Cracking device and process for obtaining hydrogen and pyrolysis oils

Abstract

The present invention relates to a cracking device and to a method for producing hydrogen gas and pyrolysis oils from the recovery of waste material, comprising selective pyrolysis, based on: a first step of pyrolysis of the biogenic fraction of the waste material, with a subsequent cracking step, and a second step of pyrolysis of the synthetic fraction of the waste material, with at least one subsequent condensation step, wherein the first and second pyrolysis steps are configured in series.

Description

[0001]

[0002] Cracking device and process for obtaining hydrogen and pyrolytic oils

[0003] TECHNICAL SECTOR

[0004] The present invention falls within the field of devices, systems and methods for producing hydrogen gas and pyrolytic oils from the recovery of waste material.

[0005] BACKGROUND OF THE INVENTION

[0006] Conventional hydrogen production technologies include steam reforming of natural gas (methane) and oil, catalytic decomposition of natural gas, partial oxidation of heavy hydrocarbons, and gasification of coal or coke.

[0007] Waste conversion processes can be divided into thermochemical and biochemical techniques, which differ in energy requirements, operating conditions (temperatures and pressures), feedstock inputs, efficiencies, reaction times, and final yields. In general, thermochemical processes, i.e., gasification and pyrolysis, are faster than biochemical processes (e.g., fermentation), have higher stoichiometric hydrogen yields, higher conversion efficiencies, and shorter reaction times. However, biochemical processes are less energy-intensive, as they operate under moderate energy conditions, leading to lower hydrogen yields.

[0008] Hydrogen can be produced from a mixture of waste waste and biomass through thermal gasification, followed by cleaning and purification of the resulting synthesis gases. However, these processes are primarily based on gasification, where the pyrolysis and gasification reactions occur in the same reactor, making it impossible to precisely control the parameters of each reaction. In these processes, all fractions present in the raw materials used are gasified (both biogenic and plastic fractions), resulting in both renewable and non-renewable hydrogen.

[0009] The invention described describes a system and process for the recovery of rejected material that allows the production of hydrogen and pyrolytic oils, two compounds with high added value, through a pyrolysis / gasification process that combines different stages and processes. The characteristic of this process lies in the extraction of the compound with the highest added value from each fraction (biogenic and plastic) from a heterogeneous mixture of these fractions and without prior physical separation.

[0010] EXPLANATION OF THE INVENTION

[0011] In a first aspect, the invention provides a biogenic material cracking device for the generation of chemical products including syngas (synthesis gas), as defined in the claims.

[0012] The cracking device, hereinafter referred to as the device, is intended to be fed with gases from thermal processes for the treatment of organic matter, such as, for example, biomass or some waste, where these thermal treatments may correspond to torrefaction, pyrolysis, gasification or any other process that results in a gaseous stream that requires post-treatment. In particular, the gases with which the device is fed are gases from a previous stage of selective pyrolysis of a biogenic fraction of a reject material, where said pyrolysis is carried out at less than 350 ° C, in which partially pyrolyzed reject material and a mixture of permanent gases, condensable volatile gases and condensable compounds are obtained, where the condensable volatile gases are converted into permanent gases by cracking in the device.

[0013] The device comprises a cracking chamber through which the gases to be cracked move, coming from an inlet that enables their entry into said chamber to an outlet through which the cracked gas / syngas exits, where, preferably, the cracking of the gases is carried out at a temperature between 700 and 1200°C.

[0014] Inside the cracking chamber, there is a cracking assembly configured to preheat the gas to be cracked and to crack the preheated gas, generating syngas (synthesis gas). The chamber-cracking assembly arrangement allows the inlet gas temperature to be used to preheat the gases to be cracked and also to reuse the heat from the already cracked gases to preheat the gases to be cracked, increasing the device's thermal efficiency.

[0015] The cracking assembly comprises at least one outer tube arrangement to which an inner tube is concentric, preferably a plurality of said arrangements conveniently distributed in the chamber, where, in each arrangement, gases from the inlet circulate along the outside of the outer tube, such that the gases to be cracked circulate through a space between the outer tube and the inner tube, and where combustion gas circulates through an interior of the inner tube to crack the gas circulating in the space between the outer tube and the inner tube. In this way, the gases moving along the outside of the outer tube exchange heat with the gas moving through the space between the outer tube and the inner tube, producing preheating. In addition, the gases moving along the outside of the outer tube are directed towards the space between the outer tube and the inner tube to be cracked.

[0016] The device also comprises at least one burner linked to each arrangement of outer tube and inner tube, the burner being configured to heat the inner tube to produce cracking, where a fraction of the inlet gas is selectively distributed towards said burner.

[0017] Gas cracking is carried out at a temperature of at least 1200°C, with the gas's travel through the space between the outer and inner tubes maintaining this temperature for at least two seconds. In this way, the burner raises the tube temperature above 1500°C as it burns the combustion gas.

[0018] In addition to the above, the cracking device incorporates baffle plates arranged at a distance inside the cracking chamber, where said baffle plates support the cracking assembly, forming a circuit through which the gases from the inlet move around the outer tube of the arrangement or arrangements. In one embodiment, the device comprises a manifold connected to the burner, i.e., to each burner, where said manifold is configured to direct the gas to be burned toward said burner and a pressurization chamber intended to introduce pressurized air toward each burner.

[0019] In another embodiment of the device, it comprises a regulating valve configured to divide the gas into a stream to be burned that is directed to the burner and a stream of gas to be cracked that is directed towards the cracking chamber, where said regulating valve is controlled based on the temperature of the gas to be cracked.

[0020] As can be seen from the above, one of the advantages of the cracking device of the invention is that it does not use any catalyst for cracking. Furthermore, the cracking of the gases is carried out indirectly, thus avoiding the mixing of the combustion gases with the cracked gases to thermally sustain the cracking process, thus achieving greater purity and higher calorific value.

[0021] In a second aspect, the invention relates to a process for obtaining hydrogen and pyrolytic oils comprising the following steps: a) selective pyrolysis of the biogenic fraction of the reject material at less than 350 ° C, where partially pyrolyzed reject material and a mixture of permanent gases and condensable compounds are obtained; b) selective pyrolysis of the synthetic fraction of the partially pyrolyzed reject material resulting from the previous step, at high temperature, between 400-520 ° C, where synthetic coal and pyrogas are obtained; c) indirect thermal cracking of the mixture obtained in step a) between 700 and 1,200 ° C, where syngas is obtained, and where the thermal cracking occurs in a cracking device according to the first aspect of the invention; d) gasification of the coal generated in step b) at temperatures between 800 and 1.200 °C by means of air and / or water vapor currents; e) condensation of the synthetic pyrogas generated in the high-temperature pyrolysis stage to obtain pyrolytic oils; f) catalytic water displacement reaction from the syngas obtained in stage c); g) separation and storage of the hydrogen gas resulting from the previous stage, where stages a) to d) are carried out in independent reactors.

[0022] The invention describes a process for the recovery of waste material that allows the production of hydrogen and pyrolytic oils, two compounds with high added value, through a pyrolysis / gasification process that combines different stages and processes. The advantage of this process lies in the extraction of the compound with the highest added value from each fraction (biogenic and plastic), from a heterogeneous mixture of these fractions and without prior physical separation.

[0023] In the process of the invention, the different stages of pyrolysis, gasification, and indirect cracking occur in dedicated reactors, thus achieving precise control of the parameters of each reaction. The process allows the production of hydrogen gas and pyrolytic oils from the rejected material. The biogenic fraction of this material, which includes paper, cardboard, biomass, and organic waste, is used for the production of renewable hydrogen. It should be noted that hydrogen is considered renewable when it is produced from these biogenic wastes. Furthermore, the process of the invention allows the synthetic fraction of the rejected material, such as plastics that can no longer be recycled, to be used to obtain pyrolytic oils that can be used in the manufacture of recycled plastics, such as polyethylene, polypropylene, and polystyrene.

[0024] Additionally, the process allows for the recovery of rejected material, a waste that can no longer be recycled and has traditionally ended up buried in landfills or sent to incinerators.

[0025] BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1.- Cracking device.

[0027] Figure 2. Diagram of the process for obtaining hydrogen gas and pyrolytic oils from rejected material comprising a biogenic fraction and a synthetic fraction.

[0028] List of references and figures: 1. Gas inlet to the cracking chamber 7

[0029] 2. Cracked gas outlet

[0030] 3. Cracking chamber housing

[0031] 4. Burner / Burners

[0032] 5. Inner tube

[0033] 6. Outer tube

[0034] 7. Cracking chamber

[0035] 8. Baffle plates

[0036] 10. Reject material input line

[0037] 20. Pirogas line of the biogenic fraction

[0038] 30. Syngas line of the biogenic fraction

[0039] 40. Syngas line mixing the biogenic fraction

[0040] 50. Enriched H2 line

[0041] 60. H2 line

[0042] 70. Synthetic fraction pyrolysis line

[0043] 80. Permanent gas line of the synthetic fraction

[0044] 90. Permanent gas line of the biogenic fraction

[0045] 100. Combustion smoke line

[0046] 110. Pyrolytic oil line

[0047] 120. Char line

[0048] 130. Ash line

[0049] 140. Gasifier syngas line

[0050] 150. Pyrolysis stage of the biogenic fraction

[0051] 160. Pyrolysis stage of the synthetic fraction

[0052] 170. Char gasification stage

[0053] 180. Pirogas filtering stage

[0054] 190. Pyrogas cracking stage of the biogenic fraction

[0055] 200. Cleaning and conditioning stage of the syngas mixture

[0056] 210. Water displacement reaction stage

[0057] 220. H2 separation stage

[0058] 230. H2 storage stage

[0059] 240. Stage of cleaning and conditioning of synthetic fraction pyrogas

[0060] 250. Pyrolytic oil condensation stage

[0061] 260. Combustion stage of permanent gas streams

[0062] 270. Combustion smoke cleaning stage PREFERRED EMBODIMENT OF THE INVENTION

[0063] In the preferred embodiment, the invention provides a device for cracking biogenic material for the generation of chemical products including syngas (synthesis gas), where the gases to be cracked come from previous pyrolysis processes of reject material, and where the gases from a selective pyrolysis process of a biogenic fraction of the reject material at less than 350 °C enter the cracking device, in which partially pyrolyzed reject material and a mixture of permanent gases and condensable compounds are obtained.

[0064] As can be seen in Figure 1 , in the preferred embodiment, the cracking device comprises a cracking chamber 7 whose body resembles an exchanger made up of two groups of concentric tubes and a shell. Inner tubes 5, where the combustion that raises the temperature to carry out the cracking of the gases takes place, are made from a special refractory material resistant to high temperatures and with a high coefficient of thermal conductivity. Outer tubes 6, each placed concentrically to the inner tubes 5, are also made from a refractory material, but with different characteristics, since they do not have to withstand the high temperatures of combustion nor do they need such high conductive power.

[0065] Returning to the cracking chamber 7, it is preferably square in cross-section to optimize the arrangement of inner tubes 5 and outer tubes 6, and is optionally metallic to reduce the weight of the device in general. Each arrangement of inner tubes 5 and outer tubes 6 will be supported by deflector plates 8 distributed along the cracking chamber 7, also serving as a labyrinth for the circulation of the gases to be cracked, which are preheated before the actual cracking, and also to optimize the internal preheating of the chamber 7.

[0066] Now, as stated above, the cracking device is preferably configured in a form similar to a shell-and-tube heat exchanger, and therefore comprises concentric tube arrangements supported by baffle plates 8 inside the cracking chamber 7. This tube arrangement is primarily intended for the indirect heating of the gases to be cracked, using the gases in process or already cracked. Thus, each arrangement consists of an inner tube 5 concentric to an outer tube 6, said tubes 5, 6 being made of refractory steel, through whose interior space, that is, through the space or interstice between said tubes 5, 6, the gases to be cracked circulate; having an outer casing 3 which, together with the baffle plates 8, create a labyrinth that increases heat exchange. Said casing 3 will be conveniently insulated since the cracking temperature will be up to 1,200°C.

[0067] The inner tubes 5, in which combustion occurs, are hermetically sealed from the casing 3 to prevent the combustion fumes from mixing with the gases to be cracked or cracked. The front end of said inner tubes 5 is placed on a base plate, which has a combustion chamber (not shown) for the plenum supply of combustion air used in the burners 4.

[0068] Furthermore, each of the inner tubes 5 is connected to a burner 4, which is automatically ignited, has ionization flame control, and operates automatically without a pilot burner. Gas is supplied to said burners 4 via a blower (not shown) at a pressure of 0.5 bar, which also regulates the temperature by means of a cracked gas signal.

[0069] The combustion chamber includes an air inlet (not shown) via a centrifugal fan (not shown) with the appropriate pressure to supply the burners 4, which will therefore be combined with the blower. Both the fan and the blower can be powered by the same motor, which facilitates regulation.

[0070] Furthermore, the cracking device includes a diverter valve (not shown) for the gases to be combusted in the inner tube 5, depending on the cracking temperature demand. This valve will be automatically controlled by a positioner, which at start-up will direct a greater amount of gas to be combusted until the operating temperature is reached. This operation will be perfectly balanced since the gases to be combusted and the gases to be cracked are simultaneously balanced continuously and automatically.

[0071] The cracking device also comprises an exchanger located at the combustion gas outlet, which is configured to preheat the air or fuel to be used in combustion and thus increase the thermal efficiency of the device.

[0072] Now, with respect to the gas cracking process by means of the device of the invention, it comprises the steps of: distribution of the gas to be cracked into two streams, channeling part of this gas for combustion towards the burners 5 and thus providing the energy necessary for cracking, and another part to direct it towards the inlet 1 and introduce it into the cracking chamber 7, the diverter valve controlled by the temperature of the gas to be cracked is responsible for directing the gas flow; directing the gas to be burned / combusted towards a collective manifold that is responsible for distributing said gas towards the burners 4 arranged inside the inner tube 5 that admits temperatures greater than 1,500 ° C; introduction of air for combustion into the slightly pressurized chamber (0.5 Bar) from which the necessary air is supplied to each burner 5, where said air has been preheated in an exchanger taking advantage of any heat source available in the installation, for example, from the already cracked gases or the combustion gases themselves; introduction of the gases to be cracked into the cracking chamber 7 where the tube arrangement 5, 6 are located, where the deflector plates 8 circulate the gas to be cracked in a labyrinth around the outer tubes 6 producing a preheating of the same; the gases to be cracked already preheated to a temperature close to the cracking temperature, pass through the space between the outer tubes 6 and the inner tubes 5, in which combustion takes place, where in passing through this space the gases reach a temperature of more than 1,200 ° C and are maintained for more than 2 seconds, thus guaranteeing total cracking of all the gases; and the gas already cracked at a temperature higher than 1.200 °C is used to preheat the cracked gas from the thermal process of the reject material, so the consumption of the gas to be burned for cracking will be lower and the performance of the installation can be optimized.

[0073] The second aspect of the invention relates to a process for obtaining hydrogen gas and pyrolytic oils from reject material comprising the following steps: a) selective pyrolysis of the biogenic fraction of the reject material at less than 350 ° C, where partially pyrolyzed reject material and a mixture of permanent gases and condensable compounds are obtained; b) selective pyrolysis of the synthetic fraction of the partially pyrolyzed reject material resulting from the previous step at a high temperature between 400-520 ° C where synthetic coal and pyrogas are obtained; c) indirect thermal cracking of the mixture obtained in step a) between 700 and 1200 ° C, where syngas is obtained, and where the thermal cracking occurs in a cracking device according to the first aspect of the invention; d) gasification of the coal generated in step b) at temperatures between 800 and 1 .200 °C by means of air and / or water vapor currents; e) condensation of the synthetic pyrogas generated in the high-temperature pyrolysis stage to obtain pyrolytic oils; f) catalytic water displacement reaction from the syngas obtained in stage c); g) separation and storage of the hydrogen gas resulting from the previous stage, where stages a) to d) are carried out in independent reactors.

[0074] Pyrolysis of the different fractions of the reject material in different reactors allows precise control of the reaction conditions so that the products obtained, that is, biogenic and synthetic pyrolysis, have particularly interesting characteristics for obtaining hydrogen gas and pyrolytic oils.

[0075] The term "reject material" refers to waste that traditionally cannot be separated mechanically and therefore cannot be recovered. Traditionally, this material is disposed of in landfills or used as fuel in incinerators. This material comprises a heterogeneous mixture of plastic fractions (polyethylene, polypropylene, polystyrene, etc.) and biogenic fractions (wood, paper, cardboard, biomass, organic waste, etc.) in varying proportions.

[0076] The term “partially pyrolyzed reject material” refers to the solid material resulting from the selective pyrolysis at low temperatures of reject material where only the biogenic fraction of the reject material has been pyrolyzed.

[0077] The term "char" refers to the carbonaceous material resulting from the high-temperature pyrolysis of the reject material, commonly also referred to as char. 1 '.

[0078] The term “permanent gases” refers to the gases obtained in a pyrolysis stage, these are usually gaseous mixtures of H2, carbon monoxide (CO), carbon dioxide (CO2) and water (H2O) in different proportions.

[0079] The term “syngas” refers to a mixture containing hydrogen (H2), carbon monoxide (CO) and other gaseous components, such as carbon dioxide (CO2), methane (CH4) and water vapor (H2O) in different proportions.

[0080] The term "pyrogas" refers to the gaseous mixture obtained from pyrolysis processes. This mixture generally contains hydrogen (H2), carbon monoxide (CO), and unreacted light and heavy hydrocarbons (especially methane (CH4), ethane (C2H6), propane (CsHs), and tar). Depending on the type of starting material, the composition of the pyrogas can vary; generally, it can be biogenic pyrogas or synthetic pyrogas.

[0081] The term "condensable products" refers to components resulting from pyrolysis that are in liquid or solid form at room temperature and atmospheric pressure. These products are condensed and collected during the process, after the pyrolysis gases have cooled and become liquid or solid.

[0082] The term "pyrolytic oils" refers to liquid products obtained through the pyrolysis of organic and / or synthetic materials. Their composition consists primarily of saturated, unsaturated, and aromatic hydrocarbons, and their characteristics can vary depending on the source of the materials and the processing conditions.

[0083] In the preferred embodiment of the process of the second aspect, the process comprises, prior to step a), a pretreatment step of the reject material comprising drying, crushing, removal of inert materials and / or removal of metals.

[0084] In another preferred embodiment of the process of the second aspect, the operating temperature of the first pyrolysis stage is between 280°C and 350°C; while the operating temperature of the second pyrolysis stage is between 500°C and 520°C.

[0085] In the most preferred embodiment of the process of the second aspect, the operating temperature of the first pyrolysis stage is between 280°C and 350°C; while the operating temperature of the second pyrolysis stage is between 500 and 520°C and the indirect cracking temperature of the biogenic pyrolysis is between 700 and 1200°C.

[0086] The feed to the first pyrolysis stage (stage a) is carried out at room temperature and the feed temperature of the partially pyrolyzed material to the second pyrolysis reactor (stage b) is carried out between 280 and 350 °C.

[0087] The temperature conditions in the selective pyrolysis stages and their corresponding feed stages allow a temperature gradient (temperature ramp) of 1°C / min-20°C / min, preferably 1°C / min-10°C / min, and even more preferably a gradient of 5°C / min. This gradient allows the production of various products with excellent quality.

[0088] Additionally, the pyrolysis oil obtained in the second stage of selective pyrolysis continues to a condensation stage where the pyrolysis oil resulting from stage b) is condensed to obtain excellent quality pyrolytic oils.

[0089] The process of the invention allows the production of two distinct fractions of pyrolysis oils with different compositions. The first comes from the selective pyrolysis of the biomass fraction of the reject material and is rich in oxygenated compounds (compounds that contain oxygen in their structure, in addition to carbon and hydrogen: benzoic acid, acetic acid, phenols, furfural, etc.) and nitrogenated compounds, such as caprolactams. This fraction, of low industrial value, is ideal for revaluation by its transformation into hydrogen gas.

[0090] The second fraction obtained from the pyrolysis of the synthetic fraction of the reject material is rich in paraffins (linear hydrocarbons composed exclusively of carbon and hydrogen: heptane, octane, nonane...), defins (linear hydrocarbons containing at least one carbon-carbon double bond, which are composed exclusively of carbon and hydrogen: 1-heptene, 1-octene, 1-nonene... ) and aromatic compounds (hydrocarbons formed by cyclic compounds that form carbon-carbon double bonds: benzene, toluene, styrene, naphthalene), this fraction being of high industrial value.

[0091] In a preferred embodiment, the condensation units consist of a combination of tube and shell type heat exchangers, in which a refrigerant fluid, such as air, thermal oil or water, circulates through the tubes, and the combustible gas circulates through the shell, creating homogeneous cooling and progressive condensation.

[0092] In another embodiment of the process of the second aspect, the process includes stages for filtering the pyrolysis product obtained in the selective pyrolysis stages a) and b). During the filtering, ceramic filters and / or cyclones are used to retain solid impurities, mainly the particles generated in the pyrolyzers.

[0093] Preferably, the pyrophosphate obtained in step b) undergoes a filtering step and a cleaning step. In a preferred embodiment, the pyrophosphate cleaning process will be carried out by adding Ca(OH)2 and / or NaHCCl to remove acid gases and / or metals; and by adding carbon to remove dioxins and / or furans.

[0094] In another preferred embodiment, and in parallel to the previous embodiments, the process includes a step of washing the gas resulting from indirect cracking.

[0095] In another preferred embodiment, the residence time of the reject material in the reactor of the first selective pyrolysis is between 1 and 3 hours, preferably approximately 2 hours.

[0096] In another preferred embodiment, the residence time of the reject material in the reactor of the second selective pyrolysis is between 1 and 3 hours, preferably approximately 2 hours.

[0097] In another preferred embodiment, the residence time of the mixture of permanent gases and condensable compounds (biogenic pyrogas) in the indirect cracking reactor is between 1 and 5 seconds, preferably about 2 seconds.

[0098] In the most preferred embodiment, the residence times of the reject material in the reactor of the first and in the reactor of the second selective pyrolysis are between 1 and 3 hours, preferably about 2 hours.

[0099] In this step, the carbon monoxide (CO) present in the synthesis gas obtained in step c) reacts with water molecules (H2O). This reaction is known as the "water shift reaction". The water shift reaction from syngas, a mixture of hydrogen (H2) and carbon monoxide (CO), to react with water (H2O) and produce additional hydrogen gas (H2) and carbon dioxide (CO2). As a result of this reaction, hydrogen (H2) and carbon dioxide (CO2) are formed. The hydrogen produced is collected as a valuable product, while the remaining permanent gases are diverted to a cogeneration system.

[0100] In another preferred embodiment, the process includes a step for cleaning syngas resulting from the indirect cracking of step c). This step will be carried out by adding Ca(OH)2 and / or NaHCCh to remove acid gases and / or metals; and by adding carbon to remove dioxins and / or furans. The objective is to eliminate any impurities that impede the subsequent water displacement reaction of step d).

[0101] Preferably, the hydrogen obtained in step f) of the water shift reaction is separated by pressure swing adsorption (PSA). This method takes advantage of the differences in the adsorption properties of the different gaseous components to achieve the separation. PSA is used industrially for the separation of H2 from synthesis gas and allows H2 to be obtained practically at the inlet pressure and a tail gas stream containing a mixture of N2, CO2, CO, and CH4.

[0102] In step d), the coal resulting from the second selective pyrolysis undergoes a gasification process. The coal is converted into a combustible gas by reacting with a gasifying agent, such as water vapor (H2O), air, or carbon dioxide (CO2), at elevated temperatures. This process is carried out in the absence of oxygen (anoxia) or under oxygen-limiting conditions to prevent complete combustion of the coal and obtain a gas rich in hydrogen and carbon monoxide, known as synthesis gas or syngas.

[0103] In step d) the mixture of coal and gasifying agent is introduced into the gasification reactor, which is heated to elevated temperatures in the range of 800°C to 1,200°C. Preferably, the temperature of the gasification reactor during gasification is approximately 1,000°C. In step d) air and water vapor are used as the gasifying agent in a ratio of 4:1.

[0104] In another preferred embodiment, the permanent synthetic gas, which comes from the second stage of condensation of the synthetic fuel, will be recirculated to a cogeneration system, capable of generating thermal and electrical energy to supply the different elements of the process itself.

[0105] Likewise, the excess thermal energy from the cogeneration system can be redirected to raise and / or maintain the temperature of the pyrolysis stages so that complete thermal and electrical utilization of the permanent gases obtained from the synthetic fraction of the rejected material is achieved.

[0106] In this way, and according to previous embodiments, the reuse of permanent gases is achieved, allowing operating temperatures to be reached and maintained without the need for external fuel gases. Furthermore, part of the permanent synthetic gas can be reused for power generation, allowing the plant in which the method object of the present invention is installed to be self-sufficient.

[0107] Preferably, the process includes a stage for cleaning the flue gases resulting from the cogeneration system. This stage comprises: a catalytic stage for the removal of NOx, the injection of a powder additive (NaHCO2 or Ca(OH)2) for the removal of acid gases (SO2, HCl), and a filtration stage for the removal of solid material that may be generated during combustion.

[0108] Having sufficiently described the nature of the present invention, as well as the manner of putting it into practice, it is not considered necessary to explain it further so that any expert in the field may understand its scope and the advantages derived from it, stating that, within its essence, it may be put into practice in other embodiments that differ in detail from the one indicated as an example, and to which it will also achieve the protection sought provided that its fundamental principle is not altered, changed or modified.

Claims

CLAIMS 1. Device for cracking biogenic material for the generation of chemical products that include syngas (synthesis gas), comprising: a cracking chamber (7) through which the gases to be cracked move from an inlet (1) that enables the entry of the same to an outlet (2) of cracked gas / syngas;a cracking assembly arranged inside the cracking chamber (7) configured to preheat the gas to be cracked and to crack the preheated gas generating syngas, said cracking assembly comprising at least one outer tube (6) to which an inner tube (5) is concentric, where the gases coming from the inlet (1) circulate through the outside of the outer tube (6), where the gases to be cracked circulate through a space between the outer tube (6) and the inner tube (5) for cracking at a temperature of at least 1200 ° C sustained for at least 2 seconds, and where a combustion gas circulates through an interior of the inner tube (5) to crack the gas circulating in the space between the outer tube (6) and the inner tube (5), and where the gases moving through the outside of the outer tube (6) exchange heat with the gas moving through the space between the outer tube (6) and the inner tube (5);and where the gases moving along the outside of the outer tube (6) are directed towards the space between the outer tube (6) and the inner tube (5); and at least one burner (4) configured to heat the inner tube (5), where a fraction of the gas at the inlet (1) is selectively distributed towards said burner (4).

2. Cracking device according to the preceding claim comprising deflector plates (8) arranged at a distance from the interior of the cracking chamber (7), where said deflector plates (8) support the cracking assembly forming a circuit through which the gases coming from the inlet (1) move around the outer tube (6).

3. Device according to the preceding claim comprising a manifold connected to the burner (4) configured to direct the gas to be burned towards said burner (4) and a pressurization chamber provided to introduce air towards the burner (4).

4. Device according to any of the preceding claims comprising a regulating valve controlled by the temperature of the gas to be cracked, configured to divide the gas into a stream to be burned that is directed to the burner (4) and a stream of gas to be cracked that is directed towards the cracking chamber (7); 5. Device according to any of the preceding claims wherein the cracking assembly comprises a plurality of concentric outer tube (6) and inner tube (5) arrangements with a burner (4) associated with each inner tube (5).

6. Process for obtaining hydrogen gas and pyrolytic oils from reject material characterized in that it comprises the following stages: a) selective pyrolysis of the biogenic fraction of the reject material at less than 350 ° C, where partially pyrolyzed reject material and a mixture of permanent gases and condensable compounds are obtained; b) selective pyrolysis of the synthetic fraction of the partially pyrolyzed reject material resulting from the previous stage at a high temperature between 400-520 ° C where synthetic coal and pyrogas are obtained; c) indirect thermal cracking of the mixture obtained in step a) between 700 and 1200 ° C, where syngas is obtained, and where the thermal cracking occurs in a cracking device according to any of claims 1 to 5; d) gasification of the coal generated in step b) at temperatures between 800 and 1.200 °C by means of air and / or water vapor streams; e) condensation of the synthetic pyrogas generated in the high-temperature pyrolysis stage to obtain pyrolytic oils; f) catalytic water displacement reaction from the syngas obtained in stage c); g) separation of the hydrogen gas resulting from the previous stage. where stages a) to d) are carried out in independent reactors.

7. The process for obtaining hydrogen from rejected material according to the preceding claim, wherein the process comprises prior to step a) of pretreatment of the rejected material, which comprises drying, crushing, removal of inert materials and / or removal of metals.

8. The process for obtaining hydrogen from waste material according to any of the preceding claims 6-7, wherein the first pyrolysis stage Selective pyrolysis of the biogenic fraction is carried out at a temperature between 280°C and 350°C, and the second stage of selective pyrolysis of the synthetic fraction is carried out at a temperature between 500°C and 520°C.

9. The process for obtaining hydrogen from reject material according to any of the preceding claims 6-8, wherein the feeding stage of the second pyrolysis stage is carried out at a temperature between 280°C and 350°C.

10. The process for obtaining hydrogen from reject material according to any of the preceding claims 6-9, wherein the residence time of the reject material in the first pyrolysis reactor is between 1 and 3 hours.

11. The process for obtaining hydrogen from reject material according to any of the preceding claims 6-10, wherein the residence time of the partially pyrolyzed reject material in the second pyrolysis reactor is between 1 and 3 hours.

12. The process for obtaining hydrogen from reject material according to any of the preceding claims 6-11, wherein the residence time of the pyrolysis resulting from selective pyrolysis of the biogenic fraction in the indirect cracker is between 1 and 5 seconds, preferably approximately 2 seconds.

13. The process for obtaining hydrogen from rejected material according to any of the preceding claims 6-12, wherein the synthetic pyrogas resulting from step b) goes through the steps of: cleaning the synthetic pyrogas at a temperature between 450°C and 520°C; and condensation in a condensation unit, configured to separate at least one liquid fraction, and at least one permanent synthetic gas fraction.

14. The process for obtaining hydrogen from rejected material according to any of the preceding claims 6-13, characterized in that it comprises a stage of storing hydrogen gas from stage g) in a gas tank.

15. The process for obtaining hydrogen from rejected material according to any of the preceding claims 6-14, wherein the permanent gases resulting from steps e) and f) are used as fuel in a cogeneration system for the production of thermal and electrical energy.

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