Syngas production system and syngas production process
A combined dense and circulating fluidized bed reactor system optimizes pyrolysis and gasification processes to produce high-purity, low-pollutant syngas efficiently, addressing the limitations of existing technologies by enhancing yield and reducing environmental impact.
Patent Information
- Application Number
- PCT/EP2025/051717
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2024-01-25
- Filing Date
- 2025-01-23
- Publication Date
- 2025-07-31
Smart Images

Figure EP2025051717_31072025_PF_FP_ABST
Abstract
Description
SYNTHESIS GAS PRODUCTION SYSTEM AND SYNTHESIS GAS PRODUCTION METHOD
[0001] The invention relates to the field of energy. In particular, the invention relates to a system for producing synthesis gas.
[0002] The invention further relates to a method for producing synthesis gas.
[0003] Below we describe the known prior art from which the invention was developed.
[0004] Fossil fuels accounted for more than 80% of global energy consumption in 2020, the most common of which are natural gas, oil, and coal. These fossil fuels are a significant cause of global warming and CO2 emissions. To combat this warming and CO2 emissions, the French government has set itself the goal of reducing greenhouse gas emissions resulting from the excessive use of fossil fuels by 81% by 2050 (Ecological Transition). One of the most promising avenues for promoting the ecological transition and reducing CO2 emissions appears to be the production of synthetic gas that can be converted into hydrogen (H2), or synthetic natural gas (CH4).
[0005] Syngas can be produced using a variety of techniques. Production techniques, as well as the quantity and quality of the resulting syngas, depend largely on the raw materials used and the technique used (pressure, temperature, reaction rate). These techniques include, for example, gasification, pyrolysis, and extraction methods.
[0006] Depending on the raw materials used, pyrolysis techniques produce reaction by-products such as chlorine, sulfur, nitrogen, tar, ash, or even char. These by-products are considered pollutants. Indeed, they greatly reduce the purity of the synthesis gas produced (and therefore the quality of the synthesis gas). In addition, their accumulation in production equipment leads to fouling, which can cause blockages while being corrosive.
[0007] Also, other processes exist and are developing, such as the pyrogasification of organic matter. The pyrogasification of organic matter appears to be a promising technology for the production of synthesis gas. Pyrogasification generates a "synthesis gas or syngas," consisting mainly of carbon monoxide (CO) and hydrogen (H2). The hydrogen produced by this reaction subsequently requires a purification step to eliminate pollutants. This solution allows for a virtually neutral greenhouse effect balance, because the CO2 emitted by the combustion of carbon monoxide is equivalent to that which would have been released by the degradation of the organic raw material.
[0008] First generation processes (or integrated processes) combine the combustion of the energy vector in the same equipment as the thermal gasification equipment. Although by reducing the amount of fumes emitted into the atmosphere (3,500 to 4,000 Nm 3 / t, compared to 6,500 to 7,500 Nm 3 / t in traditional combustion), the technology results in the production of a synthesis gas with low calorific value on the one hand and of poor quality on the other. Indeed, since the process is integrated, the reaction conditions cannot be controlled and the quantity of pollutant produced is significant.
[0009] Second-generation processes (or non-integrated processes) are characterized by the fact that the recovery of the energy compounds produced in the thermal gasification unit is carried out in a separate unit (boiler burner, industrial process, gas engine, etc.). Thus, unlike the first-generation process, control of the reaction conditions is possible and the quality of the synthesis gas produced could be improved.
[0010] Within each of these two process families, there are a large number of pyrogasification technologies. The most widespread are countercurrent or cocurrent fixed bed technologies or entrained bed technologies.
[0011] Countercurrent fixed-bed technologies are characterized by inputs forming a dense bed in the reactor and moving vertically under the action of gravity. These processes accept high humidity levels and produce a tar-containing gas, which is formed during the pyrolysis stage. The limitations of this technology are mainly related to poor hot spot control and poor heat and mass transfer efficiency.
[0012] In co-current fixed-bed technology, the inputs are fed into the upper part of the reactor, and the air is fed into the intermediate zone with a diameter restriction. The generated gas is cracked through the high-temperature oxidation zone, so that less tar is entrained. However, this technology is also used for small plants and the main limitations of this technology are related to the risk of ash melting and the fact that the fuels must have a moisture content of less than 20%.
[0013] Finally, entrained bed technology is a process in which direct contact between the solid and the gas takes place. This is done in the presence of air or water at a high temperature (1200-1400 °C). This process requires extensive preparation of the inputs to be treated. In addition, this process requires significant CAPEX (process under high pressure and temperature).
[0014] Thus, all the pyrogasification technologies mentioned above have numerous limitations. On the one hand, fixed bed technologies have a double limitation: difficulty in controlling hot spots and poor heat and mass transfer efficiency. On the other hand, entrained bed technologies require exorbitant CAPEX for technical efficiency and unguaranteed profitability. In addition, these technologies face major challenges such as the presence of tars, but also fine particles, hydrogen sulfide, chlorides, alkali sulfide and ammonia, which constitute pollutants and deteriorate the quality of syngas and equipment.
[0015] Faced with these numerous limitations, researchers have developed the use of fluidized bed technologies. This technology suspends inert particles in a reactor to promote heat exchange. The syngas obtained are richer than with fixed-bed reactors. However, the tar content remains high (> 2g / Nm 3 ) and the risk of ash agglomeration is significant depending on the temperature regimes chosen. In addition, given the size of the infrastructure using this technology, the CAPEX is also very high.
[0016] In view of the above, it is clear that tar formation is a limiting factor in existing processes. Indeed, during gasification, many reactions are involved, both endothermic and exothermic.
[0017] Furthermore, the reactions are highly dependent on the environmental conditions. For example, high pressure is not conducive to steam gasification and the Boudouard reaction, but will favor the production of hydrocarbons. Another example is related to temperature: the lower the operating temperature of the gasifier, the more tar is produced by internal tar cracking. Therefore, for a fixed-bed gasifier, the tar concentration for countercurrent operation is 10-150 g / Nm 3 of synthesis gas, while the tar concentration for co-current operation is 0.01-6 g / Nm 3 Thus, gasification technology, especially from organic raw material, is faced with the problem of purity of synthesis gas (the high presence of tar and other particles).
[0018] Thus, in order to obtain a suitable synthesis gas composition, the operating parameters (temperature, pressure, oxygen equivalence ratio, steam / fuel ratio) must systematically be optimized for each gasification unit.
[0019] Several researchers (AWAIS et al, 2018; Evaluating removal of tar contents in syngas produced from downdraft biomass gasification system, International Journal of Green Energy, 15(12), 724-731; HERVY et al, 2019; Reactivity and deactivation mechanisms of pyrolysis chars from bio-waste during catalytic cracking of tar, Applied Energy, 237, 487-499, NAKAMURA et al., 2016; Biomass gasification process with the tar removal technologies utilizing bio-oil scrubber and char bed, Applied Energy, 170, 186-192, VREUGDENHIL et al, 2009 Tar formation in pyrolysis and gasification) then mention the inhibition of tar formation in a reducing environment (i.e., in an unconventional way), by ex-situ demolition (downstream treatment of tars and catalytic cracking). and thermal of syngas) or by in-situ slaughter, for example in fluidized bed gasifiers.In this case, the reforming process converts the tars into carbon monoxide and hydrogen under the action of catalysts. Thus, these two tar destruction systems are often used together. However, in the literature, destruction by catalytic cracking is the most emphasized.
[0020] Indeed, researchers Corella, De Andre, Naqvi, et al. (CORELLA et al, 2004; Olivine or Dolomite as in-bed additive in biomass gasification with air in fluidized bed, Which is better?, Energy & Fuels 18(3), 713-720 DE ANDRES et al., 2011; Behavior of dolomite, olivine and alumina as primary catalysts in air-steam gasification of sewage sludge, Fuel, 90(2), 521-527, NAQVI et al, 2016, An experimental study on hydrogen enriched gas with reduced tar formation using pre-treated olivine in dual bed steam gasification of mixed biomass compost, International journal of hydrogen energy, 41(25), 10608-10618) tested catalysts such as olivine, nickel and dolomite. Tested under experimental conditions in pilot plants (fluidized beds), dolomite made it possible to reduce the tar content at the outlet of the first bed (pyrolysis) by up to 76% (DE ANDRES, 2011). As for the use of olivine, this made it possible to reduce tar by up to 98% (NAQVI; 2016).Besides the fact that the use of olivine seems more interesting than the use of dolomite, dolomite generates on average 5 times more polluting particles (notably NH3) than olivine. Therefore, the use of olivine seems more judicious (CORELLA, 2004; FREDRIKSSON et al, 2013; Olivine as tar removal catalyst in biomass gasification: Catalyst dynamics under model conditions. Applied Catalysis B: Environmental, 130-131; 168-177, TURSUN et al, 2019 Biomass gasification for hydrogen rich gas in a decoupled triple bed gasifier with olivine and NiO / Olivine. Bioresource Technology, 272, 241-248). Indeed, since the formation of tar takes place mainly during the pyrolysis reaction and during the production of syngas, the tars formed must be cracked immediately.For example, the GoBiGas process (process for producing methane from biomass gasification) (LARSSON et al; 2015- The GoBiGas Project, demonstration of the production of biomethane from biomass via gasification (Anton Larsson, Ingemar Gunnarsson, Freddy Tengberg; Götborg Energi AB) Monitoring the bed material activation in the GoBiGas gasifier) through the use of olivine and potassium carbonate (to activate the olivine) produced methane without tar production (Transformation and Release to the Gas Phase of Cl, K, and S during Combustion of Annual Biomass, 2004, Knudsen, Jensen, Dam-Johansen).
[0021] More specifically, HERVY et al. (HERVY, 2019) studied the cracking of tar compounds (ethylbenzene and benzene). The cracking tests were carried out in a wide temperature range: ethylbenzene cracking from 400 to 650°C, benzene cracking from 850 to 950°C. The performance of several ethylbenzene cracking tests at 650°C showed that mesoporous catalysts are more resistant to coke deactivation (coal) than microporous catalysts (HERVY, 2019). Furthermore, other researchers (AWAIS, 2018, NAKAMURA, 2016) rather mention as solutions to the inhibition of tar formation the optimization of cleaning units (cyclone separator, wet scrubber, biomass filter and auxiliary filter). Indeed, AWAIS et al. showed that an optimized cleaning system can reduce the concentration of tars in wood chips from 6,600 to 112 mg / Nm 3; or by using by-products (bio-oil and coal) as tar absorbents. Indeed, given their porosity, for example, the carbon bed filter can remove up to 81.5% of the tar from the production gas at the start of the operation.
[0022] However, all these methods have only been tested on a pilot scale and have not yet demonstrated their viability on all types of installations, so much research still needs to be carried out with the aim of producing pollutant-free syngas.
[0023] Thus, whatever the pyrogasification technology, there are many limitations to producing a syngas with improved quality, acceptable calorific value and whose production technique allows to reduce the formation of pollutants, to control the reaction conditions while presenting an acceptable CAPEX. Furthermore, it appears essential to develop a technology to optimize the process of separation of pollutants and to reduce the rate of tars in current processes. There is also the problem of determining the optimal pyrolysis conditions preferably from organic matter (conversion rate to char) on the one hand to ensure the departure of certain molecules that are expensive to filter during pyrolysis and on the other hand to preserve a maximum of hydrogen and carbon to optimize the conversion rate to hydrogen or synthetic natural gas.It also appears necessary to ensure the adaptability of the process to the heterogeneity of the inputs and the reliability of the pyrogasification installation in order to guarantee proper operation, regardless of the nature of the input, and to ensure industrial-type operation.
[0024] There is therefore an urgent need to be able to produce clean synthesis gas (with a reduced or pollutant-free level) in an economical (resource and financial) and industrial manner, allowing CO2 emissions to be reduced and presenting high purity as well as improved production yields.
[0025] The invention aims to overcome the drawbacks of the prior art. In particular, the invention aims to propose a system for producing synthesis gas and preferably intended for the production of hydrogen and / or synthetic natural gas, said system being less expensive economically and energetically, and making it possible to produce a synthesis gas free of pollutants while maximizing yields. Indeed, the invention aims to propose a new system for producing synthesis gas (preferably intended for the production of hydrogen, synthetic natural gas) making it possible to reduce the pollutants present in the gases produced, to maximize production yields while limiting the consumption of energy, resources and reducing the carbon footprint compared to existing solutions. Furthermore, it is also an objective of the invention that the system can be integrated into various applications.
[0026] The invention further aims to propose a process for producing synthesis gas, said process making it possible to produce a synthesis gas free of pollutants economically, with little or no energy consumption and whose yields can be maximized.
[0027] The invention also aims to provide a system for the production of synthesis gas, preferably for the production of hydrogen and / or synthetic natural gas and preferably of decarbonized and / or recovered hydrogen and / or of decarbonized and / or recovered synthetic natural gas and a method for the production of synthesis gas, preferably of hydrogen and / or synthetic natural gas and more preferably of decarbonized and / or recovered hydrogen and / or of decarbonized and / or recovered synthetic natural gas.
[0028] The invention aims to overcome the disadvantages of the prior art. The following presents a simplified summary of selected aspects, embodiments and examples of the present invention for the purpose of providing a basic understanding of the invention. However, this summary does not constitute an exhaustive overview of all aspects, embodiments and examples of the invention. Its sole purpose is to present selected aspects, embodiments and examples of the invention in a concise form as an introduction to the more detailed description of the aspects, embodiments and examples of the invention which follow the summary.
[0029] The invention relates in particular to a system intended for the production of synthesis gas comprising at least one first dense fluidized bed reactor, at least one second dense fluidized bed reactor, at least one circulating fluidized bed reactor, at least one separator, at least one steam generator in which: the at least one first dense fluidized bed reactor is configured for a raw material pyrolysis reaction and to supply pyrolyzed solids to the at least one second dense fluidized bed reactor and to supply a first fluid to the at least one circulating fluidized bed reactor, the at least one second dense fluidized bed reactor is configured for a vapor-gasification reaction of pyrolyzed solids and to discharge a synthesis gas and to supply fluidization media to the at least one circulating fluidized bed reactor,the at least one circulating fluidized bed reactor is configured for an oxidation reaction of a first fluid and to supply fluidization media and fumes to the at least one separator, the at least one separator is configured to separate the fluidization media from the fumes, and to supply fluidization media to the at least one first dense fluidized bed reactor and / or the at least one second dense fluidized bed reactor, and / or the at least one circulating fluidized bed reactor and to supply fumes to the at least one steam generator.,
[0030] The applicant has developed a new system capable of producing syngas. Such a system makes it possible to avoid the use of fossil fuels and reduce CO2 emissions. In addition, the system according to the invention makes it possible to improve the yields of syngas produced while improving its quality (i.e. purity). Thus, the quantity of pollutants is reduced. In addition, such a system is suitable for industrial production and various applications. In addition, the system's equipment is less damaged (less subject to alterations, particularly corrosion).
[0031] The applicant has developed in particular a particular arrangement and sequence between the different reactors and separator and generator, which also makes it possible to reduce the need for resources.
[0032] According to other optional features of the system, the latter may optionally include one or more of the following features, alone or in combination:the at least one separator is configured to supply fluidization media to a distributor the feedstock is selected from inputs having at least 30% carbon such as biomass, SRF (solid recovered fuel), waste, and / or wood by-products, preferably in the syngas production system and more preferably in the at least one first reactor of the syngas production system the feedstock is selected from inputs having a moisture content of less than or equal to 40%,preferably in the synthesis gas production system and more preferably in the at least one first reactor of the synthesis gas production system, the at least one steam generator is configured to supply non-oxidizing fluid to the at least one dense fluidized bed reactor and the at least one second dense fluidized bed reactor.,
[0033] According to a second object, the invention relates to a system intended for the production of hydrogen, preferably decarbonized and / or recovered, comprising at least one system intended for the production of synthesis gas according to the invention, the system intended for the production of hydrogen further comprising: A filtration means configured to filter the synthesis gas, A carbon monoxide conversion means configured to convert carbon monoxide and water vapor into carbon dioxide and hydrogen A purification means configured to separate (i.e. purify) the hydrogen and obtain hydrogen, preferably decarbonized and / or recovered hydrogen
[0034] According to other optional features of the system, the latter may optionally include a conversion means configured to convert hydrogen to ammonia and / or a cracking means configured to reduce tars.
[0035] According to a third object, the invention relates to a system for the production of synthetic natural gas, preferably decarbonized and / or recovered, comprising at least one system for the production of synthesis gas according to the invention, the system for the production of synthetic natural gas further comprising: A filtration means configured to filter the synthesis gas, A carbon monoxide conversion means configured to convert carbon monoxide and water vapor into carbon dioxide and hydrogen A methanation means configured to convert hydrogen and / or carbon dioxide into synthetic natural gas
[0036] Depending on other optional features of the system, the system may optionally include a cracking means configured to reduce tars.
[0037] According to a fourth object, the invention relates to a process for the production of synthesis gas capable of being implemented in (i.e.by) a system for the production of synthesis gas according to the invention, comprising:A step of pyrolysis from raw material in at least one first dense fluidized bed reactor so as to form a first fluid and pyrolyzed solids,A step of vapo-gasification in at least one second dense fluidized bed reactor from the pyrolyzed solids so as to form a synthesis gas,An oxidation step in at least one circulating fluidized bed reactor from the first fluid so as to generate fumes,A step of heat transfer by at least one separator from a fluidization medium between the at least one separator and the at least one first dense fluidized bed reactor and / or the second dense fluidized bed reactor and / or the at least one circulating fluidized bed reactora step of generating steam from the fumes by a steam generator.
[0038] According to a fifth object, the invention relates to a method for the production of hydrogen, preferably decarbonized and / or recovered, capable of being implemented in (i.e. by) a system for the production of hydrogen according to the invention, the method for the production of hydrogen comprising a method for the production of a synthesis gas according to the invention and further comprising: A step of filtration by a filtration means, of the synthesis gas, A step of enrichment, by a means for converting carbon monoxide, of the synthesis gas, A step of purification by a purification means to separate the hydrogen and obtain a hydrogen, preferably decarbonized and / or recovered hydrogen.
[0039] According to other optional features of the process, the latter may optionally include a conversion step by a means for converting hydrogen into ammonia and / or a cracking step by a cracking means to reduce tars.
[0040] According to a sixth object, the invention relates to a method for the production of synthetic natural gas, preferably decarbonized and / or recovered, capable of being implemented in (i.e. by) a system for the production of synthetic natural gas according to the invention, the method for the production of synthetic natural gas comprising a method for the production of a synthesis gas according to the invention and further comprising: A step of filtration by a filtration means, of the synthesis gas, A step of enrichment, by a carbon monoxide conversion means, of the synthesis gas, A step of methanation by a methanation means to convert the carbon monoxide and / or the hydrogen and / or the carbon dioxide into synthetic natural gas.
[0041] According to other optional features of the process, the latter may optionally include a cracking step by a cracking means to reduce the tars.
[0042] The invention also relates to a synthesis gas production unit comprising at least one system intended for the production of synthesis gas according to the invention.
[0043] The invention also relates to the use of a system for the production of synthesis gas according to the invention in the production of electricity, in the production of hydrogen, in the production of synthetic natural gas, in the production of methane, in the production of ammonia, in the production of steam, in the production of heat, in the production of substitute fuel, in the recovery of CO2 (preferably from biomass), in the production of methanol, in electrical networks, in transport, in fuel cells, in industrial production (for example, fine or basic chemistry such as for hydrogenation reactions).
[0044] Other characteristics and advantages of the invention will be better understood on reading the description which follows and with reference to the appended drawings, given for illustrative purposes and in no way limiting.
[0045] The figure represents a diagram of a system for the production of a synthesis gas according to one embodiment of the invention.
[0046] The figure represents a diagram of a system for the production of a synthesis gas according to one embodiment of the invention.
[0047] ] Represents a diagram of a process for the production of a synthesis gas according to an embodiment of the invention.
[0048] The figures are not necessarily to scale, particularly in size and thickness, for illustrative purposes.
[0049] Below, we describe a summary of the invention and the associated vocabulary, before presenting the disadvantages of the prior art, and finally showing in more detail how the invention overcomes them.
[0050] In the remainder of the description, the expression "supply" or "receive" may correspond to a direct (without intermediary) or indirect (with intermediary, for example a means of regulation and / or control such as a sensor, valve, pump) cooperation between two elements. For example, an output that supplies an input should be understood as the fact that said output cooperates with said input so as to allow a transfer. A transfer may be a fluid or solid transfer.
[0051] In the remainder of the description the terms “configured for”, “adapted for”, “designed for” or “specifically designed for” may be used interchangeably, i.e. may be used in place of each other.
[0052] In the remainder of the description, the expression "decarbonized" can be interpreted as free of carbon of fossil origin. Thus, by decarbonized we mean hydrogen and / or synthetic natural gas preferably derived from biomass.
[0053] In the remainder of the description the expression “recovery” can be interpreted as hydrogen and / or synthetic natural gas produced from CSR.
[0054] In the remainder of the description the term “pollutant-free” or “pollutant-reduced” may be used to be defined as less than 1% by mass of pollutant present in the gas produced (synthesis gas, hydrogen, methane, ammonia).
[0055] The invention proposes to take into consideration the disadvantages of the prior art which may occur during the production of synthesis gas and during the production of gas such as hydrogen and / or ammonia and / or synthetic natural gas such as methane. In particular, the invention proposes a new system for the production of synthesis gas, a new system for the production of hydrogen, a new system for the production of ammonia, a new system for the production of synthetic natural gas, making it possible to reduce the pollutants present in the gases produced, to maximize production yields while limiting the consumption of energy, resources and reducing the carbon footprint compared to existing solutions. For this, the invention proposes a particular combination of elements and a particular arrangement of the elements of said system for the production of gas and the selected inputs.
[0056] Thus, the invention relates in a first aspect to a system for the production of synthesis gas, preferably a system for producing synthesis gas and more preferably to a system designed for the production of synthesis gas and even more preferably to a system specifically designed for the production of synthesis gas. Such a system can be illustrated in connection with the or 2.
[0057] A system 100 intended for the production of synthesis gas comprises at least one first dense fluidized bed reactor 10, at least one second dense fluidized bed reactor 11, at least one circulating fluidized bed reactor 12, at least one separator 13, at least one steam generator 30.
[0058] The system 100 intended for the production of synthesis gas can be configured so that the at least one first dense fluidized bed reactor 10, the at least one second dense fluidized bed reactor 11, the at least one circulating fluidized bed reactor 12 are distinct (separable) or inseparable (integrated forming a single element, for example concentrically). At least one first dense fluidized bed reactor 10, at least one second dense fluidized bed reactor 11, at least one circulating fluidized bed reactor 12, at least one separator 13 comprise an inner wall and an outer wall. An outer wall is by definition oriented towards the outside, the outside of the reactor and the separator, as opposed to an inner wall. Advantageously, an inner wall is configured to be covered by a refractory lining. A refractory lining makes it possible to resist the stresses of the environment (for example temperature or erosion).For example, it could be a steel and / or concrete coating.
[0059] A system according to the invention may comprise at least one first dense fluidized bed reactor 10. A system according to the invention may comprise at most 9 first dense fluidized bed reactors 10. A system according to the invention may comprise a number of first dense fluidized bed reactors 10 ranging from 1 to 9.
[0060] At least one first dense fluidized bed reactor 10 may comprise an inlet 1 for non-oxidizing fluid. An inlet may be adapted to supply the first dense fluidized bed reactor 10 with non-oxidizing fluid. At least one first dense fluidized bed reactor 10 may be adapted to be fluidized with steam, preferably with water vapor. In a particular, but non-limiting, embodiment of the invention, the at least one first dense fluidized bed reactor 10 may be configured to be fluidized with a mixture of steam and recycled syngas, preferably water vapor and recycled syngas. By recycled syngas, it should be understood that the syngas produced by the system according to the invention may be partly recovered and reinjected into said system.
[0061] At least one first dense fluidized bed reactor 10 may be configured to include a raw material inlet 2. A raw material may be selected from inputs having at least 30% carbon. For example, it may be biomass, CSR (solid recovered fuel), waste and / or wood by-products. A wood by-product may, for example, be selected from scrap, bark, related (thinnings) forestry operations, wood chips, vine stocks, orchards, oaths, woody biomass, grape marc, sawmill waste, furniture waste. The raw material may be selected from inputs having a moisture content of less than or equal to 40%. This makes it possible to avoid the use of fossil fuels.
[0062] At least one first dense fluidized bed reactor 10 may for example be a pyrolysis and / or drying reactor, preferably a pyrolysis reactor. The at least one first dense fluidized bed reactor 10 makes it possible to carry out a pyrolysis reaction releasing a first pyrolysis fluid or gas from the raw material. According to a particular embodiment of the invention, but not limiting, the at least one first dense fluidized bed reactor may be configured to carry out drying (evaporation of water) of the raw material. Thus, the at least one first dense fluidized bed reactor may be configured to carry out simultaneously a pyrolysis reaction and drying. Preferably, the at least one first dense fluidized bed reactor is configured to carry out a pyrolysis reaction of raw materials. Pyrolysis makes it possible to extract moisture, volatiles and pollutants.
[0063] Thus, the at least one first dense fluidized bed reactor can be configured to support (i.e. implement, allow) a raw material pyrolysis reaction in a non-oxidizing medium.
[0064] The at least one first dense fluidized bed reactor 10 may be configured to comprise an outlet 5 for the first fluid. An outlet 5 may be configured to discharge a first fluid from the first reactor. An outlet 5 may be configured to supply a first fluid to an inlet 6 of the circulating fluidized bed reactor 12. A first fluid may be selected from pyrolysis gases. The composition of the pyrolysis gases may vary depending on the raw material. The pyrolysis gases may, for example, comprise sulfur, chlorine, ethylene, nitrogen, nitrogen, hydrogen sulfide, water vapor, hydrochloric acid, carbon dioxide, methane. The nature of the gases formed and the quantity of tars (xylenes, phthalenes, etc.) depends on the pyrolysis temperature, but also on the kinetics of the temperature rise, which is very rapid in the case of fluidized beds.Thus, the at least one first dense fluidized bed reactor 10 can be configured to evacuate the pyrolysis gases and the water vapor by means of an outlet 5, preferably to an inlet 6 of the at least one circulating fluidized bed reactor 12. Advantageously, the system does not comprise a means for cooling the pyrolysis gases between the at least one first dense fluidized bed reactor 10 and the at least one circulating bed reactor 12. This allows for an absence of condensation of the tars. The remaining non-volatile compounds are the ash (minerals) and char (otherwise called fixed carbon). Thus, the at least one first reactor 10 makes it possible to evacuate pollutants formed during the pyrolysis reaction of the raw material, but also moisture and volatiles. In addition, this allows for a thermal input of the at least one circulating fluidized bed reactor 12. In addition, this allows for material exchanges and heat exchanges between the different reactors.This helps reduce resource requirements.
[0065] Furthermore, the at least one first dense fluidized bed reactor 10 may be configured to comprise an outlet 3 for pyrolyzed solids. An outlet 3 may be configured to supply pyrolyzed solids to an inlet 4 of the at least one second dense fluidized bed reactor 11. The solids may be selected from pyrolyzed raw material, preferably pyrolyzed biomass, fluidization media, char (also called fixed carbon), and / or ash. This allows for material exchanges and heat exchanges between the different reactors.
[0066] Thus, the at least one first reactor 10 may be configured to supply pyrolyzed solids to the at least one second dense fluidized bed reactor 11 and / or to supply a first fluid to the at least one circulating fluidized bed reactor 12. Preferably, the at least one first dense fluidized bed reactor may be configured to supply pyrolyzed raw material, and / or fluidization media and / or char and / or ash to the at least one second dense fluidized bed reactor 11 and / or to supply pyrolysis gas to the at least one circulating fluidized bed reactor 12.
[0067] At least one first dense fluidized bed reactor 10 may be configured to comprise a fluidization media inlet 7. A fluidization media inlet 7 may be configured to supply the first dense fluidized bed reactor 10 with fluidization media. A fluidization media may for example comprise sand, nickel, dolomite and / or olivine. This makes it possible to reduce the formation of hydrocarbons and in particular tar which forms during the pyrolysis reaction. In addition, the system being configured to allow circulation of the fluidization media, this allows exchanges of materials and heat exchanges between the different reactors. Indeed, a fluidization media inlet 7 may be configured to receive the fluidization media from an outlet 8 of the at least one separator 13.
[0068] Furthermore, the at least one first dense fluidized bed reactor 10 may be configured to operate at a temperature ranging from 350°C to 550°C. This makes it possible to influence both the quantity and the quality of the carbon sent to the at least one second dense fluidized bed reactor 11. Indeed, a high temperature reduces the quantity, but improves the quality while a lower temperature increases the quantity, but increases the risk of pollutants in the char.
[0069] Thus, the at least one first dense fluidized bed reactor 10 makes it possible to retain a maximum of usable material while ensuring the removal of undesirable molecules while allowing exchanges of materials and heat exchanges between reactors.
[0070] A system according to the invention may comprise at least one second dense fluidized bed reactor 11. A system according to the invention may comprise at most 9 second dense fluidized bed reactors 11. A system according to the invention may comprise a number of second dense fluidized bed reactors 11 ranging from 1 to 9.
[0071] At least one second dense fluidized bed reactor 11 may comprise a non-oxidizing fluid inlet 9. A non-oxidizing fluid inlet 9 may be configured to supply the second dense fluidized bed reactor 11 with non-oxidizing fluid. At least one second dense fluidized bed reactor 11 may be configured to be fluidized with steam, preferably with water vapor. In a particular, but non-limiting, embodiment of the invention, the at least one second dense fluidized bed reactor 11 may be configured to be fluidized with a mixture of steam and recycled syngas, preferably water vapor and recycled syngas.
[0072] At least one second dense fluidized bed reactor 11 may be configured to comprise a pyrolyzed solids inlet 4. A pyrolyzed solids inlet 4 may be configured to receive pyrolyzed solids. Preferably an inlet 4 may be configured to receive pyrolyzed raw materials and / or fluidization media and / or chars and / or ash, preferably from the at least one first dense fluidized bed reactor 10 and preferably from the outlet 3 of the at least one first dense fluidized bed reactor 10. This allows material exchanges and heat exchanges between the different reactors.
[0073] At least one second dense fluidized bed reactor 11 may for example be a gasification reactor. A second dense fluidized bed reactor makes it possible to implement a gasification reaction, preferably a steam gasification reaction, releasing a synthesis gas. Thus, at least one second dense fluidized bed reactor 11 may be configured to comprise a synthesis gas outlet 15. A synthesis gas may comprise carbon monoxide, hydrogen, and water vapor. A synthesis gas may comprise traces of CO2. Indeed, thanks to the implementation of a controlled endothermic pyrolysis of raw material, preferably from biomass, in a non-oxidizing medium and a steam gasification reaction of the pyrolyzed raw material (preferably pyrolyzed biomass) in a non-oxidizing medium, very little CO2 is formed.This reduces CO2 emissions and CO2 generation during the production of synthesis gas and preferably in the production of gases such as hydrogen, ammonia, synthetic natural gas. Furthermore, in the presence of water vapor and at high temperature (greater than or equal to 800°C), the fixed carbon is converted into carbon monoxide and hydrogen (water gas reaction). The risk of producing tars associated with this vapour-gasification is very low, because the tars are rather formed in the at least one first dense fluidized bed reactor 10 configured to implement a pyrolysis reaction. Advantageously, the at least one second dense fluidized bed reactor 11 is configured to gasify all or part, preferably all, of the fixed carbon.
[0074] Thus, the at least one second dense fluidized bed reactor 11 is configured to implement a gasification reaction, preferably steam-gasification of pyrolyzed solid materials. The at least one second dense fluidized bed reactor 11 may be configured to discharge a synthesis gas. The at least one second dense fluidized bed reactor 11 may be configured to supply fluidization media to the at least one circulating fluidized bed reactor 12. The at least one second dense fluidized bed reactor may be configured to implement a gasification reaction, preferably steam-gasification in a non-oxidizing medium, preferably of pyrolyzed solid materials. The at least one second dense fluidized bed reactor 11 may be configured to discharge a synthesis gas, preferably resulting from a steam-gasification reaction in a non-oxidizing medium of pyrolyzed solid materials.
[0075] The at least one second dense fluidized bed reactor 11 may be configured to operate at a temperature ranging from 800°C to 1000°C. This allows a water gas reaction to be carried out, a reaction between carbon and water vapor generating carbon monoxide and hydrogen. This also allows a synthesis gas to be obtained comprising very few pollutants. (sulfur and chlorine compounds)
[0076] Furthermore, at least one second dense fluidized bed reactor 11 may be configured to comprise a discharge device. Such a discharge device may for example correspond to a siphon. This makes it possible to maximize the retention of the char (fixed carbon) in the at least one second dense fluidized bed reactor 11. Indeed, since the gasification reaction and more particularly the vapo-gasification reaction is slow, this makes it possible to increase the residence time in the at least one second dense fluidized bed reactor 11. This also makes it possible to improve the efficiency of the at least one circulating fluidized bed reactor 12.
[0077] At least one second dense fluidized bed reactor 11 may be configured to supply fluidization media to the at least one circulating fluidized bed reactor 12. Thus, the at least one second dense fluidized bed reactor 11 may be configured to comprise a fluidization media outlet 16. A fluidization media outlet 16 may be configured to supply fluidization media to the at least one circulating fluidized bed reactor 12. This allows for material exchanges and heat exchanges between the different reactors. In addition, the fluidization media also allows for tar formation to be reduced.
[0078] At least one second dense fluidized bed reactor 11 may be configured to include a fluidization media inlet 17. A fluidization media inlet 17 may be configured to supply fluidization media to the second dense fluidized bed reactor 11. A fluidization media inlet 17 may be configured to receive fluidization media from an outlet 8 of the at least one separator 13.
[0079] A system according to the invention may comprise at least one circulating fluidized bed reactor 12. A system according to the invention may comprise at most 9 circulating fluidized bed reactors 12. A system according to the invention may comprise a number of circulating fluidized bed reactors 12 ranging from 1 to 9.
[0080] The at least one circulating fluidized bed reactor 12 may be configured to comprise an oxidizing fluid inlet 18. An oxidizing fluid inlet 18 may be configured to supply the circulating fluidized bed reactor 12 with oxidizing fluid. At least one circulating fluidized bed reactor 12 may be configured to be fluidized with air, preferably in the presence of oxygen and more preferably in the presence of oxygen and little or no water (trace). Furthermore, the at least one circulating fluidized bed reactor 12 may be configured to be a combustion (i.e. oxidation) reactor. Thus, the at least one circulating fluidized bed reactor may be configured to implement a combustion reaction and preferably a combustion reaction in an oxidizing medium and more preferably a combustion of the pyrolysis gases in an oxidizing medium.Furthermore, the oxidation of the pyrolysis gases makes it possible to use the pyrolysis gases on the one hand and to reduce the cost of flue gas treatment on the other hand. In addition, the oxidation of the pyrolysis gases makes it possible to provide an energy source to the system 100 intended for the production of syngas. The combustion allows the heating of the solids by direct contact. The at least one circulating fluidized bed reactor 12 can be configured to operate at a temperature ranging from 900 to 1200°C. The combustion therefore simultaneously ensures the oxidation reaction of the pyrolysis gas and the heat transfer, preferably to the fluidization medium. Combustion in an external burner would require an additional device for transferring heat from the combustion fumes to the fluidization medium, which would make the system intended for the production of syngas less efficient.Thus, the at least one second circulating fluidized bed reactor is configured to implement an oxidation reaction of a first fluid and to supply fluidization media and fumes to the at least one separator.
[0081] The at least one circulating fluidized bed reactor 12 may be configured to include a fluidization media inlet 21. A fluidization media inlet 21 may be configured to receive the fluidization media, preferably from the outlet 16 of the second dense fluidized bed reactor. This allows for material exchanges and heat exchanges between the different reactors.
[0082] The at least one circulating fluidized bed reactor 12 may be configured to comprise an inlet 6 for the pyrolysis gases, preferably from the outlet 5 of the first dense fluidized bed reactor 10. This allows the gases to be supplied to the circulating fluidized bed reactor to carry out the combustion reaction, preferably in an oxidizing medium.
[0083] The at least one circulating fluidized bed reactor 12 may be configured to comprise a fluidization media outlet 19. A fluidization media outlet 19 may be configured to supply fluidization media and / or ash and / or fumes to the at least one separator 13. More specifically, an outlet 19 may be configured to supply an inlet 20 of the separator 13. The fumes may correspond to fumes resulting from combustion. The fumes may comprise N2, CO2, H2O, O2, SO2, and HCl. This makes it possible to evacuate pollutants.
[0084] Thus, oxidation of pyrolysis gases in a circulating fluidized bed makes it possible to balance the quantities of heat absorbed by the reactions of the system intended for the production of syngas. In addition, particularly advantageously, the heat balance is surplus. The excess heat makes it possible to lower the pyrolysis temperature (ranging from 350 °C to 550 °C). This excess energy has the effect of adding a portion of volatile substances to the fixed carbon of the raw material, thus increasing the total production and therefore the yields. In addition, the increase in a fraction of volatile matter makes it possible to reduce the risk of tar formation, as does the use of the fluidization medium.
[0085] Furthermore, the at least one circulating fluidized bed reactor 12 may be configured to comprise a fluidization media inlet 27. A fluidization media inlet 27 may be configured to supply the at least one circulating fluidized bed reactor 12 with fluidization media. A fluidization media inlet 27 may be configured to receive the fluidization media from an outlet 8 of the at least one separator 13.
[0086] A system according to the invention may comprise at least one separator 13. A system according to the invention may comprise at most 9 separators 13. A system according to the invention may comprise a number of separators 13 ranging from 1 to 9.
[0087] The at least one separator 13 is configured to separate the solids from the gases. Preferably, the at least one separator 13 is configured to separate the fluidization medium from the fumes. Indeed, the at least one separator may be configured to comprise an inlet 20 for the fluidization medium. An inlet 20 for the fluidization medium may be configured to receive the fluidization medium and / or the fumes, preferably from the outlet 19 of the at least one circulating fluidized bed reactor 12.
[0088] The at least one separator 13 may be configured to supply fluidization media to the at least one first dense fluidized bed reactor 10 and / or the at least one second dense fluidized bed reactor 11, and / or the at least one circulating fluidized bed reactor 12. Thus, the at least one separator 13 may be configured to comprise at least one fluidization media outlet 8.
[0089] In a particular, but non-limiting, embodiment, the at least one separator 13 may be configured to be coupled with at least one distributor 14. The at least one separator and the at least one distributor may be configured to be arranged in a dissociable or inseparable manner. Thus, the at least one separator 13 is configured to cooperate, preferably to communicate preferably mechanically with the at least one distributor 14. This communication allows a transfer of the fluidization media from the separator to the distributor.
[0090] The at least one distributor 14 may be configured to distribute the fluidization medium preferably between the at least one first dense fluidized bed reactor 10 and / or the at least one second dense fluidized bed reactor 11, and / or the at least one circulating fluidized bed reactor 12. Preferably, a system according to the invention is configured to comprise as many separators as distributors. Thus, the at least one separator 13 may be configured to supply fluidization media to at least one distributor 14.
[0091] At least one distributor 14 may be configured to comprise at least one fluidization media inlet 23. A fluidization media inlet 23 may be configured to receive the fluidization media, preferably from the outlet 8 of the at least one separator 13. At least one distributor 14 may be configured to comprise at least one fluidization media outlet 24. A fluidization media outlet 24 may be configured to supply fluidization media to the at least one first dense fluidized bed reactor 10, the at least one second dense fluidized bed reactor 11 and / or the at least one circulating fluidized bed reactor 12. Preferably, the at least one distributor 14 is configured to comprise a fluidization media outlet 24 for each reactor of the system.Thus, in a non-limiting embodiment of the invention, a distributor may be configured to comprise an outlet 24 configured to supply fluidization media to an inlet 7 of the at least one first dense fluidized bed reactor. A distributor may be configured to comprise an outlet 24 configured to supply fluidization media to an inlet 17 of the at least one second dense fluidized bed reactor. A distributor may be configured to comprise an outlet 24 configured to supply fluidization media to an inlet 27 of the at least one circulating fluidized bed reactor. Thus, a fluidization media inlet 7 of the at least one first dense fluidized bed reactor may be configured to receive the fluidization media from an outlet 24 of the at least one distributor 14.A fluidization media inlet 17 of the at least one second dense fluidized bed reactor may be configured to receive the fluidization media from an outlet 24 of the at least one distributor 14. A fluidization media inlet 27 of the at least one circulating fluidized bed reactor may be configured to receive the fluidization media from an outlet 24 of the at least one distributor 14. Preferably, the at least one distributor is configured to comprise a control means configured to be arranged at the at least one outlet 24. A control means may for example correspond to a needle valve and / or metering screw and / or discharge means.Advantageously, a distributor may be configured to comprise a control means arranged at each of the outlets 24, preferably arranged at an outlet 24 configured to supply fluidization media to a fluidization media inlet 7 of the at least one first dense fluidized bed reactor and at an outlet 24 configured to supply fluidization media to a fluidization media inlet 17 of the at least one second dense fluidized bed reactor and at an outlet 24 configured to supply fluidization media to a fluidization media inlet 27 of the at least one circulating fluidized bed reactor 12. A control means makes it possible to regulate the fluidization media as a function of the quantity of fluidization media in each reactor and / or as a function of the temperature of each reactor. This allows for better resource management and improved system efficiency.
[0092] Returning to the separator, the at least one separator 13 may further be configured to supply fumes to at least one steam generator 30. A steam generator may be configured to generate steam from the fumes. A steam generator may for example correspond to a heat recovery boiler. A separator may be configured to comprise at least one fume outlet 22. A fume outlet 22 may be configured to supply fumes to at least one steam generator 30. Furthermore, a steam generator 30 may be configured to supply non-oxidizing fluid (preferably water vapor) to the at least one dense fluidized bed reactor 10 and the at least one second dense fluidized bed reactor. A steam generator may be configured to supply non-oxidizing fluid (preferably water vapor) to an inlet 1 of the at least one dense fluidized bed reactor 10.A steam generator may be configured to supply non-oxidizing fluid (preferably water vapor) to an inlet 9 of the at least one dense fluidized bed reactor 11. A steam generator 30 makes it possible to reduce the overall energy consumption. In addition, a steam generator may be configured to supply steam to the distributor 14 in order to fluidize it.
[0093] Thus, a system 100 according to the invention intended for the production of syngas allows a reduction in energy consumption, a reduction in the need for fossil raw materials, a reduction in the carbon footprint, particularly in the syngas production industry. Furthermore, a system intended for the production of syngas according to the invention makes it possible to combine dense and circulating fluidized bed technologies. The combination of these two technologies makes it possible to set up a staged pyrolysis divided into three stages: pyrolysis (temperature below 550°C), gasification (steam gasification) (temperature approximately 850°C) and oxidation by a sequence and a particular arrangement of the dense and circulating fluidized beds. This allows circulation of the fluidization medium allowing exchanges of materials and heat between the different beds (reactors).This also increases yields and reduces pollutants. Furthermore, the quality of the resulting synthesis gas is improved.
[0094] According to another aspect, the invention relates to at least one system for the production of gas, preferably for the production of hydrogen and / or ammonia and / or synthetic natural gas, preferably for the production of decarbonized and / or recovered hydrogen and / or for the production of decarbonized and / or recovered synthetic natural gas. A synthetic natural gas may for example comprise methane. A system for the production of hydrogen and / or ammonia and / or synthetic natural gas may be configured to comprise a system for the production of synthesis gas according to the invention.
[0095] A system for producing hydrogen and / or synthetic natural gas according to the invention may comprise a filtration means. A filtration means may for example correspond to ceramic candles or metallic frits. A filtration means may be configured to filter the synthesis gas. A filtration means makes it possible to reduce dust (ash and fluidization media that have undergone attrition) that may persist in the synthesis gas produced. This makes it possible to further improve the purity of the gas to be produced (hydrogen and / or ammonia and / or synthetic natural gas, preferably methane).
[0096] Furthermore, a system for the production of hydrogen and / or synthetic natural gas may comprise a cracking means, preferably regenerative thermal cracking. A cracking means may be configured to reduce / convert tars into shorter carbon chain molecules. This further improves the purity of the gas produced. A cracking means may for example be selected from: a thermal device, preferably an electrical resistance device, and / or an oxygen injection device, and / or a scrubbing device.
[0097] Furthermore, a system for the production of hydrogen and / or synthetic natural gas may comprise a carbon monoxide conversion means. A carbon monoxide conversion means may be configured to implement a WGS (water gas shift) type reaction. A carbon monoxide conversion means may be configured to comprise an inlet configured to supply water vapor to the carbon monoxide conversion means. This makes it possible to provide excess moisture to the synthesis gas. Preferably, a carbon monoxide conversion means comprises a catalyst. A catalyst may correspond to a so-called high temperature catalyst (HTS) as opposed to low temperature catalysts (LTS). A catalyst is preferably configured to tolerate impurities, for example up to 50 ppm of sulfur compound.Furthermore, a catalyst can be configured to hydrolyze HCN compounds to convert them into NH3 and CO compounds. This further favors the reactants of the carbon monoxide conversion means. A conversion means also converts carbon monoxide and water vapor into carbon dioxide and hydrogen. In addition, this increases the yield.
[0098] Furthermore, a system for the production of hydrogen and / or synthetic natural gas may comprise a condensation means. A condensation means may, for example, correspond to a hydroejector. A condensation means may be configured so that the NH3 and HCl molecules are trapped by water. This makes it possible to increase the purity of the hydrogen and / or synthetic natural gas by removing the NH3 and HCl compounds. In addition, such a condensation means makes it possible to concentrate the proportions of CO2 and H2.
[0099] Advantageously, the system for the production of hydrogen and / or synthetic natural gas may comprise an additional filtration means configured to filter out residual undesirable compounds and thus improve the purity and yield of the hydrogen and / or synthetic natural gas produced. For example, this may be an activated carbon filter.
[0100] Furthermore, a system for the production of hydrogen and / or synthetic natural gas may comprise a compression means. A compression means may, for example, correspond to a gas compressor. This makes it possible to compress the hydrogen and / or synthetic natural gas to a predetermined pressure.
[0101] Furthermore, a system for producing hydrogen may include a purification means. A purification means may, for example, correspond to a PSA (Pressure Swing Adsorption). A purification means may be configured to separate hydrogen from other molecules, for example CO2, CO, H2O. Thus, a purification means may be configured to separate the hydrogen produced and obtain hydrogen, preferably decarbonized and / or recovered hydrogen.
[0102] A system for the production of hydrogen and / or synthetic natural gas according to the invention allows, for example, the production of hydrogen and / or synthetic natural gas (preferably methane) while reducing the need for energy, fossil raw materials and CO2 emissions. In addition, this makes it possible to increase yields while reducing pollutants and tars.
[0103] In a particular embodiment, a system for producing hydrogen according to the invention may comprise a conversion means. A conversion means may, for example, correspond to a reactor, preferably a reactor equipped with at least one catalyst. A conversion means may be configured to convert hydrogen into ammonia. For example, it may be a nitrogen hydrogenation reaction, a plasma technology by hydride reaction (of the BaHN type). A catalyst may be selected from iron, nickel, aluminum oxide and / or potassium nitrate. This makes it possible to store and transport hydrogen in the form of ammonia more easily. In addition, this also makes it possible to produce ammonia that is available for various applications and whose production system has the same effects and advantages.
[0104] In a particular embodiment, a system for the production of synthetic natural gas and preferably a system for the production of decarbonized and / or recovered synthetic natural gas and preferably methane according to the invention may comprise a methanation means. A methanation means may for example correspond to a catalytic reactor or a biological reactor. A methanation means may be configured to convert hydrogen and / or carbon dioxide into synthetic natural gas and preferably into methane. This makes it possible to produce synthetic natural gas in a clean manner and of improved quality which is available for various applications and whose production system has the same effects and advantages.
[0105] According to another aspect the invention relates to a process for the production of synthesis gas, preferably a process for the production of synthesis gas, more preferably a process for the production of synthesis gas.
[0106] An embodiment of such a method may be illustrated in connection with the.
[0107] A method 200 for the production of synthesis gas is capable of being implemented by a system 100 for the production of synthesis gas according to the invention, preferably, a method 200 for the production of synthesis gas is implemented by a system 100 for the production of synthesis gas according to the invention.
[0108] A process 200 intended for the production of synthesis gas may comprise a pyrolysis step 220, a gasification step 230, preferably vapo-gasification, a combustion step 240, a heat transfer step 250, a steam generation step 260.
[0109] A process 200 for producing synthesis gas may comprise a drying step 210. A drying step may be carried out by at least one first dense fluidized bed reactor 10. In one embodiment, the drying step may be carried out simultaneously with a pyrolysis step 220. A drying step makes it possible to dry and therefore reduce the humidity of the raw material in the first dense fluidized bed reactor.
[0110] A process 200 for the production of synthesis gas may comprise a pyrolysis step 220 from raw material, preferably in a first dense fluidized bed reactor 10. A pyrolysis reaction makes it possible to form first fluids and pyrolyzed solids, preferably pyrolysis gases and pyrolyzed solids. Advantageously, the pyrolysis step 220 is an endothermic pyrolysis step. Furthermore, the pyrolysis step is preferably carried out in a non-oxidizing medium, preferably in the presence of water vapor. The pyrolysis step may be carried out at a temperature less than or equal to 550°C. The pyrolysis step may be carried out at a temperature greater than or equal to 300°C. The pyrolysis step may be carried out at a temperature ranging from 300°C to 550°C. The pyrolysis step can be carried out in a time ranging from 0.1 seconds to 10 seconds, preferably in less than 5 seconds.
[0111] A process 200 for the production of synthesis gas may comprise a gasification step 230, preferably steam gasification, in a second dense fluidized bed reactor 11 from the pyrolyzed solids so as to form a synthesis gas. Furthermore, a gasification step may comprise a conversion of fixed carbon into carbon monoxide and hydrogen. A gasification step makes it possible to form a synthesis gas. Furthermore, the gasification step is preferably carried out in a non-oxidizing medium, preferably in the presence of water vapor.
[0112] The gasification step can be carried out at a temperature less than or equal to 1000°C. The gasification step can be carried out at a temperature greater than or equal to 850°C. The gasification step can be carried out at a temperature ranging from 850°C to 1000°C. The gasification step can be carried out for a duration ranging from 1 minute to 60 minutes, preferably in less than 45 minutes.
[0113] A method 200 for the production of synthesis gas may comprise a combustion step 240, preferably in a fluidized bed reactor 12 circulating from the first fluid and preferably from the pyrolysis gases so as to generate thermal energy and fumes. The combustion step further allows oxidation of the pyrolysis gases. Furthermore, the combustion step is preferably carried out in an oxidizing medium, preferably in the presence of air. Advantageously, the combustion step comprises a direct heat exchange between the fumes resulting from the combustion and the fluidization medium.
[0114] The combustion step may be carried out at a temperature greater than or equal to 900°C. The combustion step may be carried out at a temperature less than or equal to 1200°C. The combustion step may be carried out at a temperature ranging from 900°C to 1200°C. The combustion step may be carried out for a duration ranging from 0.5 seconds to 4 seconds, preferably in less than 2 seconds.
[0115] A process 200 for the production of synthesis gas may comprise a heat transfer step 250 preferably from a fluidization medium between the at least one separator 13 and the first dense fluidized bed reactor and / or the second dense fluidized bed reactor and / or the third circulating fluidized bed reactor. A process 200 for the production of synthesis gas may comprise a heat transfer step 250 by at least one separator preferably from a fluidization medium between the at least one separator 13 and a distributor and / or the first dense fluidized bed reactor and / or the second dense fluidized bed reactor and / or the third circulating fluidized bed reactor.Advantageously, the heat transfer step comprises circulating the fluidization medium through the at least one separator, and / or the at least one first dense fluidized bed reactor and / or the at least one second dense fluidized bed reactor and / or the at least one circulating fluidized bed reactor. Preferably, the heat transfer step comprises circulating the fluidization medium through the at least one separator, and / or the at least one distributor and / or the at least one first dense fluidized bed reactor and / or the at least one second dense fluidized bed reactor and / or the at least one circulating fluidized bed reactor. Furthermore, in a particular, but non-limiting, embodiment, a step of circulating the fluidization medium may comprise a step of regulating, preferably regulating, the fluidization medium.A regulation step may preferably be implemented by a control means preferably of the needle valve type and / or metering screw and / or discharge means. More particularly, a step of circulation of the fluidization medium may be regulated by a control means through the at least one first dense fluidized bed reactor and / or the at least one second dense fluidized bed reactor and / or the at least one circulating fluidized bed reactor. This allows a distribution of the fluidization medium. Advantageously, this allows a regulated distribution of the fluidization medium. In addition, this makes it possible to ensure a heat exchange and therefore to reduce the resource requirement.
[0116] Furthermore, a method 200 intended for the production of synthesis gas may comprise a step of generating steam 260 from the fumes, preferably by a steam generator 30.
[0117] A steam generation step 260 makes it possible to generate steam, preferably water vapor. Furthermore, a steam generation step may comprise a step of supplying steam to the at least one first dense fluidized bed reactor. A steam generation step may comprise a step of supplying steam to the at least one second dense fluidized bed reactor. This makes it possible to ensure a non-oxidizing environment within the at least one first dense fluidized bed reactor and / or the at least one second dense fluidized bed reactor.
[0118] Furthermore, in a particular, but non-limiting, embodiment of the invention, the method may comprise a step of injecting into the at least one first dense fluidized bed reactor and / or the second dense fluidized bed reactor 11 a mixture of recycled steam and syngas, preferably water vapor and recycled syngas. By recycled syngas, it should be understood that the syngas produced by the method according to the invention may be partly recovered and reinjected into said system.
[0119] These steps and therefore the process for the production of syngas make it possible to obtain clean syngas, while minimizing energy consumption. In addition, such a process makes it possible to reduce the carbon footprint. A process according to the invention also makes it possible to avoid the use of fossil fuels. In addition, it makes it possible to increase yields and reduce pollutants and therefore to increase the quantity and quality of syngas.
[0120] According to another aspect, the invention relates to a process for the production of gas, preferably for the production of hydrogen and / or synthetic natural gas and more preferably for the production of decarbonized and / or recovered hydrogen and / or decarbonized and / or recovered synthetic natural gas.
[0121] A method for the production of hydrogen is capable of being implemented by a system for the production of hydrogen according to the invention, preferably implemented by a system for the production of hydrogen according to the invention.
[0122] A method for the production of synthetic natural gas is capable of being implemented by a system for the production of synthetic natural gas, preferably implemented by a system for the production of synthetic natural gas according to the invention.
[0123] A process for the production of hydrogen and / or synthetic natural gas may comprise a process for the production of a synthesis gas according to the invention.
[0124] Furthermore, a process for the production of hydrogen and / or synthetic natural gas may comprise a filtration step, preferably by a means for filtering the synthesis gas. This makes it possible to reduce dust (ash and fluidization media that have undergone attrition) that may persist in the synthesis gas produced. This makes it possible to further improve the purity of the gas to be produced (hydrogen and / or ammonia and / or synthetic natural gas, preferably methane).
[0125] A process for the production of hydrogen and / or synthetic natural gas may comprise a cracking step, preferably regenerative thermal cracking, by a cracking means. Such a step may comprise a step of heating the synthesis gas, preferably filtered synthesis gas. A cracking step may also comprise a step of cooling the synthesis gas, preferably filtered and heated synthesis gas.
[0126] A process for the production of hydrogen and / or synthetic natural gas may comprise a step of enriching (WGS) the synthesis gas, preferably by means of converting carbon monoxide. Such a step may comprise a step of supplying steam, preferably water vapor. This allows excess moisture in the synthesis gas.
[0127] A process for the production of hydrogen and / or synthetic natural gas may comprise a condensation step, preferably by a condensation means.
[0128] A process for the production of hydrogen and / or synthetic natural gas may comprise a compression step, preferably by a compression means.
[0129] A process for the production of hydrogen may comprise a purification step by a purification means to separate (purify) the hydrogen and obtain hydrogen, preferably decarbonized and / or recovered hydrogen. A purification step may comprise a PSA in the production of hydrogen.
[0130] In a particular, but non-limiting, embodiment of the invention, the hydrogen production process may comprise a conversion step, by a means of converting hydrogen into ammonia. A conversion step makes it possible to obtain decarbonized and / or recovered ammonia.
[0131] A process for producing synthetic natural gas may comprise a methanation step, by a methanation means to convert hydrogen and / or carbon dioxide into synthetic natural gas, preferably methane.
[0132] A process for producing synthesis gas and / or hydrogen and / or synthetic natural gas according to the invention allows the production of synthesis gas, hydrogen, ammonia or synthetic natural gas, preferably clean methane, with high efficiency. In addition, a process for producing synthesis gas and / or hydrogen and / or synthetic natural gas according to the invention makes it possible to reduce the need for resources (energy and fossils). A process for producing synthesis gas and / or hydrogen and / or synthetic natural gas thus makes it possible to participate in the decarbonization of industry, for example, to reduce the need for resources of fossil origin, to reduce CO2 emissions.Furthermore, a process for producing synthesis gas and / or hydrogen and / or synthetic natural gas according to the invention allows the production of hydrogen, synthesis gas, ammonia, synthetic natural gas, preferably clean methane, with high yield and low resource consumption. Furthermore, the quantities produced are sufficient to be used directly. Indeed, thanks to the invention, yields are improved.
[0133] According to another aspect, the invention relates to the use of a system for the production of synthesis gas according to the invention in the production of electricity, in the production of hydrogen, in the production of synthetic natural gas, in the production of methane, in the production of ammonia, in the production of steam, in the production of heat, in the production of substitute fuel, in the recovery of CO2 (preferably from biomass), in the production of methanol, in electrical networks, in transport, in fuel cells, in industrial production (for example, fine or basic chemistry such as for hydrogenation reactions).
[0134] Such use avoids the use of fossil fuels. Furthermore, such use reduces the carbon footprint and promotes the ecological transition. Furthermore, such use reduces the need for resources.
[0135] Furthermore, and preferably in a particular embodiment, such a system according to the invention intended for the production of synthesis gas may be more particularly intended for and preferably designed for and more preferably specifically designed for or even for the production of at least one substitute fuel for transport and / or the generation of electricity.
[0136] Alternative fuels for transport are synthetic fuels derived from synthesis gas and / or synthetic biofuels derived from synthesis gas. Furthermore, transport can be road transport, naval transport and / or aviation transport. Electricity generation can, for example, include a generator.
[0137] According to another aspect, the invention relates to a synthesis gas production unit comprising at least one system for producing synthesis gas according to the invention. A unit is not limited by the number of systems for producing synthesis gas. However, a unit may be limited by its location. Thus, for example, a synthesis gas production unit may comprise at most 100 systems 100 for producing synthesis gas. A unit may comprise a number of systems according to the invention ranging from to 100. Such a unit also makes it possible to avoid the use of fossil energy. In addition, such a unit makes it possible to reduce the carbon footprint and promote the ecological transition. In addition, such a unit makes it possible to reduce the need for resources. EXAMPLES
[0138] The examples below describe a particular and non-limiting embodiment purely for illustrative purposes. The order described below is presented in the reverse direction of circulation of the raw material in order to illustrate the thermal order in a decreasing manner. The three loops below can be summarized in a single diagram integrating the circulations of material and heat for example illustrated in.
[0139] Oxidation of pyrolysis gases (combustion)
[0140] A first loop provides both thermal energy (heat used in the rest of the process intended for the production of synthesis gas and in the system intended for the production of synthesis gas) and potential energy (gravity flow).
[0141] The combustion of the pyrolysis gases in the at least one circulating fluidized bed reactor allows the heating of the solids (i.e. fluidization medium) by direct contact; preferably the at least one circulating fluidized bed reactor is fluidized with air. Solids and fumes are separated in the separator. The solids then return to the bottom of the at least one circulating fluidized bed reactor, for example via a distributor. This entire loop can be operated at 950 °C. The combustion in a circulating fluidized bed therefore simultaneously ensures the oxidation reaction of the pyrolysis gases and the heat transfer to the fluidization medium. The hot gases (fumes separated by the separator) are directed to a steam generator (heat generator) which ensures the production of steam used in fluidization.
[0142] Gasification – Vapor gasification
[0143] A second loop diverts a portion of the fluidization media from the previous loop to 950°C to reheat the at least one second dense fluidized bed reactor, preferably fluidized with steam. The flow rate of fluidization media may be regulated by means of a distributor comprising a control means (i.e. a needle valve). The reactors, separator and / or distributor have an internal wall covered by a refractory material. This makes it possible, for example, in gasification to maintain a temperature of 850°C in this loop.
[0144] Furthermore, the at least one second dense fluidized bed reactor can receive fixed carbon from the at least one first dense fluidized bed reactor. In the at least one second dense fluidized bed reactor, gasification with water vapor (C + H2O -> CO + H2) takes place.
[0145] The fluidization media conveyed in this loop then reaches the foot of at least one circulating fluidized bed reactor.
[0146] In the presence of water vapor and at high temperature (850°C), fixed carbon is converted into carbon monoxide and hydrogen (water gas reaction). The risk of tar production associated with this gasification is very low, as tars are rather formed during the pyrolysis reaction. Tar production is also reduced by the use of olivine in the fluidization medium, a reducing agent for tar formation.
[0147] The intended composition of the synthesis gas produced in the at least one second dense fluidized bed reactor may be as follows:
[0148] [Table 1] Estimated composition of the synthesis gas in the at least one second dense fluidized bed reactor: Composition % vol kg / kg (H2) CO, carbon monoxide 25% 9.2 H2, hydrogen 25% 0.7 H2O, water vapor (excess fluidization) 50% 11.8 NH3 10 ppm 2.2 x 10 -4 HCN10 ppm3.5x10 -4 H2S + COS + CS2 < 1 ppm4.5x10 -6 HCl< 1 ppm4.7x10 -6
[0149] Drying and pyrolysis of biomass
[0150] The third loop also diverts a portion of the fluidization media from the first loop to 950°C to reheat the at least one first dense fluidized bed reactor, preferably fluidized with steam. The flow rate of diverted media is regulated to maintain a temperature between 350°C and 550°C in this loop, for example by a distributor comprising a needle valve type control means.
[0151] This at least first dense fluidized bed reactor receives the raw material. Pyrolysis reactions take place in this reactor, releasing a combustible gas used as heat input in the first loop (circulating fluidized bed reactor). Sulfur and chlorine compounds are released with the pyrolysis gases and reach the circulating fluidized bed reactor and are then evacuated with the flue gases.
[0152] The operating temperature influences both the quantity and quality of the fixed carbon sent to at least one second dense fluidized bed reactor. Drying (evaporation of water) of the biomass can be carried out simultaneously with pyrolysis: as the raw biomass heats up, free and bound water are evaporated. The inputs have a variable moisture content depending on the season. For example, freshly cut forest chips have a moisture content of 50% and this moisture content decreases to 30% after a few months of storage.
[0153] Pyrolysis reactions take place as the temperature continues to rise in the at least one first dense fluidized bed reactor. These may, for example, be dissociation and fractionation reactions of biomass polymers, mainly cellulose, hemicellulose and lignin. The nature of the gases formed and the quantity of tars (xylenes, phthalenes, etc.) depend on the pyrolysis temperature, but also on the kinetics of the temperature rise, which is very rapid in the case of fluidized beds. In the first dissociation reactions during the temperature rise, sulfur and halogens (chlorine) are also volatilized (in the form of H2S and HCl, i.e. sulfur and / or chlorine compounds: pollutants). The pyrolysis gases and the evaporated water vapor are discharged to the at least one circulating fluidized bed reactor for oxidation.The calorific value of this gas is used as a heat input in the rest of the system for the production of synthesis gas and the process for the production of synthesis gas. The absence of cooling of the pyrolysis gases between the at least one first dense fluidized bed reactor and the at least one circulating fluidized bed reactor or between the pyrolysis stage and the oxidation stage ensures the absence of condensation of the tars. The remaining non-volatile compounds are ash (minerals) and char (otherwise called fixed carbon).
[0154] At high temperature (550°C), all the volatile part and moisture are found in the gas which is oxidized (i.e. 85% of the incoming raw material). At this pyrolysis temperature, only 13% of fixed carbon is used in the gasification stage. At lower temperatures, pyrolysis is incomplete and molecules containing carbon, hydrogen and oxygen remain with the fixed carbon and the ash. This fraction, which can reach 35% of the incoming material, is used for gasification. Thus, lowering the pyrolysis temperature makes it possible to increase the fraction used in gasification while controlling the quality of the gas obtained at this gasification stage. The solids (fixed carbon and fluidization media) are evacuated by overflow to at least one second dense fluidized bed reactor for gasification.
[0155] Syngas Filtration & Cracking
[0156] As previously stated, the risk of tars being present in the syngas is very low. However, a filter can be provided to capture any residual dust, for example, and filter the syngas. In addition, thermal cracking equipment can convert molecules into shorter ones. Thermal cracking will operate similarly to a regenerative thermal oxidizer. The dedusted syngas will pass through a fixed bed of hot ceramics. The heat exchange will heat the gas up to 1100°C, and the ceramics will gradually lose their heat. The syngas will then pass through an electrical resistor, which will raise this temperature to 1250°C. It will pass through a second bed of cooler ceramics. The heat exchange will lower the gas temperature to 650°C, and the ceramics will gradually gain heat.When the heat exchange is reduced, there will be an inversion of the cycle, the bed of "hot" ceramics will take on the role of the bed of "cold" ceramics.
[0157] Water Gas Shift
[0158] The synthesis gas, a mixture of carbon monoxide and hydrogen, will then be enriched with hydrogen by a "water gas shift" (WGS) reaction on a catalyst, during which the carbon monoxide and water vapor will be converted into carbon dioxide and hydrogen. Preferably high-temperature catalysts also allow the hydrolysis of the HCN compound to convert it into NH3 and CO. The composition of the synthesis gas expected at the water gas shift outlet is as follows:
[0159] [Table 2] Estimated composition of synthesis gas at WGS outletComposition%volkg / kg(H2)CO, carbon monoxide2%0.8H2, hydrogen48%1.3CO2, carbon dioxide23%13.1H2O, water vapor (excess)27%6.4NH320 ppm4.5x10 -4H2S + COS + CS2 < 1 ppm4.5x10 -6 HCl< 1 ppm4.7x10 -6
[0160] The synthesis gas will then be condensed before reaching a compressor. During this condensation, the highly soluble molecules NH3 and HCl will be trapped in the water. The composition of the synthesis gas could then be as follows:
[0161] [Table 3] Estimated composition of synthesis gas after condensation / compression.Composition%volkg / kg(H2)CO, carbon monoxide3%0.8H2, hydrogen65%1.3CO2, carbon dioxide31%13.1H2O, water vapor (saturated)1%0.2H2S + COS + CS2< 1 ppm4.5x10 -6
[0162] Furthermore, activated carbons can allow the capture of residual sulfur compounds.
[0163] PSA purification
[0164] Finally, the hydrogen will be separated from the other gases in the mixture on a PSA (Pressure Swing Adsorption, adsorption / desorption cycles) in order to produce hydrogen, preferably decarbonized and / or recovered hydrogen. During this operation, 20% of the hydrogen production can be used to sweep the PSA capacity in the desorption phase (a less stringent specification on hydrogen quality would tend to reduce this value). Optionally, the hydrogen can be converted into ammonia.
[0165] Methanation
[0166] According to another embodiment, catalytic or biological methanation can be carried out in order to obtain a synthetic natural gas, preferably a decarbonized and / or recovered synthetic natural gas and more preferably methane. During this operation, preferably decarbonized and / or recovered hydrogen is combined with CO2. The synthetic natural gas produced, preferably methane, in addition to being decarbonized and / or recovered, results from a process and / or system which makes it possible to reduce CO2 emissions and improve yields. In addition, the quality of the gas produced is improved.
[0167] The invention may be the subject of numerous variations and applications other than those described above. In particular, unless otherwise indicated, the different structural and functional features of each of the implementations described above should not be considered as combined and / or closely and / or inextricably linked to each other, but on the contrary as simple juxtapositions. Furthermore, the structural and / or functional features of the different embodiments described above may be the subject in whole or in part of any different juxtaposition or any different combination.
Claims
System (100) for the production of synthesis gas comprising at least one first dense fluidized bed reactor (10), at least one second dense fluidized bed reactor (11), at least one circulating fluidized bed reactor (12), at least one separator (13), at least one steam generator (30) in which:the at least one first dense fluidized bed reactor (10) is configured for a raw material pyrolysis reaction and for supplying pyrolyzed solids to the at least one second dense fluidized bed reactor (11) and for supplying a first fluid to the at least one circulating fluidized bed reactor (12),the at least one second dense fluidized bed reactor (11) is configured for a vapor-gasification reaction of pyrolyzed solids and for discharging a synthesis gas and for supplying fluidization media to the at least one circulating fluidized bed reactor (12),the at least one circulating fluidized bed reactor (12) is configured for an oxidation reaction of a first fluid and for supplying fluidization media and fumes to the at least one separator (13), the at least one separator (13) is configured to separate the fluidization media from the fumes, and to supply fluidization media to the at least one first dense fluidized bed reactor (10) and / or the at least one second dense fluidized bed reactor (11), and / or the at least one circulating fluidized bed reactor (12) and for supplying fumes to the at least one steam generator (30)., System (100) for the production of synthesis gas according to claim 1, characterized in that the at least one separator (13) is configured to supply fluidization media to a distributor (14). System (100) for the production of synthesis gas according to claim 1 or 2, characterized in that the raw material is selected from inputs having at least 30% carbon such as biomass, CSR (solid recovered fuel), waste and / or wood by-products. System (100) for the production of synthesis gas according to one of the preceding claims, characterized in that the raw material is selected from inputs having a humidity level less than or equal to 40%. System (100) for the production of synthesis gas according to one of the preceding claims, characterized in that the at least one steam generator (30) is configured to supply non-oxidizing fluid to the at least one first dense fluidized bed reactor (10) and the at least one second dense fluidized bed reactor (11). A system for producing hydrogen comprising at least one system (100) for producing synthesis gas according to one of claims 1 to 5, the system for producing hydrogen further comprising:A filtration means configured to filter the synthesis gas,A carbon monoxide conversion means configured to convert carbon monoxide and water vapor into carbon dioxide and hydrogen,A purification means configured to purify the hydrogen and obtain hydrogen. System for the production of hydrogen according to claim 6, characterized in that it comprises a conversion means configured to convert hydrogen into ammonia. A system for producing synthetic natural gas comprising at least one system (100) for producing synthesis gas according to one of claims 1 to 5, the system for producing synthetic natural gas further comprising:A filtration means configured to filter the synthesis gas,A carbon monoxide conversion means configured to convert carbon monoxide and water vapor into carbon dioxide and hydrogenA methanation means configured to convert hydrogen and / or carbon dioxide into synthetic natural gas. A method (200) for producing synthesis gas that can be implemented in a system (100) for producing synthesis gas according to one of claims 1 to 5, comprising:A pyrolysis step (220) from raw material in at least one first dense fluidized bed reactor (10) so as to form a first fluid and pyrolyzed solids,A vapor-gasification step (230) in at least one second dense fluidized bed reactor (11) from the pyrolyzed solids so as to form a synthesis gas,An oxidation step (240) in at least one fluidized bed reactor (12) circulating from the first fluid so as to generate fumes,A heat transfer step (250) by at least one separator (13) from a fluidization medium between the at least one separator (13) and the at least one first dense fluidized bed reactor (10) and / or the at least one second dense fluidized bed reactor (11) and / or the at least one circulating fluidized bed reactor (12), a steam generation step (260) from the fumes by at least one steam generator (30)., A method for producing hydrogen that can be implemented in a system for producing hydrogen according to claim 6, the method for producing hydrogen comprising a method (200) for producing a synthesis gas according to claim 9 and further comprising:A step of filtering the synthesis gas by a filtration means,A step of enriching the synthesis gas by a carbon monoxide conversion means,A step of purifying the hydrogen by a purification means to purify the hydrogen and obtain hydrogen. Process for the production of hydrogen according to claim 10, characterized in that it comprises a conversion step by a means for converting hydrogen into ammonia. A method for producing synthetic natural gas capable of being implemented in a system for producing synthetic natural gas according to claim 8, the method for producing synthetic natural gas comprising a method (200) for producing a synthesis gas according to claim 9 and further comprising:A step of filtering, by a filtration means, the synthesis gas,A step of enriching, by a carbon monoxide conversion means, the synthesis gas,A step of methanation by a methanation means for converting hydrogen and / or carbon dioxide into synthetic natural gas. Synthesis gas production unit comprising at least one and at most 100 system(s) (100) intended for the production of synthesis gas according to one of claims 1 to 5. Use of a system (100) for the production of synthesis gas according to one of claims 1 to 5 in the production of electricity, in the production of hydrogen, in the production of synthetic natural gas, in the production of methane, in the production of ammonia, in the production of steam, in the production of heat, in the production of substitute fuel, in the recovery of CO2, in the production of methanol, in electrical networks, in transport, in fuel cells, in industrial production. System for the production of synthesis gas according to one of claims 1 to 5 for the production of at least one substitute fuel for transport and / or the generation of electricity.
Citation Information
Patent Citations
Circulation fluidized bed gasification reactor
JP2010215888A
Integrated pyrolysis and gasification of biomass
US20230109160A1
Apparatus and methods for gasification
WO2015007285A1