixture to raw gas, its desulphurisation and separation into hydrogen and methane using a process of producing hydrogen in a reaction of methane with steam in the presence of a catalyst and heat supplied from outside is characterized in that a comminuted dry plant-based raw material or a waste raw material is subjected, individually or in specified sets, to a pyrolysis process, either in the temperature range of 170°C-270°Cat standard pressure to produce semi-carbon and a pyrolytic gas or in the temperature range of 270°C-300°C to produce bio-carbon and a pyrolytic gas or in the temperature range higher than 300°C, with a part of the pyrolytic gas directed to carry out pyrolysis of biomass in a biomass pyrolysis apparatus, and
• the former or the latter mixture is fed to a first carbon hydrogasification reactor where a process of complete hydrogasification is carried out using bio-hydrogen to produce raw gas and ash, or a process of incomplete hydrogasification of coal with bio-carbon or lignite with semi-carbon is carried out to produce raw gas and fine coke.
• the fine coke is directed to preheating the heating gas in a preheater and burned.
• the raw gas obtained, cooled down in a second heat exchanger, is subjected to desulphurisation, followed by separation into hydrogen, residual gases, and a methane mixture consisting of pure bio-methane and eco-methane.
• Heat from cooling the raw gas is sent to preheat the heating gas in the preheater and to the first heat exchanger in the waste heat boiler that generates process steam and power steam.
• Methane is sent to a gas distribution pipeline or a compressor or a condenser or to feed the power generation unit that generates electricity and thermal energy.
• a part of the methane, in the form of bio-methane, is fed to a third bio-hydrogen manufacture reactor where, in a reaction of hot steam supplied from the waste heat boiler and with heat supplied to that reaction by the heating gas, at temperature of approximately 500°C to 700°C in the presence of a catalyst, a mixture of bio-hydrogen and CO 2 is produced which, after cooling down in the waste heat boiler, is separated into bio-hydrogen, sent to the carbon mixture hydrogasification process in the first reactor, and CO2.
• the heating gas is preheated in a preheater to a temperature of approx.
• the comminuted dry mixture of semi-carbon with lignite or bio-carbon with coal is supplied from a carbon mixture preparation unit to the first reactor.
• the process of hydrogasification of the carbon mixture occurs, first in the internal chamber in a suspended bed falling in co-current with a gas introduced at the top of the internal chamber, said gas containing approximately 50% of 3 ⁇ 4 and 50% of CH 4 at a temperature about 815°C at a pressure of approx. 2.5 MPa do 7.5 MPa.
• the raw gas obtained in this process is passed from the first reactor into a separator of vapour and gases, where it is cleaned off dust and admixed gases and, in particular, undergoes desulphurisation, after which it is separated into a clean methane mixture consisting of bio-methane and eco-methane, and into pure hydrogen, partly recycled back to the bio-hydrogen stream.
• the other part of hydrogen, being the excess hydrogen, is sent to a burner in the preheater.
• a partly reacted carbon mixture is fed to an external chamber in the first reactor, where it is made to completely react with hydrogen to produce ash and hydrogen-and- methane gas, or to partially react to form fine coke and hydrogen-and-methane gas.
• the fine coke is sent to either combustion or storage and the hydrogen-and-methane gas is top-fed to the internal chamber of the reactor.
• the carbon mixture after combining it with mineral oil, is fed at a pressure of around 6.8 MPa in the form of a suspension, using a spray nozzle, to the topmost section of the first high pressure reactor, called the evaporation section.
• the oil evaporates and its vapours are discharged together with a hot raw gas leaving the middle section, called the first stage of carbon hydrogasification, to the vapour and gas separator.
• the separated mineral oil subsequently condensed in a condenser, is recycled back to the carbon suspension in oil preparation unit, and purified raw gas, especially after desulphurisation, is separated into a methane mixture and pure hydrogen to be combined with bio-hydrogen.
• Dry particles of the carbon mixture at a temperature of about 300°C, drop into a middle section of the reactor, where they are subjected to fluidization in a stream of biohydrogen-containing gas leaving the reactor bottom section called the second stage of carbon hydrogasfication, and in the middle section, called the first stage of hydrogasification, at a temperature raised to approximately 650°C and at a pressure of 6.8 MPa there occurs degassing and partial hydrogasification of carbon and bio-carbon particles.
• Partly reacted carbon mixture is subjected to complete hydrogasification in a fluidised bed in the bottom reactor section at a temperature of 750-950°C using bio-hydrogen and hydrogen fed to that section.
• the heating gas that carries heat to the third reactor, to the reaction of bio-methane with steam at an amount necessary to carry out the reaction of bio-hydrogen and CO2 formation approx. 155 kJ/mol - 165 kJ/mol of CFU at a temperature of approx. 500°C - 700°C in the presence of a ⁇ / ⁇ 2 ⁇ 3 catalyst is a gas which is inert toward the third reactor's materials, preferably CO2, nitrogen, helium or argon, or a gas with high specific heat, or a liquid with high boiling point.
• the heating gas preheater is supplied with high-temperature heat taken from the raw gas and heat supplied from solar collectors.
• Bio-methane and steam as the reactants producing bio-hydrogen in the presence of a N1/AI2O3 nickel catalyst in a temperature range of approx. 500°C-700°C and at a pressure of 1.5 MPa - 4.5 MPa in the first part of the third reactor are additionally heated in the reactor tubes by the hot heating gas at a temperature of about 800°C-1200°C.
• a Cu-Zn/A Cb catalyst is used in the temperature range of approximately 200°C-300°C or an Fe AhCb catalyst in the higher temperature range of 350°C-500°C followed by a C11/AI2O3 catalyst in the range of approx. 200°C-300°C or an Fe 2 03+Cr 2 03 in the temperature range of 300°C - 450°C.
• the system for the manufacture of bio-methane and eco-methane as well as heat and electricity consisting of a carbon hydrogasification reactor, a bio- hydrogen production reactor, a gas-vapour separator, a biomass pyrolysis reactor, a carbon mixture preparation unit, a waste heat boiler, a heating gas preheater, heat exchangers, conveyors, pumps and pipelines for liquids, vapours and gases, is characterised in that the first carbon hydrogasification reactor has two inlets, one for hydrogen and the other connected to the carbon mixture or carbon slurry preparation unit connected to the second biomass pyrolysis reactor.
• the first reactor has two outlets: the second one for fine coke or ash and the first one for raw gas, connected via a second heat exchanger to a vapour-gas separator.
• the vapour-gas separator has a first outlet in the form of a pipeline connected to the outlet of bio-hydrogen from the third reactor, a second outlet for methane and a third outlet for dust, vapours and residual gases.
• the first hydrogen outlet of the vapour-gas separator is split into two pipelines, of which recycled hydrogen pipeline is connected to the first bio- hydrogen inlet to the first reactor, whereas excess hydrogen pipeline is connected to the preheater' s gas burner.
• the second outlet for methane from the vapour-gas separator is also connected to the third hydrogen production reactor whose first outlet for a bio-hydrogen and CO2 mixture is connected via the waste heat boiler to a separator of the bio-hydrogen and CO2 mixture, whose outlet through a bio-hydrogen pipeline is connected to the first reactor.
• the waste heat boiler has a process steam outlet connected to the third reactor and a power steam outlet.
• the second outlet at the third reactor is connected to a pipeline for the heating gas with a preheater.
• the raw gas heat exchanger is connected via a pipeline to the preheater and, next, via a preheater exit gas pipeline to the waste heat boiler.
• the second biomass pyrolysis reactor has a dry biomass inlet connected to a biomass conveyor and a bio-carbon outlet connected to the carbon mixture preparation unit, as well as a pyrolytic gas outlet connected to a gas burner placed in the biomass pyrolysis reactor and to a gas burner placed in the heating gas preheater.
• the preheater has a third heat exchanger connected on one side to the heating gas pipeline and on the other side, via the heating gas pipeline, to a nozzle installed at the inlet of the third reactor.
• the preheater is equipped with a gas burner connected via a pyrolytic gas pipeline to the second biomass pyrolysis reactor and with a pulverised fuel burner connected via a fine coke conveyor to the fine coke outlet at the first reactor, and, additionally, the preheater is connected to the waste heat boiler via the preheater exit gas pipeline. Additionally, the preheater has a heat exchanger connected to a solar connector unit.
• the third bio-hydrogen production reactor has internal tubes containing a nickel catalyst supported on a ceramic substrate N1/AI2O3 located in the first part of the third reactor, said first part connected to an inlet of the heating gas that heats these tubes, as well as tubes containing either a CU-Z11/AI2O3 catalyst or an Fe/AhCh and C11/AI2O3 catalyst, said tubes located in the second part of the third bio-hydrogen production reactor, whereas the third reactor has an inlet for bio- methane, an inlet for process steam, and an outlet for a mixture of bio-hydrogen and CO2.
• the hydrogen and CO2 mixture separator has a pure CO2 outlet to atmosphere and/or for downstream processing and/or sequestration.
• An advantage of the method of producing bio-methane and eco-methane as well as electricity and thermal energy according to the present invention is the use of bio-carbon from biomass renewable on a yearly basis to produce bio-methane and to transfer heat to the bio-hydrogen production reaction through the heating gas that makes it possible to control that heat, and the heat for preheating the heating gas is obtained from cooling the raw gas exiting the first reactor, from the combustion of the pyrolytic gas, from excess hydrogen, as well as from fine coke and solar energy, which allows for low consumption of elemental carbon C from fossil carbon to convert it with bio- hydrogen to eco-methane - to produce one molecule of CH4 at most one carbon atom C of fossil carbon is consumed.
• the advantage is simultaneous hydrogasification of bio-carbon and fossil carbon in one reactor using bio-hydrogen. Hydrogasification of carbon is an exothermic process; it does not need heat to be supplied to the reaction, therefore, heat exchangers in the hydrogasification reactor are unnecessary.
• the appropriately high temperature of 800°C - 1200°C is achieved in the heating gas preheater by using a gas burner and a pulverized fuel burner.
• the temperature of the heating gas, up to 1200°C, is achieved in the solar collector unit, thus creating a new method of using solar energy - it its accumulated in the heating gas, and, subsequently, in the gaseous fuel produced, namely bio- methane and eco-methane.
• the efficiency of the production of electricity from solar energy is at the level of 48%.
• the present invention is illustrated in an embodiment in the attached drawing, which depicts a schematic diagram of the process indicating the ties between the sub-systems and the equipment applied in the process for the production of bio-methane and eco-methane.
• Example I
• the first bio-carbon and fossil carbon hydrogasification reactor 1 shown in the drawing there is carried out a complete gasification of bio-carbon and fossil carbon using bio-hydrogen.
• the biomass for the full pyrolysis process carried out in a second biomass pyrolysis reactor 2 at about 300°C dry wood chips were used, fed into the second pyrolysis reactor 2 using a biomass conveyor 21.
• the product of the biomass pyrolysis is bio-carbon as well as vapours and a combustible pyrolytic gas supplied via pipeline 22a to a gas burner 13 in the second reactor 2 and via pipeline 22b to a gas burner 14 located in the heating gas preheater 9, said heating gas being a stream of CO2.
• the bio-carbon is conveyed from the second reactor 2, using a bio-carbon conveyor 23, to a carbon mixture preparation unit 25, where it is mixed and appropriately comminuted together with coal fed to the unit 25 through a conveyor 24.
• This mixture without any special pre-treatment, is fed by a conveyor 26 to the top of the first carbon hydrogasification reactor 1 where it is hydrogasified to bio-methane and eco-methane at approx.
• bio-hydrogen that exits the bio-hydrogen and CO2 separator 815°C by bio-hydrogen that exits the bio-hydrogen and CO2 separator 8, wherefrom bio- hydrogen flowing through a bio-hydrogen pipeline 18a is fed together with hydrogen recycled via pipeline 19a through pipeline 18b to the bottom of the first reactor 1.
• the bio-hydrogen passing through a fluidised bed of a carbon mixture with fine coke in the thermally-insulated external chamber of the first reactor 1 causes fluidisation of that bed and reacts with bio-carbon and coal to give a reactive gas containing approx.
• said gas flows through openings located in the upper part of the shell of an internal chamber and, flowing in that chamber concurrently with the descending suspended bed of the carbon mixture reacts with that mixture which is fed to the internal chamber using a carbon mixture conveyor 26 from the carbon mixture preparation unit 25 through the carbon mixture inlet at the internal chamber.
• the raw gas undergoes desulphurisation and separation on a membrane through which only hydrogen can pass, said hydrogen sent via a hydrogen pipeline 19 to a recycled hydrogen pipeline 19a, combining with bio-hydrogen in a pipeline 18b, and also sent to an excess hydrogen pipeline 19b connected to a gas burner in the preheater 9.
• the third bio-hydrogen production reactor 3 comprises inside tubes 3a filled with a catalyst, i.e. nickel on a ceramic support. These tubes are supplied with bio-methane using pipeline 20a and hot steam at approx. 400°C using steam pipeline 11a.
• the reaction of bio-methane with steam leads to the formation of a mixture of bio-hydrogen with CO2 fed via pipeline 10b and heat exchanger 4a in the waste heat boiler 4 and further by pipeline 10c into the bio-hydrogen and CO 2 mixture separator 8.
• the main part of energy for the formation of bio-hydrogen and CO2 from bio-methane and steam is contributed by the heating gas at temperature approx. 900°C, which is fed to the third reactor 3 through nozzle lOd and flows around tubes 3a of the reactor 3, the remaining part of energy brought about by hot 400°C steam.
• the heat evolving in the coal and bio- carbon hydrogasification reaction in the first reactor 1 and supplied by heat pipeline 7b to the preheater 9 is significantly higher than the heat needed to make up the thermal energy supplied to the bio-hydrogen production reaction.
• the excess heat is discharged from the heating gas preheater 9 via pipelines 7c and 7a to the waste heat boiler 4.
• the heating gas cooled down during the process in the third reactor 3 is supplied by pipeline 10a to the heat exchanger 9a of the preheater 9, where it is heated up to 900°C and flows again through pipeline 10 to the nozzle lOd at the third reactor 3.
• the bio-hydrogen production reaction takes place at a temperature of about 500°Cat appropriately increased pressure. Increasing the pressure to 3 MPa causes and increase in reaction speed and allows for reducing the size of the third reactor 3.
• the waste heat boiler 4 is also supplied with make-up water from an external source of water using a water pipeline 12.
• the waste heat boiler 4 produces process steam at about 400°C, which is supplied through process steam pipeline 11a to the third bio-hydrogen production reactor 3, and power steam at a temperature of about 585°C supplied via a power steam pipeline lib to the power turbine TP in the power generation unit.
• Example II Example II.
• Bio-carbon with elemental carbon content C of 77% was supplied using bio-hydrogen to the bio-carbon hydrogasification process.
• a full conversion of the bio-carbon is carried out.
• the biomass subjected to the process of full pyrolysis to bio-carbon at a temperature of about 300°C dry straw was used, producing about 350 kg of bio-carbon per 1 tonne of dry straw plus pyrolytic gas.
• Dry straw is fed, using a biomass conveyor 21, to the second biomass pyrolysis reactor 2; next, the bio-carbon produced is fed to a bio-carbon preparation unit 25 where it is appropriately comminuted, and the pyrolytic gas is in part fed via pipeline 22a to a gas burner 13 in the reactor 2 and in another part sent via pipeline 22b to a gas burner 14 in the heating gas pre-heater 9.
• the bio-carbon, appropriately comminuted in the bio-carbon preparation unit 25, is fed via bio-carbon conveyor 26 at the top of the first bio-carbon hydrogasification reactor 1 where it undergoes complete hydrogasification to bio-methane using bio- hydrogen at a temperature of approx. 815°C according to a method provided in Example I.
• Example I From the first reactor 1, raw gas is fed via a pipeline 6 through a heat exchanger 6a to a gas and vapour separator 5.
• the composition of the raw biogas is provided in Example I.
• the vapour and gas separator 5 the raw gas is desulphurised and separated, and then is sent via pipeline 19 to pipeline 19a connected to the bio-hydrogen pipeline 18a and, further, flows through pipeline 18b to enter the first reactor 1 at its bottom, whereas excess hydrogen flows through pipeline 19b to the gas burner 14 in the preheater 9.
• Bio-methane stream fed to pipeline 20 is split into two streams: bio-methane sent through pipeline 20a to the third bio-hydrogen production reactor 3, and bio-methane sent through pipeline 20b to feed a power generation unit in the form of a fuel cell. Excess bio-methane is fed to a compressed bio-methane tank.
• the manufacture of bio-hydrogen in the third reactor 3 is carried out according to a method provided in Example I.
• the operation of the waste heat boiler 4
• the heating gas flowing out from the third reactor 3 to pipeline 10a is fed into the preheater 9 of that gas, where it is preheated using gas burner 14 supplied with pyrolytic gas and, partly, bio-methane and excess hydrogen to a temperature of approx. 900°C and, subsequently, recycled via pipeline 10 to nozzle lOd in the third reactor 3.
• gas burner 14 supplied with pyrolytic gas and, partly, bio-methane and excess hydrogen to a temperature of approx. 900°C and, subsequently, recycled via pipeline 10 to nozzle lOd in the third reactor 3.
• the heating of tubes 3a in that reactor and the production of the bio-hydrogen and CO2 mixture in those tubes is carried out according to the method provided in Example I.
• biomass subjected to the partial pyrolysis process carried out in the second biomass pyrolysis reactor 2 at about 170°C - 270°C dry wood chips were used, fed into the second reactor 2 using a biomass conveyor 21.
• the product of the partial pyrolysis of biomass is semi-carbon as well as vapours and combustible pyrolytic gas, a part of said gas is supplied via a pipeline 22a to a gas burner 13 in the second biomass pyrolysis reactor 2, and the other part is supplied through a pipeline 22b to a gas burner 14 located in the preheater 9 of the heating gas being a stream of nitrogen.
• the semi-carbon is conveyed from the second biomass pyrolysis reactor 2, using a bio-carbon conveyor 23, to a first carbon slurry preparation unit 25, where it is mixed and appropriately comminuted together with lignite fed to the unit 25 through a coal conveyor 24, and mineral oil is supplied thereto.
• the mixture formed of carbon and oil, containing 75% vol. of mineral oil and 25% vol. of comminuted carbon, is fed via supply pipeline 26 to a spray nozzle which feeds the carbon slurry to the topmost section of the first reactor 1, called the evaporation section, at a pressure of 6.8 MPa.
• the oil evaporates and its vapours are discharged together with hot raw gas leaving the middle section, called the first stage of carbon hydrogasification, to the vapour and gas separator 5 via heat exchanger 6a.
• the recovered mineral oil subsequently condensed in a condenser, is recycled back to the carbon preparation unit 25, and the raw gas is subjected to purification and desulphurisation.
• Dry carbon and bio-carbon particles at a temperature of about 300°C are directed to the central section, subjected to fluidization in a stream of biohydrogen-containing gas leaving the reactor bottom section called the second stage of carbon hydrogasfication, and in the central section, at a temperature elevated to 650°C and at a pressure of 6.8 MPa degassing and partial hydrogasification of carbon particles takes place.
• the partially converted carbon mixture is subjected to complete hydrogasification in a fluidised bed in the bottom section of the first reactor 1 at a temperature of 750-950°C using bio- hydrogen and hydrogen fed to that section.
• Purified raw gas undergoes further separation in the vapour and gas separator 5 where unused hydrogen is separated from the methane mixture of bio- methane and eco-methane and is recycled back, via hydrogen pipeline 19, to recycled hydrogen pipeline 19a, combining in pipeline 18b with bio-hydrogen fed at the bottom of the first reactor 1, as well as to excess hydrogen pipeline 19b connected to the gas burner 14 in the preheater 9.
• the methane mixture flows through pipeline 20 which splits into bio-methane pipeline 20a that supplies bio-methane to the third bio-hydrogen production reactor 3, and into pipeline 20b that supplies eco- methane to a gas distribution system. Production of bio-hydrogen takes place in the third reactor 3 as a result of reaction between bio-methane and steam.
• the required energy for the endothermic reaction is brought about by a heating gas supplied to the third reactor 3 by pipeline 10 and nozzle lOd and hot steam supplied by steam pipeline 11a, whereas the amount of energy to be supplied can be controlled, among other things, by controlling the flow rate and the temperature of the heating gas that flows around tubes 3a in the third reactor 3.
• the bio-hydrogen formation reaction occurs at a temperature about 500°C in the presence of a catalyst - nickel supported on a ceramic substrate, inside the tubes 3a which are heated by hot stream of heating gas at a temperature of 900°C.
• the produced and cooled down bio-hydrogen is sent to the first carbon and bio-carbon hydrogasification reactor 1.
• the reaction of bio-hydrogen with elemental carbon C from the semi-carbon and with elemental carbon C from the lignite produces bio-methane and eco-methane and heat related to the carbon hydrogasification reaction.
• the heat from the cooling down of the raw gas in heat exchanger 6a is supplied via heat pipeline 7b to the heating gas preheater 9 and, subsequently, the heat from the hot gases from the preheater 9 is supplied via pipelines 7c and 7a to the waste heat boiler 4.
• the waste heat boiler 4 receives heat from many sources, especially from the cooling down of bio-hydrogen in a heat exchanger and from the bio-hydrogen and CO 2 mixture leaving the third bio-hydrogen production reactor 3, said mixture flowing through pipeline 10b to heat exchanger 4a in the waste heat boiler 4 and leaving the waste boiler 4 through pipeline 10c to a separator 8 where it is separated into bio-hydrogen fed via pipelines 18a and 18b to the first reactor 1 and into carbon dioxide sent to a CO2 sequestration plant.
• the CO 2 stream exiting the separator 8, previously cooled down in heat exchanger 4a in the waste heat boiler 4 flows through CO2 pipeline lOe to a CO 2 sequestration process, especially through silicates, for example serpentine. Products of such fixation, magnesium carbonate, silica and water, are durable and easy to store.
• the heating gas preheater 9 is connected to a system of solar collectors.
• a CO2 stream as the heat carrier is heated up to approx. 1200°C and is recycled back to a heat exchanger 30 located in the preheater 9, from which heat is supplied via heating gas pipeline 10 to the third reactor 3 which produces a bio- hydrogen and CO 2 mixture separated in the separator 8 into bio-hydrogen and CO2, said separator 8 being a potassium scrubber.
• Solar heat is transferred by the heat carrier at a high efficiency up to 80% to the third reactor 3 where it is converted to the chemical energy of bio-hydrogen and, subsequently, to the chemical energy of bio-methane and eco-methane in the first reactor 1.
• the first carbon and bio-carbon hydrogasification reactor 1 has two inlets, 18b and 26, of which the first one, 18b, is for hydrogen and the other one, 26, as a conveyor of the carbon mixture is connected to carbon mixture preparation unit 25 connected to the second biomass pyrolysis reactor.
• the second pyrolysis reactor 2 is equipped with pyrolytic gas pipelines 22a and 22b, of which pipeline 22a is connected to gas burner 13 located in that reactor and pipeline 22b is connected to gas burner 14 located in the heating gas preheater 9.
• the second pyrolysis reactor 2 is equipped with two conveyors, of which conveyor 21 is a biomass conveyor and conveyor 23 is a bio-carbon conveyor connected to the carbon mixture preparation unit 25.
• That unit has an inlet 16 and outlet 16a for a purging gas, and is also equipped with a coal conveyor 24 and a carbon mixture conveyor 26.
• the first reactor 1 has two outlets, 6 and 28, of which the second one, fine coke outlet 28, is connected to fine cone transporter 28a that feeds pulverised fuel burner 15 located in the preheater 9, and to conveyor 28b to a storage, and the first outlet 6 for raw gas is connected through heat exchanger 6a to vapour and gas separator 5.
• the vapour and gas separator 5 has a first hydrogen outlet 19, a second methane outlet 20, and a third waste outlet 17.
• the first hydrogen outlet 19 from the separator 5 is split into two pipelines, 19a and 19b, of which pipeline 19a is connected to the first inlet 18b of the first reactor 1, and pipeline 19b is connected to the burner 14 in the preheater 9, and the second methane outlet 20 from the separator 5 is also connected to the third reactor 3, whose first outlet 10b is connected via heat exchanger 4a of the waste heat boiler 4 and via pipeline 10c to the separator 8, whose first bio-hydrogen outlet is connected via pipelines 18a and 18b to the first reactor 1, and the second CO 2 outlet is connected through pipeline lOe to a CO2 sequestration plant, not shown in the drawing.
• the waste heat boiler 4 has a process steam outlet connected via steam pipeline 11a to the third bio-hydrogen and CO2 production reactor 3, as well as a power steam outlet connected via pipeline lib to a steam turbine in the power generation unit, not shown in the drawing.
• the waste heat boiler 4 also has a connection to a water pipeline 12.
• the second outlet of the third reactor 3 is connected to heating gas pipeline 10a connected to heat exchanger 9a in the preheater 9, said exchanger is connected via pipeline 10 to a heating gas nozzle lOd located in the third reactor 3.
• the heat exchanger 6a taking heat from the heating gas is connected via pipeline 7b, preheater 9 and pipelines 7c and 7a to the waste heat boiler 4.
• the preheater 9 is equipped with a heat exchanger 30 connected to a solar collector unit and the third reactor has a set of tubes 3a with catalysts.

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• 2015
  • 2015-07-02 PL PL412999A patent/PL231090B1/pl unknown
• 2016
  • 2016-07-02 WO PCT/IB2016/053994 patent/WO2017002096A1/en active Application Filing
  • 2016-07-04 CN CN201610519331.5A patent/CN106318417B/zh not_active Expired - Fee Related

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