CN106318417B

CN106318417B - Method and system for producing biomethane and ecological methane

Info

Publication number: CN106318417B
Application number: CN201610519331.5A
Authority: CN
Inventors: 亚当·克里洛维奇; 雅罗斯瓦夫·克里洛维奇
Original assignee: Bicarbo SpZOO
Current assignee: Bicarbo SpZOO
Priority date: 2015-07-02
Filing date: 2016-07-04
Publication date: 2020-10-27
Anticipated expiration: 2036-07-04
Also published as: CN106318417A; PL231090B1; WO2017002096A1; PL412999A1

Abstract

The invention discloses a method for producing biomethane and ecological methane, and a system for producing biomethane and ecological methane. The methods include processes in which biomass is pyrolyzed to biochar and mixed with pulverized and possibly suitably prepared fossil carbon, and processes in which a carbon mixture is hydro-gasified. The system consists of a carbon hydrogenation gasification reactor, a biological hydrogen generation reactor, a steam and coal gas separator, a biomass pyrolysis reactor, a carbon mixture preparation device, a waste heat boiler, a heating gas preheater, a heat exchanger, a conveyor, a pipeline and a pump for liquid, steam and gas.

Description

Method and system for producing biomethane and ecological methane

Technical Field

The subject of the invention is a process for producing biomethane and ecological methane by hydro-gasification of biochar and fossil carbon, in which biohydrogen is the gasifying agent.

Background

Biohydrogen is a product formed from biomass by the reaction of biomethane with water vapor. Biomethane is the product of the hydro-gasification of biochar using biohydrogen. The product of hydro-gasification of coal or lignite using bio-hydrogen is ecological methane. Biochar is the product of pyrolysis of dry biomass, preferably with a high content of cellulose, hemicellulose and lignin. Further advantageous pyrolysis products are combustible vapors and gases, hereinafter referred to as pyrolysis gases. The product of incomplete pyrolysis of biomass at 170 ℃ to 270 ℃ is a half-carbon containing about 60% to 65% elemental carbon C' with a chemical nature similar to that of lignite. The product of the complete pyrolysis of biomass at temperatures above 270 ℃ (preferably 300 ℃) is biochar containing about 65% to 80% elemental carbon C' with chemical properties similar to those of coal or coke.

According to Jerzy Szuba, Lech michallik is entitled: "Karbohemia",

the publication of 1983 knows to use hydrogen obtained mainly by steam and oxygen based gasification of fine coke or coalA process for the hydro-gasification of gas.

The HYGAS process developed by Institute of Gas Technology (USA) is known from this book. The HYGAS process is a high pressure process for coal hydro-gasification combined with fine coke gasification, which is capable of obtaining high calorific value gas (a substitute for natural gas). There are three versions of the process tested, differing in the method of producing hydrogen for hydro-gasification. Hydrogen is obtained by oxygen-steam gasification or electric heat gasification, or as a result of oxidation-reduction of iron oxides (steam-iron system) with gas from fine coke gasification.

Known from this book is the Hydrane method developed by Pittsburgh Energy Research Center (USA). The Hydrane process consists in obtaining a high calorific value gas by direct reaction of coal with hydrogen. The coal feed (any grade) is reacted with hydrogen contained in a hot gas. The gasification process takes place at 815 ℃. Coal gasification occurs in co-current (co-current), falling (falling) and reduced bed (thin bed) suspended in an internal reactor. The fine coke thus produced is precipitated in the fluidized bed of the internal reactor to undergo further reaction with hydrogen. The inner reactor and the outer reactor form a single unit. The hydrogen used in the process is obtained in a separate reactor by steam-oxygen gasification of a portion of the fine coke.

Known from patent specification US 2011/0126458a1 is a process for producing a methane-rich gaseous fuel by the combination of hydro-gasification of a coal feedstock with hydrogen and steam. The aqueous slurry of coal is gasified with hydrogen and superheated steam at a temperature in the range of about 700 ℃ to 1000 ℃ and a pressure in the range of about 132kPa to 560 kPa. The products of this gasification are hydrogen, methane, carbon monoxide and carbon dioxide. Hydrogen is separated from the mixture in a separator and recycled back to the SHR carbon gasification furnace, which is also supplied with steam, and CH₄CO and CO₂The mixture of (A) is rich in methane (up to 40% CH)₄) The fuel gas of (1).

According to Bohdan Stali ń ski, Janusz

The topic of (1) is: the book "Wod Lo i woodki", Wydawnictow Naukowo-Techniczne, Warszawa,1987 discloses a process for producing hydrogen gas in the reaction of natural gas methane with steam in the presence of a catalyst (nickel supported on a ceramic substrate) in a steel tube heated from the outside to a temperature of about 500 ℃ by burning natural gas. The tube was heated using about 25% of the gas entering the reactor.

All of these methane production processes are characterized by a large consumption of the element carbon C-for the production of two molecules of CH₄In other words, at least 5 elemental carbon atoms C are consumed. This limits the efficiency of the carbon hydro-gasification process. Said method is characterised in that CO₂High emissions to the atmosphere and increased emissions of solid waste to the environment.

Disclosure of Invention

The present invention solves the following problems: the application of plant-based raw materials and organic wastes from cultivated crops and the complete use of biomass with high content of cellulose, hemicellulose and lignin for the production of biochar and biomethane, and the subsequent biohydrogen for the hydro-gasification of biochar to biomethane and of fossil carbon to biomethane, and the production of high conversion efficiency of the chemical energy conversion of the resulting fuel to electricity of more than 60%. These effects are obtained by the following steps: biochar is produced in the biomass pyrolysis process, a mixture of biochar and fossil carbon is formed, and the mixture is gasified using biohydrogen obtained using biomethane, steam in the presence of a catalyst and heat supplied from the outside by heating gas (the heating gas is preheated using heat energy from combustion of fine coke, excess hydrogen and pyrolysis gas, and using solar energy), which results in accumulation of solar energy.

The method for producing biomethane and ecological methane and electrical and thermal energy is carried out using the following processes: the process of pyrolysis of biomass into biocarbon mixed with crushed and possibly suitably prepared fossil carbon, and the process of hydro-gasification of carbon mixtures into raw gas, desulfurization of said raw gas and separation into hydrogen and methane, using methane and methane in the presence of a catalyst and heat supplied from the outsideProcess for the production of hydrogen in the reaction of steam, characterized in that comminuted dried plant-based or waste raw material is subjected individually or in the form of specific groups to a pyrolysis process, which is carried out either in the temperature range of 170 ℃ to 270 ℃ at standard pressure to produce semi-carbon and pyrolysis gases, or in the temperature range of 270 ℃ to 300 ℃ to produce biochar and pyrolysis gases, or in the temperature range above 300 ℃, part of which is passed to a biomass pyrolysis device for the pyrolysis of biomass and another part of which is passed to a preheater for preheating the heating gases. The obtained half-carbon containing about 60 to 65% of elemental carbon is preferably mixed with pulverized lignite, while biocarbon containing about 65 to 80% of elemental carbon is mixed with pulverized coal, the ratio of elemental carbon C 'from biocarbon to elemental carbon C from fossil carbon preferably being C': C1: 1. The former mixture or the latter mixture is supplied to a first carbon hydro-gasification reactor, in which a full hydro-gasification process using bio-hydrogen is performed to produce raw gas and ash, or an incomplete hydro-gasification process of coal and bio-carbon or lignite and semi-carbon is performed to produce raw gas and fine coke. The fine coke is passed to a preheater to preheat and combust the heating gas. The raw gas obtained (cooled in the second heat exchanger) is subjected to desulfurization and subsequently separated into hydrogen, residual gas and a methane mixture consisting of pure biomethane and ecological methane. Heat from the cooling of the raw gas is sent to a preheater to preheat the heating gas and to a first heat exchanger in a waste heat boiler that generates process steam and electricity steam. The methane is sent to a gas distribution line or compressor or condenser or to a power plant that produces electrical and thermal energy. Supplying a portion of the methane (in the form of biomethane) to a third biohydrogen producing reactor, wherein in a reaction of hot steam supplied by a waste heat boiler and heat supplied to the reaction by a heating gas, biohydrogen and CO are produced at a temperature of about 500 ℃ to 700 ℃ in the presence of a catalyst₂After cooling down in a waste heat boiler, to CO₂And sent to the first reactionThe carbon mixture in the vessel is hydrogenated to the bio-hydrogen of the gasification process. The heating gas is preheated in a preheater to a temperature of about 800 ℃ to 1200 ℃ required for the biohydrogen generating reaction in the third reactor, using a gas burner supplied with pyrolysis gas from the second biomass pyrolysis reactor and/or using excess hydrogen recovered from the raw gas and using a powder fuel burner supplied with ground fine coke or coal or biochar. The heated gas stream thus heated enters a third reactor to heat the biomass and CO generated therein₂The resulting tube of the process.

Pulverized and dried mixture of semi-carbon and lignite or biochar and coal in the presence of CO₂Air is supplied from the carbon mixture preparation apparatus to the first reactor after being removed therefrom. In the first reactor, the process of hydro-gasification of the carbon mixture is first carried out in a suspension bed in an internal chamber in concurrent flow with a gas introduced from the top of said internal chamber, said gas comprising about 50% of H at a temperature of about 815 ℃ at a pressure of about 2.5MPa to 7.5MPa₂And 50% of CH₄. The raw gas obtained in the process, which is passed through the first reactor into a vapor and gas separator, is freed of dust and blended gases and is in particular desulfurized, after which it is separated into a clean methane mixture consisting of biomethane and ecological methane and pure hydrogen, the hydrogen being partly recycled back into the biomethane stream. The other part of the hydrogen (which is excess hydrogen) is sent to the burner in the preheater. The partially reacted carbon mixture is fed to an outer chamber in the first reactor where it is either fully reacted with hydrogen to produce ash and hydrogen + methane gas or partially reacted to form fine coke and hydrogen + methane gas. The fine coke is sent to combustion or storage, while the hydrogen + methane gas is supplied overhead to the inner chamber of the reactor.

The carbon mixture, after being combined with the mineral oil, is supplied in the form of a suspension at a pressure of about 6.8MPa to the highest section of the first high-pressure reactor, called the evaporation section, using a nozzle. At the temperatures prevailing here (about 315 ℃), the oil is evaporated and its vapours are discharged to a vapour and gas separator together with the hot raw gas leaving the intermediate section of the first stage, known as carbon hydro-gasification. The separated mineral oil which has subsequently been condensed in the condenser is recirculated back to the carbon-in-oil suspension production plant and the purified raw gas, in particular after desulfurization, is separated into a methane mixture and pure hydrogen to be combined with biohydrogen. At a temperature of about 300 ℃, the dry particles of the carbon mixture fall into the intermediate section of the reactor, where they are fluidized in the flow of the biohydrogen-containing gas leaving the bottom section of the reactor, called the second stage of carbon hydro-gasification, and in the intermediate section, called the first stage of hydro-gasification, degassing and partial hydro-gasification of the carbon and biochar particles takes place at a temperature raised to about 650 ℃ and a pressure of 6.8 MPa. In the fluidized bed of the bottom section of the reactor, the partially reacted carbon mixture is subjected to complete hydro-gasification at a temperature of 750 ℃ to 950 ℃ using the biohydrogen and hydrogen supplied to said section.

The heating gas is a gas inert to the material of the third reactor, preferably CO₂Nitrogen, helium or argon or a gas with a high specific heat or a liquid with a high boiling point, the heated gas carrying heat into the reaction of biomethane and steam in the third reactor, the amount of heat being Ni/Al at a temperature of about 500 ℃ to 700 ℃₂O₃Sufficient to carry out the biological hydrogen and CO in the presence of a catalyst₂About 155kJ/mol to 165kJ/mol CH of the formation reaction₄。

From biological hydrogen and CO at a temperature of about 500 deg.C₂Is conveyed to the waste heat boiler, heat from the flow of steam at a temperature of about 600 ℃ of the gas leaving the preheater, and heat from external systems, in particular from power plants which generate electrical and thermal energy when the plants are supplied with the produced ecological or biomethane.

The heating gas preheater is supplied with high temperature heat taken from the raw gas and heat supplied by the solar collector.

In the first section of the third reactor, at a temperature in the range of about 500 ℃ to 700 ℃ and 1.5MPa to 4.At a pressure of 5MPa in Ni/Al₂O₃Biomethane and steam, which are reactants for generating biohydrogen in the presence of a nickel catalyst, are additionally heated in the reactor tubes by means of hot heating gases at temperatures of approximately 800 ℃ to 1200 ℃.

For a biohydrogen formation reaction of carbon monoxide and water vapor in a third reactor, the gas mixture in the biohydrogen formation reaction flows from a first section of the third reactor to a second section of the third reactor, the second section of the third reactor is operated at a lower temperature range than the first section, or Cu-Zn/Al is used in a temperature range of about 200 ℃ to 300 ℃₂O₃Catalyst, or use of Fe/Al in higher temperature range of 350-500 deg.C₂O₃The catalyst is then used with Cu/Al in the range of about 200 ℃ to 300 ℃₂O₃Catalysts or use of Fe in the temperature range of 300 ℃ to 450 ℃₂O₃+Cr₂O₃The reaction is carried out.

Another subject of the invention is a system for producing biomethane and ecological methane, as well as heat and electricity. The system for producing biomethane and ecological methane and heat and electricity consists of: a carbon hydrogasification reactor, a biohydrogen generating reactor, a gas-vapor separator, a biomass pyrolysis reactor, a carbon mixture preparation device, a waste heat boiler, a heating gas preheater, a heat exchanger, a conveyor, lines and pumps for liquid, vapor and gas, the system being characterized in that the first carbon hydrogasification reactor has two inlets, one for hydrogen and the other connected to a carbon mixture or carbon slurry preparation device connected to the second biomass pyrolysis reactor. The first reactor has two outlets: a second outlet for fine char or ash and a first outlet for raw coal gas, the first outlet being connected to a vapour-gas separator via a second heat exchanger. The vapour-gas separator has a first outlet in the form of a pipeline connected to the biohydrogen outlet of the third reactor, a second outlet for methane and a third outlet for dust, vapour and residual gases. The first hydrogen outlet of the vapor-gas separator is divided into two lines,wherein the recycle hydrogen line is connected to the first bio-hydrogen inlet of the first reactor and the excess hydrogen line is connected to the gas burner of the preheater. The second outlet for methane from the steam-coal separator is also connected to a third hydrogen generation reactor for biological hydrogen and CO₂The first outlet of the mixture is connected to the bio-hydrogen and CO via a waste heat boiler₂A separator of the mixture, the outlet of the separator being connected to the first reactor by a biohydrogen line. The waste heat boiler has an electrical steam outlet and a process steam outlet connected to the third reactor. The second outlet of the third reactor is connected to the line of the preheater for heating the gas. The raw gas heat exchanger is connected via a line to the preheater and then, via a preheater outlet gas line, to the waste heat boiler.

The second biomass pyrolysis reactor has a dry biomass inlet connected to the biomass conveyor and a biochar outlet connected to the carbon mixture preparation device, and a pyrolysis gas outlet connected to a gas burner disposed in the biomass pyrolysis reactor and a gas burner disposed in the heating gas preheater.

The preheater has a third heat exchanger connected at one end to a heating gas line and at the other end via the heating gas line to a nozzle installed at the inlet of the third reactor. The preheater is equipped with a gas burner connected to the second biomass pyrolysis reactor via a pyrolysis gas line and with a pulverized fuel burner connected to the fine coke outlet of the first reactor via a fine coke conveyor, and furthermore the preheater is connected to a waste heat boiler via a preheater outlet gas line. Furthermore, the preheater has a heat exchanger connected to the solar collector device.

Preferably, the third biohydrogen generating reactor has an inner tube comprising a nickel catalyst Ni/Al supported on a ceramic substrate in the first part of the third reactor₂O₃The first part is connected to the inlet of the heating gas to heat the tubes and comprises Cu-Zn/Al₂O₃Catalyst or Fe/Al₂O₃And Cu/Al₂O₃A tube of catalyst located in a second part of a third biological hydrogen generating reactor, the third reactor having an inlet for biomethane, an inlet for process steam and for biological hydrogen and CO₂Outlet of the mixture of (a).

Hydrogen and CO₂Mixture separator with pure CO to atmosphere and/or for downstream processing and/or sequestration₂And (7) an outlet.

One advantage of the method for producing biomethane and ecological methane and electrical and thermal energy according to the invention is the use of biochar from annually renewable biomass for producing biomethane and transferring the heat to the biohydrogen production reaction by means of the heating gas, which process enables the control of the heat, and the heat for preheating the heating gas is obtained from cooling the raw coal gas leaving the first reactor, from the combustion of the pyrolysis gas, from the excess hydrogen and from fine coke and solar energy, which allows a low consumption of elemental carbon C from fossil carbon to convert it with biohydrogen into ecological methane, generating one molecule of CH₄At most one carbon atom C of fossil carbon is consumed. This significantly reduces CO to the environment₂Emissions and carbon related solid waste emissions. In the production of gaseous fuels: this significantly reduces the consumption of biochar and fossil carbon when biomethane or ecological methane. The fuel is capable of generating electricity in a power plant with an energy efficiency of over 60%.

The advantage is the simultaneous hydro-gasification of biochar and fossil carbon in one reactor using bio-hydrogen. Hydro-gasification of carbon is an exothermic process; no heat needs to be supplied to the reaction and therefore no heat exchanger in the hydro-gasification reactor is needed. A suitably high temperature of 800 to 1200 c is achieved in the heated gas preheater by using a gas burner and a pulverized fuel burner. The temperature of the heated gas up to 1200 ℃ is achieved in the solar collector device, thus creating a new way of using solar energy that accumulates in the heated gas and then in the produced gaseous fuel, i.e. biomethane and ecological methane. The efficiency of solar power generation is at the level of 48%. Currently, the efficiency of photovoltaic cells is about 15%. In CO₂Pure CO obtained in a separation process from hydrogen₂The stream is readily bound to CO₂In sequestration processes, whether underground or by allowing CO to sequester₂Combine with silicates to form stable products. This results in zero emission power generation using fossil carbon for this purpose.

Drawings

The invention is illustrated in an embodiment in conjunction with the accompanying drawing, figure 1 shows a schematic diagram of a process showing the connections between subsystems and equipment used in a process for the production of biomethane and ecological methane.

Detailed Description

Example I

Biochar having an elemental carbon content C 'of 77% and coal having an elemental carbon content of 70% to 80% are supplied to a biochar and fossil carbon hydro-gasification process using bio-hydrogen, maintaining a preset biochar to coal ratio C' C1: 1. In the first biochar and fossil carbon hydro-gasification reactor 1 shown in the figure, complete gasification of biochar and fossil carbon is performed using bio-hydrogen. As biomass for the complete pyrolysis process carried out in the second biomass pyrolysis reactor 2 at about 300 ℃, dry wood chips are used, which are supplied into the second pyrolysis reactor 2 by means of the biomass conveyor 21. The products of the biomass pyrolysis are biochar and steam and combustible pyrolysis gas supplied via line 22a to the gas burner 13 in the second reactor 2 and via line 22b to the gas burner 14 in the heating gas preheater 9, which is CO₂The flow of (2). Biochar is conveyed from the second reactor 2 using a biochar conveyor 23 to a carbon mixture preparation device 25 where it is mixed with coal supplied to the device 25 by a conveyor 24 and suitably crushed together. The mixture (without any particular pre-treatment) is fed by conveyor 26 to the top of the first carbon hydro-gasification reactor 1, where it is passed at about 815 ℃ by leaving the biohydrogen and CO₂The mixture is hydrogenated and gasified into biomethane and ecological methane by the biological hydrogen of the separator 8, and raw methane flows through the mixtureThe biohydrogen of the hydrogen line 18a is supplied to the bottom of the first reactor 1 through a line 18b together with the hydrogen recycled via a line 19 a. The flow of biohydrogen through the fluidized bed of fine coke and the carbon mixture in the insulated outer chamber of the first reactor 1 causes fluidization of the bed and reaction with the biochar and coal to produce a reaction gas containing about 50% hydrogen and 50% methane which flows through the apertures located in the upper region of the shell of the inner chamber and into the inner chamber, flows in parallel with the falling suspended bed of carbon mixture, reacts with the mixture, which is supplied to the inner chamber from the mixture preparation device 25 through the carbon mixture inlet in the inner chamber using the carbon mixture conveyor 26. As a result of the reaction gas reacting with the coal and the biochar in the inner chamber of the first reactor 1, a partial reaction of the mixture with the biohydrogen takes place and the partially converted carbon mixture falls to a fluidized bed in the outer chamber where it is completely converted with the biohydrogen and the resulting ash is discharged through an ash discharge channel and transported with a conveyor 28b to an ash storage point, while the unconverted fine coke (possibly on a sieve and recovered by an air stream) is recycled back to the carbon mixture preparation unit 25. The raw gas from the first reactor is supplied via line 6 and heat exchanger 6a to a vapour and gas separator 5. The raw gas (dry) obtained had the following average composition: CH (CH)₄About 72 vol%, H₂About 24.7% by volume, 1.5% CO, CO₂About 1.6% and other impurities (including H)₂S) was about 0.2%.

In the vapour-gas separator 5, the raw gas is desulphurised and separated on a membrane through which only hydrogen can pass, said hydrogen being sent via the hydrogen line 19 to the recycle hydrogen line 19a, combined with the biohydrogen in the line 18b and also sent to the excess hydrogen line 19b connected to the gas burner in the preheater 9. Steam and residual gases are discharged through line 17 and the mixture of biomethane and ecological methane flows through line 20 and is divided into two equal streams: biomethane supplied to the third biohydrogen-generating reactor 3 via line 20a and ecological methane supplied to the gas distribution line and to the power plant via line 20 b. The third bio-hydrogen generating reactor 3 comprises a catalyst (i.e. ceramic) packedNickel on a carrier) inner tube 3 a. These tubes are supplied with biomethane using line 20a and hot steam at about 400 c using steam line 11 a. The reaction of the biomethane with steam results in the reaction of the biohydrogen with CO as a result of the reaction taking place in the tubes containing the nickel catalyst in the third reactor 3₂The formation of a mixture of said biohydrogen and CO₂Is supplied via line 10b and heat exchanger 4a in waste heat boiler 4 and further supplied via line 10c to the bio-hydrogen and CO₂ A mixture separator 8. For formation of biohydrogen and CO from biomethane and steam₂Is supplied by a heated gas at a temperature of about 900 c, which is supplied to the third reactor 3 through the nozzle 10d and flows around the tubes 3a of the reactor 3, the remainder of the energy being brought about by the hot 400 c steam. The heat generated in the coal and biochar hydro-gasification reaction in the first reactor 1 and supplied to the preheater 9 through the heating line 7b is significantly higher than that required to supplement the heat energy supplied to the bio-hydrogen generation reaction. Excess heat is discharged from the heating gas preheater 9 to the waste heat boiler 4 via

lines

7c and 7 a. The heated gas cooled during the process in the third reactor 3 is supplied via line 10a to the heat exchanger 9a of the preheater 9 where it is heated up to 900 ℃ and flows again via line 10 to the nozzle 10d of the third reactor 3.

The biohydrogen generating reaction takes place at a temperature of about 500 c under a suitably increased pressure. Increasing the pressure to 3MPa results in an increase in the reaction rate and allows a reduction in the size of the third reactor 3. The waste heat boiler 4 is also supplied with make-up water from an external water source using a water line 12. The waste heat boiler 4 generates process steam of about 400 c, which is supplied to the third bio-hydrogen generating reactor 3 through the process steam line 11a, and generates power steam of about 585 c, which is supplied to the power turbine TP of the power generating apparatus via the power steam line 11 b.

Example II

The biochar having an elemental carbon content C' of 77% is supplied to a biochar hydro-gasification process using biohydrogen. In the first biochar hydro-gasification reactor shown in the figure, complete conversion of the biochar is performed. Hay was used as biomass for a complete pyrolysis to biochar process at a temperature of about 300 ℃, producing about 350kg of biochar per 1 ton of hay, plus pyrolysis gas. Feeding hay into the second biomass pyrolysis reactor 2 using a biomass conveyor 21; the produced biochar is then supplied to a biochar preparation plant 25 where it is suitably crushed and part of the pyrolysis gas is supplied via line 22a to the gas burner 13 in the reactor 2, while another part of the pyrolysis gas is carried via line 22b to the gas burner 14 in the heating gas preheater 9. The biochar, suitably crushed in the biochar preparation unit 25, is supplied via the biochar conveyor 26 to the top of the first biochar hydro-gasification reactor 1 where it is subjected to complete hydro-gasification to biomethane using biohydrogen at a temperature of about 815 c according to the process provided in example I. From the first reactor 1, the raw gas is supplied via line 6 through heat exchanger 6a to gas and vapor separator 5. The composition of the raw biogas is given in example I. In the steam and coal gas separator 5, the raw gas is desulfurized and separated and then sent via line 19 to line 19a connected to the biohydrogen line 18a, further through line 18b into the bottom of the first reactor 1, while the excess hydrogen flows through line 19b into the gas burner 14 in the preheater. The biomethane stream supplied to line 20 is split into two streams: biomethane which is conveyed via line 20a to the third biohydrogen-producing reactor 3 and biomethane which is conveyed via line 20b to be supplied to a power plant in the form of a fuel cell. Excess biomethane is supplied to a compressed biomethane tank. The generation of biohydrogen in the third reactor 3 is carried out according to the method provided in example I. The operation of the waste heat boiler 4 is described in example I.

The heated gas flowing out of the third reactor 3 into line 10a is supplied to a preheater 9 for said gas, where it is preheated to a temperature of about 900 ℃ using a gas burner 14 supplied with pyrolysis gas and part of the biomethane and excess hydrogen, and is subsequently recirculated via line 10 to the nozzles 10d of the third reactor 3. The tubes 3a are heated in the reactor and the biohydrogen and CO are in those tubes₂Formation of the mixtureThe procedure was carried out according to the procedure provided in example I.

Example III

Semi-carbon with an elemental carbon content C 'of about 60% and lignite with an elemental carbon content C of about 60% are supplied to a biochar and fossil carbon hydro-gasification process, maintaining a pre-set preferred biochar to coal ratio C' C1: 1 in the form of a suspension of a carbon mixture in mineral oil. In the first biochar and fossil carbon hydro-gasification reactor 1 shown in the figure, partial gasification of semi-carbon and lignite is carried out using bio-hydrogen, thus forming raw coal gas which is a mixture of unreacted hydrogen, bio-methane and other gaseous components and also forms fine coke. A system for producing biomethane and ecological methane is shown in the figure. Which is a gas production plant that produces ecological methane. As biomass of the partial pyrolysis process carried out in the second biomass pyrolysis reactor 2 at about 170 to 270 ℃, dry wood chips are used, which are supplied into the second reactor 2 using the biomass conveyor 21. The products of the partial pyrolysis of the biomass are semi-carbon and steam and combustible pyrolysis gas, one part of which is supplied via line 22a to the gas burner 13 in the second biomass pyrolysis reactor 2 and another part is supplied via line 22b to the gas burner 14 in the preheater 9 where the heating gas is a nitrogen stream. The semi-carbon is transported from the second biomass pyrolysis reactor 2 to the first carbon slurry preparation apparatus 25 using the biochar conveyor 23, where it is mixed with and suitably pulverized together with the brown coal supplied to the apparatus 25 by the coal conveyor 24, and the mineral oil is supplied thereto. The mixture formed by carbon and oil (comprising 75% by volume of mineral oil and 25% by volume of comminuted carbon) is supplied via supply line 26 to a nozzle which supplies a carbon slurry at a pressure of 6.8MPa to the uppermost section of the first reactor 1, known as the evaporation section. At the temperature of 315 ℃ which is advantageous here, the oil is evaporated and its vapours are discharged via the heat exchanger 6a to the vapour and gas separator 5 together with the hot raw gas leaving the intermediate section of the first stage, known as carbon hydro-gasification. The recovered mineral oil (which is subsequently condensed in a condenser) is recycled back to the carbon production plant 25, andthe raw gas undergoes purification and desulfurization. Dry carbon and biochar particles at a temperature of about 300 ℃ are passed to the central section, which are subjected to fluidization in the gas stream containing biohydrogen leaving the bottom section of the reactor, called the second stage of carbon hydro-gasification, and in the central section degassing and partial hydro-gasification of the carbon particles takes place at a temperature raised to 650 ℃ and a pressure of 6.8 MPa. The partially converted carbon mixture is subjected to complete hydro-gasification in the fluidized bed of the bottom section of the first reactor 1 at a temperature of 750 ℃ to 950 ℃ using bio-hydrogen and hydrogen supplied to said section. The purified raw gas undergoes further separation in the vapour and gas separator 5, in which unused hydrogen is separated from the methane mixture of biomethane and ecological methane and recycled back to the recycled hydrogen line 19a via the hydrogen line 19, combined in line 18b with the supply of biohydrogen at the bottom of the first reactor 1, and recycled back to the excess hydrogen line 19b connected to the gas burner 14 in the preheater 9. The methane mixture flows through a line 20 which splits into a biomethane line 20a supplying biomethane to the third biohydrogen producing reactor 3 and a line 20b supplying biomethane to the gas distribution system. The generation of biohydrogen takes place in the third reactor 3 as a result of the reaction of the biomethane with steam. The energy required for the endothermic reaction is brought by the heating gas supplied to the third reactor 3 through the line 10 and the nozzle 10d and the hot steam supplied from the steam line 11a, and the amount of energy to be supplied can be controlled by controlling the flow rate and temperature of the heating gas flowing around the tube 3a in the third reactor 3, and the like. The biohydrogen forming reaction takes place inside the tube 3a at a temperature of about 500 ℃ in the presence of a catalyst (nickel supported on a ceramic substrate), said tube 3a being heated by a hot stream of heating gas at a temperature of 900 ℃. The produced and cooled biohydrogen is transported to the first carbon and biochar hydro-gasification reactor 1. The reaction of biohydrogen with the element carbon C' from the semi-carbon and with the element carbon C from the lignite produces biomethane and ecological methane and the heat associated with the carbon hydro-gasification reaction. The heat from the cooling of the raw gas in heat exchanger 6a is supplied via heating line 7b to the heating gas preheater 9 and, subsequently, toThe heat of the hot gas from the preheater 9 is supplied to the waste heat boiler 4 via

lines

7c and 7 a. Furthermore, the waste heat boiler 4 receives heat from a number of sources, in particular heat from the cooling of the bio-hydrogen in the heat exchanger and from the bio-hydrogen and CO leaving the third bio-hydrogen generating reactor 3₂Heat of the mixture flowing through line 10b to heat exchanger 4a in waste heat boiler 4 and leaving waste heat boiler 4 through line 10c to separator 8, in which separator 8 the mixture is separated into biohydrogen supplied to first reactor 1 via

lines

18a and 18b and is sent to CO₂And (5) sealing and storing the carbon dioxide of the equipment. CO leaving separator 8₂The stream (previously cooled in heat exchanger 4a in waste heat boiler 4) is passed through CO₂Line 10e flows to CO₂Sequestration processes, especially CO by silicates such as serpentine₂And (5) sealing and storing. The immobilized products, magnesium carbonate, silica and water, are durable and easy to store.

In another embodiment, the heated gas preheater 9 is connected to a solar collector system. CO as a heat carrier in all heat exchangers of a solar collector system₂Heated up to about 1200 ℃ and recycled back to a heat exchanger 30 located in the preheater 9, from which heat exchanger 30 heat is supplied via a heating gas line 10 to a third reactor 3, which third reactor 3 produces a separation into biohydrogen and CO in a separator 8₂Biological hydrogen and CO₂Mixture, the separator 8 being a potassium scrubber. The heat of the solar energy is transferred by means of a heat carrier with a high efficiency of up to 80% to the third reactor 3, where it is converted into chemical energy of biohydrogen, and subsequently into chemical energy of biomethane and ecological methane in the first reactor 1.

Embodiments of the device

As shown, the first carbon and biochar hydro-gasification reactor 1 has two inlets, 18b and 26, the first inlet 18b for hydrogen and the other inlet 26, as a conveyor of the carbon mixture, is connected to a carbon mixture preparation device 25 connected to the second biomass pyrolysis reactor. The second pyrolysis reactor 2 is equipped with pyrolysis gas lines 22a and22b, wherein line 22a is connected to the gas burner 13 located in the reactor and line 22b is connected to the gas burner 14 located in the heating gas preheater 9. The second pyrolysis reactor 2 is equipped with two conveyors, wherein the conveyor 21 is a biomass conveyor and the conveyor 23 is a biochar conveyor connected to a carbon mixture preparation device 25. The apparatus has an outlet 16a and an inlet 16 for the cleaning 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 outlet (fine coke outlet) 28 is connected to a fine coke conveyor 28a feeding the pulverized fuel burners 15 located in the preheater 9 and to a conveyor 28b for access to storage, and the first outlet 6 for the raw gas is connected to the vapour and coal gas separator 5 through a heat exchanger 6 a. The vapor and coal 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 of the separator 5 is split into two lines 19a and 19b, wherein line 19a is connected to the first inlet 18b of the first reactor 1 and line 19b is connected to the burner 14 in the preheater 9, and the second methane outlet 20 of the separator 5 is further connected to the third reactor 3, the first outlet 10b of said third reactor 3 is connected to the separator 8 via the heat exchanger 4a of the waste heat boiler 4 and via line 10c, the first biohydrogen outlet of said separator 8 is connected to the first reactor 1 via

lines

18a and 18b, and the second CO is₂The outlet is connected to CO via line 10e₂A sealing device (not shown in the figures). The waste heat boiler 4 has a connection to a third biological hydrogen and CO via a steam line 11a₂A process steam outlet of the generating reactor 3 and an electricity steam outlet of a steam turbine (not shown in the figure) connected to the power plant via line 11 b. The waste heat boiler 4 also has a connection to a water line 12. The second outlet of the third reactor 3 is connected to a heating gas line 10a connected to a heat exchanger 9a in the preheater 9, which exchanger is connected via line 10 to a heating gas nozzle 10d located in the third reactor 3. Furthermore, a heat exchanger 6a, which extracts heat from the heated gas, is connected to the waste heat boiler 4 via a line 7b, a preheater 9 and

lines

7c and 7 a. Furthermore, the preheater 9 is equipped with heat connected to a solar collection deviceExchanger 30 and the third reactor has a set of tubes 3a with catalyst.

Reference numerals used in the drawings

1-first reactor for the hydro-gasification of carbon and/or biochar

2-second Biomass pyrolysis reactor

3-third reactor for generating biohydrogen

3 a-tube assembly of the reactor R (III)

4-waste heat boiler

4 a-first heat exchanger of waste heat boiler

5-vapor and coal gas separator

6-crude gas pipeline

6 a-second raw gas heat exchanger

7 a-line for supplying heat to a boiler

7 b-raw gas heating pipeline

7 c-preheater heating pipeline

7 d-line for external heating

8-hydrogen separator

9–CO₂Flow preheater

Third heat exchanger of 9 a-preheater

10-heated gas flow line

10 a-recycle gas flow line

10 b-Hydrogen line

10 c-line for hydrogen off

10 d-heated flow nozzle

10 e-CO to discharge or sequestration₂Pipeline

11 a-process steam line

11 b-electric power steam line

12-Water line

13-gas burner in apparatus

Gas burner in 14-preheater

Pulverized fuel burner in 15-preheater

16-for removing carbonCO of the mixture₂Nozzle with a nozzle body

16 a-outlet for purge gas

17-lines for the exit of vapours and gases

18 a-biological hydrogen pipeline

18 b-Hydrogen trap line

19-separate Hydrogen line

19 a-recycled Hydrogen line

19 b-excess Hydrogen line

20-methane mixture pipeline

20 a-biomethane line

20 b-ecological methane pipeline

21-Biomass conveyor

22-Biomass pyrolysis device

22 a-pyrolysis vapour and gas line

22 b-pyrolysis gas line supplying preheater

23-biochar conveyor

24-carbon (lignite or coal) conveyor

25-carbon mixture preparation device

26-carbon mixture conveyor

27-powdered carbon/biochar conveyor

28-Fine Coke conveyor

28 a-ground fine coke conveyor

28 b-Fine Coke conveyor to storage

29-waste conveyor

30-fourth Heat exchanger for solar Heat

Claims

1. A method for producing biomethane and ecological methane, the method being carried out using the following process: using a process for pyrolyzing biomass to biochar and mixing with pulverized and possibly suitably prepared fossil carbon, and using a process for hydro-gasification of a carbon mixture, said process being characterized in that pulverized dry plant-based or waste-based raw materials are subjected to gasification, either alone or in specific mannerThe group of forms is subjected to a pyrolysis process either carried out at a temperature range of about 170 ℃ to 270 ℃ at standard pressure to produce semi-carbon and pyrolysis gases, or at a temperature range of about 270 ℃ to 300 ℃ to produce biochar and pyrolysis gases, or at a temperature range above 300 ℃, part of the pyrolysis gases being passed to a second biomass pyrolysis reactor for biomass pyrolysis, another part of the pyrolysis gases being passed to a preheater for preheating a stream of heating gases, while the obtained semi-carbon containing about 60% to 65% of elemental carbon is preferably mixed with pulverized lignite, while the biochar containing about 65% to 80% of elemental carbon is mixed with pulverized coal, the ratio of biochar-based elemental carbon C 'to fossil-carbon-based elemental carbon C preferably being C': C1: 1, the former mixture or the latter mixture being supplied to the first hydro-gasification reactor, wherein a complete hydro-gasification process using bio-hydrogen is carried out to produce raw gas and ash, or a partial hydro-gasification process of coal with bio-carbon or lignite with semi-carbon is carried out to produce raw gas and fine coke, while the fine coke is passed to a preheater to preheat the heating gas stream, while the obtained raw gas cooled in a second heat exchanger is subjected to a desulfurization process, followed by separation into hydrogen, residual gas and a methane mixture consisting of pure bio-methane and eco-methane, while the heat from cooling of the raw gas is passed to the preheater to preheat the heating gas and to a first heat exchanger in a waste heat boiler producing steam, while a part of the methane is passed to a gas distribution line and another part is supplied to a third bio-hydrogen generation reactor, wherein in the reaction of bio-methane with hot steam from the waste heat boiler, forming biohydrogen and CO at a temperature of about 500 ℃ to 700 ℃ and in the presence of a catalyst using heat supplied to the reaction by a heating gas₂After cooling in the waste heat boiler, the mixture being separated into CO₂And bio-hydrogen to a carbon mixture hydro-gasification process in the first reactor, while the heating gas is preheated in a preheater to about 800 ℃ to 1200 ℃ required for bio-hydrogen formation reactions in a third reactorUsing a gas burner supplied with pyrolysis gas from the second biomass pyrolysis reactor and/or using excess hydrogen recovered from the raw gas and using a powder fuel burner supplied with ground fine coke or carbon or biochar, and supplying the thus heated stream of heating gas to the third reactor.

2. The method according to claim 1, wherein the pulverized dried mixture of semi-carbon and lignite or biochar and coal is supplied from a carbon mixture preparation unit to the first reactor, where the carbon mixture hydro-gasification process is first carried out in a suspension bed in an inner chamber and flowing down with a gas supplied from the top of the inner chamber, the gas containing about 50% of H at a pressure of about 2.5MPa to 7.0MPa at a temperature of about 815 ℃₂And 50% of CH₄The raw gas obtained in the process is sent to a vapour and gas separator, where it is freed of dust and blended gases, in particular subjected to desulfurization, after which it is separated into a pure methane mixture consisting of biomethane and ecological methane and pure hydrogen, while the partially converted carbon mixture is sent to the outer chamber of the first reactor, where it is subjected to complete conversion with hydrogen to yield ash and hydrogen + methane gas, or to complete conversion with biomethane and hydrogen to yield fine coke and hydrogen + methane gas or to partial conversion into fine coke and the hydrogen + methane gas, while the hydrogen + methane gas is supplied to the inner chamber of the reactor.

3. The method according to claim 1, characterized in that in the first high-pressure reactor the carbon mixture, after being combined with mineral oil in a ratio of 1:2.5 to 1:3.5, is supplied in suspension to the highest section of the reactor, called the evaporation section, using a nozzle, wherein the oil is evaporated and its vapors are discharged with hot raw gas to a vapor-coal gas separator at a pressure of about 6.8MPa and at a prevailing temperature of about 315 ℃, where the mineral oil recovered and subsequently condensed in a condenser is recycled back to the carbon-in-oil suspension production plant, whereas the raw gas purified, in particular after desulphurization, is separated into a methane mixture and pure hydrogen combined with bio-gas, whereas the falling dry carbon and bio-carbon particles at a temperature of about 300 ℃ are transported to the middle section of the first reactor, wherein the particles are subjected to fluidization in the flow of the biohydrogen containing gas leaving the bottom section of the second stage, called carbohydrogasification, of the reactor, whereas in the intermediate section of the first stage, called carbohydrogasification, the degassing and partial hydrogasification of carbon and biochar is carried out at an elevated temperature of about 650 ℃ and a pressure of 6.8MPa, after which the partially converted carbon mixture is subjected to complete hydrogasification in the fluidized bed of the bottom section of the reactor at a temperature of 750 ℃ to 950 ℃ using biohydrogen and hydrogen supplied to the bottom section.

4. The method according to claim 1 and any one of claims 2 and 3, wherein the heating gas is a gas inert to the material of the third reactor, preferably CO₂Nitrogen, helium or argon, or a gas with a high specific heat or a liquid with a high boiling point, the heated gas carrying heat to the third reactor for bio-methane reaction with steam, the amount of heat being Ni/Al at a temperature of about 500 ℃ to 700 ℃₂O₃Sufficient to carry out the biological hydrogen and CO in the presence of a catalyst₂About 165kJ/mol CH of the formation reaction₄。

5. The method of claim 1, wherein the hydrogen and CO are derived from the organism at a temperature of about 500 ℃₂Is carried to the waste heat boiler, from the flow of gas at a temperature of about 600 ℃ leaving the preheater and from external systems, in particular from power generation devices generating electrical and thermal energy.

6. The method of claim 4, wherein high temperature heat taken from raw gas and heat supplied by solar collectors are transported to the heating gas preheater.

7. The process of claim 1, wherein in the first section of the third reactor, in a reactor tube, at a temperature range of about 500 ℃ to 900 ℃ and a pressure of 1.5MPa to 4.5MPa, Ni/Al₂O₃Production of biohydrogen and CO in the presence of a nickel catalyst₂The reactants of (a): the biomethane and steam are additionally heated by a hot heating gas stream at a temperature of about 800 ℃ to 1200 ℃.

8. The method according to any one of claims 1 and 7, wherein for the biohydrogen forming reaction of carbon monoxide and water vapour in the third reactor, the gas mixture in the biohydrogen forming reaction flows from a first section of the third reactor to a second section of the third reactor, the second section operating at a lower temperature range than the first section, or using Cu-Zn/Al in a temperature range of about 200 ℃ to 300 ℃₂O₃Catalyst, or use of Fe/Al in higher temperature range of 350-500 deg.C₂O₃The catalyst is then used with Cu/Al in the range of about 200 ℃ to 300 ℃₂O₃Catalyst, or using Fe in the temperature range of 300 ℃ to 450 ℃₂O₃+Cr₂O₃A catalyst performs the reaction.

9. A system for producing biomethane and ecological methane consisting of: a carbon hydrogasification reactor, a biohydrogen generating reactor, a vapour and coal gas separator, a biomass pyrolysis reactor, a carbon mixture preparation device, a waste heat boiler, a heating gas preheater, a heat exchanger, a conveyor, lines and pumps for liquid, vapour and gas, the system being characterized in that a first carbon hydrogasification reactor (1) has a first inlet (18b) and a second inlet (26), wherein the first inlet (18b) is for hydrogen and the second inlet (26) is connected to a carbon mixture preparation device (25) connected to a second biomass pyrolysis reactor (2), the first reactor (1) has a first outlet (6) and a second outlet (28), wherein the second outlet (28) is for fine coke and the first outlet (6) is for raw coal gas, the first outlet (6) is connected to the vapour and coal gas separator (5) by a second heat exchanger (6a), the vapour and gas separator (5) having a first hydrogen outlet (19), a second methane outlet (20) and a third waste outlet (17), wherein the first hydrogen outlet (19) of the separator (5) is divided into two lines (19a) and (19b), wherein line (19a) is connected to the first inlet (18b) of the first reactor (1) and line (19b) is connected to the burner (14) of the preheater (9), and the second methane outlet (20) of the separator (5) is further connected to the third hydrogen generating reactor (3), the first outlet (10b) of the third hydrogen generating reactor (3) is connected to the separator (8) via the boiler waste heat (4), the outlet of the separator (8) is connected to the first reactor (1) via line (18a), furthermore the waste heat boiler (4) has a process steam outlet (11a) connected to the third reactor (3), while the second outlet of the third reactor (3) is connected to a heating gas line (10a) connected to the preheater (9), furthermore a heat exchanger (6a) is connected to the waste heat boiler (4) via line (7b), preheater (9) and line (7 c).

10. The system according to claim 9, characterized in that the second biomass pyrolysis reactor (2) has a dry biomass inlet and a biochar outlet connected to the means (25), and a pyrolysis gas outlet (22a) connected to a gas burner (14) located in the heating gas preheater (9).

11. The system according to any one of claims 9 and 10, characterized in that the preheater (9) has a third heat exchanger (9a), which third heat exchanger (9a) is connected at one end to the heating gas line (10a) and at the other end via a line (10) to a nozzle (10d) installed at the inlet of the third reactor (3), while the preheater (9) is equipped with a burner (14) connected via a line (22b) to the second biomass pyrolysis reactor (2) and a pulverized fuel burner (15) connected via a conveyor (28a) to a fine coke outlet (28), and furthermore the preheater (9) is connected to the waste heat boiler (4).

12. The system according to claim 9, characterized in that the third reactor (3) has an inner tube (3a), the inner tube (3a) containing a nickel catalyst Ni/Al supported on a ceramic substrate in the first part of the third reactor (3)₂O₃Said first portion being connected to a heated gas inlet (10d), said tube (3a) further comprising Cu-Zn/Al₂O₃Catalyst, or Fe/Al₂O₃And Cu/Al₂O₃Catalyst, or Fe₂O₃+Cr₂O₃A catalyst, said tubes being located in a second part of the third reactor, while the third reactor (3) has an inlet (20a) for biomethane, an inlet (11a) for process steam and for biohydrogen and CO₂Outlet (10b) for the mixture (b).

13. The system of claim 9, wherein the hydrogen and CO are₂The mixture separator (8) has pure CO which is open to the atmosphere and/or is used for downstream processing and/or sequestration₂An outlet (10 e).