Integrated system and procedure for device for conversion of carbon-based composite material to hydrogen rich gas including options for recovery and use of exhaust and waste

Abstract

To provide an integrated system and a procedure both, for a device for efficient generation of a final gas containing hydrogen as the main volume component from a raw material gas derived from a carbon-based material.SOLUTION: An integrated system is achieved by using a hydrogen photocatalytic reaction under lower pressure and temperature than conventional gas modification systems. This invention also includes an option for obtaining a final gas free from CO2 exhausts, solid wastes and, liquid wastes.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to an integrated system of an apparatus designed to convert a carbon-based composite material into a hydrogen-rich gas. The system provides the option of recovering and utilizing its carbon dioxide (CO2) emissions as well as solid and liquid residues. The system incorporates the recirculation of heat generated by the combustion of a portion of the final gas produced. This heat is transferred to the feedstock in a first circulating metal and catalyst fluidized bed reactor, where the feed gas is first produced. After separation from the coarse ash, this feed gas is sent to a second reactor, where it undergoes a cleaning process that includes partial oxidation with steam and / or oxygen. This step removes most of the tar, and during this process, the gas is separated from the fine ash.

[0002] Optionally, an option route for the recovery and utilization of CO2 emissions as well as solid, liquid, and gaseous wastes is added.

Background Art

[0003] In conventional hydrogen production processes using carbon-based materials, steam forming, or solid or liquid gasification is used for further purification.

[0004] In these processes, generally, air or oxygen is used as an oxidant to raise the process temperature above 900°C, which can cause thermal decomposition of the feedstock. This is technically feasible, but at such temperature levels, heat-resistant materials and high energy consumption are required. In addition, the resulting gas usually does not have hydrogen as the main component. To reduce costs, heat recovery devices have been developed to transfer a portion of the heat of the combusted syngas to the feedstock or oxidant, but they must address the following problems.

Summary of the Invention

Problems to be Solved by the Invention

[0005] Double-chamber pyrolysis apparatuses use an indirect heating system in which heat is transferred to the carbon-based solid material by gas. However, since heat is transferred by convection and the thermal conductivity of solids is low, this technique is not very efficient.

[0006] On the other hand, in apparatuses with a single chamber into which air, oxygen-enriched air, or heated oxygen is injected and heat is directly supplied to the carbon-based material by convection, these gases are mixed with the resulting final gas, resulting in a low hydrogen ratio.

[0007] In addition, conventional systems for producing gases with a high hydrogen content also generate environmentally unfriendly gases, liquids (tar and wastewater), and solids (ash). In most cases, these gases also contain high levels of carbon dioxide, nitrogen oxides, and sulfur. CO2 is generally released into the environment, and the tar and water generated after gas cleaning usually cause environmental problems and high purification costs. Ash generated as solid waste is usually landfilled.

[0008] There are various methods for recovering, storing, and utilizing CO2, but they involve complexities such as using high pressures and transportation costs to the place of use. One possibility for utilization is soft drinks, but this is economically feasible only when the user is near the place where CO2 is recovered.

[0009] Other problems in conventional systems include the efficient removal of tar from pyrolysis gas and the efficient supply of heat to the carbon-based material.

[0010] In addition, regarding ash, the costs associated with recovery, storage, transportation, and landfill fees are very high. Even when used in industries such as cement, storage and transportation costs are incurred, and its purchase price is generally low.

[0011] Accordingly, an object of the present invention is to produce hydrogen from a carbon-based material in a process operating at atmospheric pressure and a moderate temperature around 600° C., in which heat is efficiently transferred to the carbon-based material by conduction and all of this is carried out within a process that does not involve the emission of CO2, tar, and ash.

Means for Solving the Problems

[0012] The present invention relates to both an integrated system (referred to as a system, SID, or SID system) and a procedure for efficiently producing a final gas having hydrogen as a main volume component from a raw material gas derived from a carbon-based material. This is achieved by using a hydro-photo catalytic reaction at a lower pressure and temperature than conventional gas reforming systems. The present invention also includes the option of obtaining a final gas without CO2 emissions and solid and liquid wastes.

[0013] The SID system comprises the following equipment: A) At least two different types of reactors, R1 and R2. R1 comprises an internal container and R2 comprises an internal chamber, both of which are equipped with peripheral equipment. These reactors may each be composed of a group of reactors. When R1 and / or R2 are composed of two or more reactors, these reactors may be arranged in series, parallel, or a combination of both. B) A suitable gas cleaning circuit comprising at least two tanks: one is designed to capture acidic compounds and the other is designed to capture alkaline compounds. C) At least two cooling and condensation devices. One is for the final gas after gas cleaning and the other is for separating water and CO2 from the combustion gas exiting R1. D) A filtration device for the final gas. It comprises one or more filters, preferably two filters, one for solids and the other for liquids. E) At least one blower for attracting and maintaining a stable pressure within the system. F) At least two ash recovery tanks. At least one is for coarse ash and at least one is for fine ash. G) At least one carbonation and / or bicarbonation tank, called a mineralisation tank. CO2 is dissolved and reacted with at least two substances selected from a specific list. H) At least one centrifuge and / or a draining press. Subsequently, at least one container equipped with a heat source for drying and / or calcining and / or purifying the product from at least one mineralisation tank is installed. I) Optionally, an apparatus for manufacturing a foaming additive. This apparatus comprises at least one container for mixing and at least one drying unit, both of which are intended to optionally manufacture the foaming additive. J) An automatic control system.

[0014] The raw materials supplied to this system include the following: a) Carbon-based materials, b) One or more reaction fluids such as, for example, water, steam, oxygen, air, and / or carbon dioxide, c) In addition, the raw materials may include the following. i) Gases and residues obtained externally or from other stages of the process of the present invention. ii) When manufacturing an additional foaming agent: in addition to ash, sodium bicarbonate, potassium bicarbonate, calcium sulfate, potassium sulfate, or ammonium sulfate.

[0015] Regarding reactors R1 and R2: R1 preferably has a cylindrical shape and comprises the following: i) Two walls, an inner wall and an outer wall, which are separated from each other and define a chamber. The inner wall is the wall of the inner container. This inner container has at least one inlet from the outside with at least one supply hopper and at least two outlets, at least one of the outlets being arranged at the upper part suitable for discharging the raw material gas, and at least one of the other outlets being arranged at the bottom suitable for discharging ash. The inner container preferably has an additional inlet at one of its ends, one for at least one reaction fluid and the other for un-gasified tar. Optionally, there may be another inlet for additional gas or high-temperature fluid coming from at least the heat source of the chamber contained within the double wall. Further, this container preferably houses at least one stirring system together with a catalytic fluidised bed mainly composed of granulated metal oxide based on iron, nickel, and copper, and optionally at least one heat source for generating a fluid that enters from the upper part and flows directly into the interior. ii) A chamber configured within the double wall. It is provided with at least one inlet, and preferably a heat source is arranged for generating a high-temperature fluid generated by the combustion of the final gas or a high-temperature fluid that receives heat from the final gas. The chamber also has at least one outlet for the high-temperature fluid generated by the heat source and at least one outlet connecting the chamber to the interior of the inner container.

[0016] R2 with at least one inlet and one outlet comprises the following: a) A cyclone with a catalyst preferably based on nickel, copper, and iron housed in the walls and the interior. b) At least one heat source for generating a high-temperature fluid with light of a wavelength of 100 - 700 nanometers (nm). The light is preferably ultraviolet light (BL / UV), preferably generated by an oxygen - hydrogen (OH) burner, or by an electric plasma of an inductive or non-transferred electric arc, or generated by a gas and / or steam (G / WV) torch. c) At least one heating zone located in front of or within the cyclone described in the previous item and equipped with a heat source for generating a high-temperature fluid. Preferred heat sources are preferably G / WV torches generated by an electric plasma or an oxygen-hydrogen burner, and the second preferred heat source is preferably an oxygen combustion burner that uses a part of the final gas. d) At least two ash outlets, each equipped with a pair of valves arranged vertically and continuously together with an intermediate tank at each outlet. One pair of these valves is arranged at the bottom of the container housing the cyclone, and the other pair is arranged at the bottom of the cyclone. Each pair of these valves has an upper valve in the "normally open" position and a lower valve in the "normally closed" position.

[0017] R1 and R2 may both be composed of one or more reactors. When there are more than two reactors, they may be arranged and interconnected in series, in parallel, or in a combination of both arrangements.

[0018] Regarding the gas cleaning circuit of item B above, the gas cleaning circuit comprises the following: a) At least two gas cleaning sub-circuits equipped with desalted and doped water. One of them contains an alkaline substance such as sodium hydroxide or potassium hydroxide, and the other contains water doped with an acidic substance such as sulfuric acid or hydrochloric acid. b) Each of these sub-circuits has at least two inlets, one for the contaminated final gas and one for the inlet of the doped water. It also has at least two outlets, one at the upper part for the already cleaned final gas and the other at the bottom for the doped water and the reaction products. The reaction products are, for example, sodium chloride or potassium chloride when the water is doped with sodium hydroxide or potassium hydroxide, or ammonium sulfate when the water is doped with sulfuric acid, etc. c) Each of these sub-circuits is equipped with at least one spray for cleaning the gas with the doped water. d) Each of these sub - circuits is provided with two valves arranged vertically and continuously with an intermediate space at each outlet for discharging the contaminated doped water. The upper valve is in the "normally open" position and the lower valve is in the "normally closed" position.

[0019] Regarding the cooling and condensation device of item C above: 1. A water vapor condensation device that includes a final gas and has at least one condenser comprises the following: a) A liquid - gas heat exchanger in which a liquid receives heat from a gas and condenses water from the water vapor that results in the final gas. It has an inlet for the wet final gas, an outlet for the dry final gas, and another outlet for the water condensed with a small amount of contaminants. b) A tank at the outlet of the condenser. It functions as a separator for the final gas and the water condensed with a part of the impurities carried by the final gas. In this tank, water and impurities sink to the bottom and the final gas exits from the upper outlet. Additionally, this tank suitable for discharging water containing contaminants is provided with two valves arranged vertically and continuously. The upper valve is in the "normally open" position and the lower valve is in the "normally closed" position.

[0020] 2. A water vapor condensation device that includes combustion gas from R1 comprises at least two types of heat exchangers, and each heat exchanger includes at least one of the following types of heat exchangers: a) A type of gas - gas heat exchanger in which a reaction fluid and CO2 absorb heat from the combustion gas that has exited R1. Both the gas receiving heat and the gas giving heat are provided with chambers each having at least one inlet and one outlet in order to maintain independent circulations. b) Another type of heat exchanger that functions as a condenser. This is a liquid - gas heat exchanger in which a liquid absorbs heat from the combustion gas and condenses the water vapor contained in the liquid. Subsequently, a tank is installed for separating CO2 from the condensed water. In this tank, water accumulates and is then discharged in a condensed state. The tank is provided with two valves arranged vertically and continuously. The upper valve is in the "normally open" position and the lower valve is in the "normally closed" position.

[0021] The final gas filtration device shown in item D has an inlet and an outlet and houses at least one solid and / or liquid filter. As the solid, activated carbon or calcium carbonate is preferred, and as the liquid, biodiesel or glycols such as propylene glycol or ethylene glycol are preferred. All filtration elements can be reprocessed together with carbon-based materials after their service life has passed.

[0022] At least one blower shown in item E has an inlet and an outlet for the final gas and serves a dual function of generating a suction force on one hand and compensating for the pressure drop in the SID system to maintain a stable pressure on the other hand.

[0023] The ash recovery tank of item F includes at least two gas washing tanks for the final gas that recover water containing ash and tar impurities, and each tank has at least two inlets and three outlets. The two inlets allow access to water contaminated with ultra-fine ash and tar. Regarding the three outlets, one is for sending the tar floating in the water to R1, another is for sending the precipitated wet ultra-fine ash to the supply port of R1, and the third is for sending the water back for gas washing and recycling. These tanks have valves and pumps that discharge ash, water, and tar in response to level sensors.

[0024] The mineralization tank of Item G comprises at least one carbonation and / or bicarbonation tank called a mineralization tank, and is suitable for dissolving and reacting CO2 with at least two of the following substances: i) sodium hydroxide or potassium hydroxide, ii) sodium sulfate or potassium sulfate, iii) sodium carbonate or potassium carbonate, iv) calcium hydroxide, v) sodium chloride, vi) methanol, vii) urea, viii) water, and ix) ammonia. Additionally, the tank includes at least one heat source and cooling source, at least one control device, temperature, pressure, and pH sensors, at least one stirring system, and optionally at least one of the following catalysts: zinc oxide and cerium dioxide.

[0025] Following the centrifuge or dewatering press described in Item H, a container tank equipped with a heat source suitable for drying and / or calcining the product from at least one mineralization tank is installed.

[0026] The optional device for manufacturing the foaming additive mentioned in Item I comprises at least one mixing container and at least one drying device, both of which are suitable for manufacturing the optional foaming additive preferably used in the building materials and plastic industries.

[0027] The automatic control system described in Item J is programmed and, based on that program, is equipped with a plurality of sensors suitable for operating or stopping electromechanical equipment and maintaining temperature, pressure, pH, H2 / CO ratio, level, and flow rate within a pre-set range.

[0028] The SID system for converting carbon-based materials into final gas, with the option of recovering and utilizing CO2 emissions and solid waste, performs the following procedure, which comprises the following steps.

[0029] 1. - First stage of raw material gas generation: In this first stage, R1 starts the process of generating raw material gas by the physicochemical decomposition of a carbon-based material. This physicochemical decomposition of the carbon-based material occurs in R1 and is due to the following reasons. a) It is exposed to at least one reaction fluid at a temperature of 400°C to 800°C. b) The carbon-based material is immersed in a granular metal oxide that acts as a fluidized bed generating a catalytic effect and is under agitation. These conditions contribute to the heat diffusion and transfer, as well as the promotion of raw material gas generation. Regarding the reaction fluid, water, steam, oxygen, air, and carbon dioxide are preferred. When using one or more reaction fluids, the reaction fluid has received heat in advance directly from the combustion gas derived from the final gas by mixing with them or indirectly by a heat exchanger placed within a double jacket.

[0030] 2. - Second stage of raw material gas reforming: In this stage, the process carried out in the first stage in R2 is continued, and most of the tar present in the raw material gas is removed by reforming the raw material gas. To perform this reforming, it is economically advantageous to utilize the heat carried by the raw material gas from R1 to perform irradiation with intense light having a wavelength of 100 to 700 nanometers (nm) on a surface covered with a catalyst in R2. Desirably, the light is BL / UV generated by a gas that can be generated by an OH burner or a PE of an induction type or non-transfer type electric arc and / or a G / WV torch. In R2, the tar present in the raw material gas is reformed by a hydrogen catalytic reaction at a pressure of -100 to 100 millibars and a temperature of 400°C to 800°C, and long molecules are changed into shorter molecules and converted into the final gas. In the final gas, more than 70% of the molecules are hydrogen and carbon monoxide, and the molar ratio of these two components is close to 2:1 respectively.

[0031] 3. - The third gas cleaning stage: It occurs in the equipment mentioned in item B of the SID system. In gas cleaning, a cyclone in R2, which is designed to separate fine ash (with a diameter of 0.5 to 0.1 millimeters) from the final gas, is used. After this separation, the gas passes through at least two tanks containing water. One contains an alkali additive and the other contains an acid additive, thereby recovering residual ultrafine ash (with a diameter of less than 0.1 millimeter), trace amounts of tar, as well as both acidic gases (such as hydrogen chloride and hydrogen sulfide) and basic gases (such as ammonia). Then, this final gas undergoes a cooling process in the cooling and condensation device described in item C to condense water that may contain trace amounts of tar. Finally, the final gas can be used after being filtered by the equipment in item D (the gas filtration device).

[0032] 4. - The fourth stage of heat recycling or reuse: The heat generated by the combustion of a part of the final gas is utilized by R1 and R2. This heat acts on the raw materials and the raw material gas through the granular metal oxide by the following routes that can be executed simultaneously, raising and maintaining their temperatures to 600 °C. - Inside the chamber formed by the double jacket of R1, at least one reaction fluid that absorbs heat from the final combustion gas and / or the final combustion gas circulates, thereby heating the outer surface of at least one inner container of R1, and thus transferring heat to the granular metal oxide. These oxides transfer the received heat to the carbon-based material flowing through the inner container of R1 by conduction. To efficiently transfer heat to the carbon-based material by conduction, it is important to inject at least one high-temperature reaction fluid under pressure or to use a stirring system such as the above-mentioned mechanical stirrer to stir the granular metal oxide at a temperature of 400 °C to 800 °C. In a chamber formed by a double jacket of -R1, the granular metal oxide and carbon-based material flowing inside are directly heated by circulating the final combustion gas and / or at least one reaction fluid that has absorbed heat from the final combustion gas (inside at least one inner container of R1). In order to efficiently transfer heat to the carbon-based material by conduction, it is necessary to inject at least one of the high-temperature reaction fluids under pressure or use a stirring system such as a mechanical stirrer to stir the granular metal oxide at a temperature of 400°C to 800°C. - Electric heating is performed on the outer wall of at least one inner container of R1 through which the granular metal oxide and the raw material pass, and / or on the outer wall of at least one duct through which at least one of the reaction fluids flows.

[0033] 5. - The fifth stage of waste recovery and reuse: This stage involves the equipment mentioned in items F, G, and H (ash recovery tank, mineralization tank, and centrifuge or press), and optionally includes a route for recovering and utilizing solid waste, liquid waste, and gaseous waste. This enables all solid waste, liquid waste, and gaseous waste to participate in the circular economy. The sub-stages included in this fifth stage are detailed below, explaining where the above-mentioned waste is located and recovered, and also indicating the destination of each waste. - Sub - stage (a): CO2 is recovered from the final combustion gas at the end of the exhaust chimney of R1 using the equipment described in section b of item C (the tank at the condenser outlet designed to separate water from the final gas) and sent to the equipment mentioned in item G (the mineralization tank). The said final combustion gas, which is used to heat R1 and contains CO2 and water vapor, has these two components separated by cooling in at least one condenser followed by a separator tank. The separated CO2 is recovered by reacting it after being dissolved in at least two of the following substances: i) sodium hydroxide or potassium hydroxide, ii) sodium sulfate or potassium sulfate, iii) sodium carbonate or potassium carbonate, iv) calcium hydroxide, v) sodium chloride, vi) methanol, vii) urea, viii) water, and ix) ammonia. By this process, sodium carbonate or potassium carbonate, sodium bicarbonate or potassium bicarbonate, or dimethyl carbonate is produced. Then, in the equipment mentioned in item H (a centrifuge or a dewatering press followed by a tank equipped with a heat source): a) in the case of sodium bicarbonate or potassium bicarbonate, when solids precipitate, centrifugation, drying, and / or purification are carried out for commercialization; b) in the case of sodium carbonate or potassium carbonate, the previous product needs to be calcined. When bicarbonates are produced, they can be sold in an already established market or used in the production of the foaming additives included in this patent. When sodium bicarbonate or potassium bicarbonate, or sodium carbonate or potassium carbonate is produced, by - products such as ammonia, calcium sulfate or ammonium sulfate, or calcium chloride or ammonium chloride can also be sold. - Sub - stage (b): The dried coarse ash (with a diameter greater than 0.5 millimeters) is recovered at the lower part of R1. This coarse ash or sandy ash is composed of various inert metals exceeding 50% produced in at least one R1 and is sent to a mixing tank capable of producing the foaming additives as mentioned in the equipment of item I. -Sub-stage (c): Fine dry ash (with a moisture content of less than 4%) is recovered at the lower part of R2. The fine ash is generated by at least one cyclone contained in at least one R2 and is sent to a mixing tank where the foaming additive mentioned in the equipment of item I is optionally manufactured. -Sub-stage (d): Ultra-fine wet ash (with a moisture content of more than 50%) is recovered at the bottom of at least one gas washing tank. This ash is mainly composed of a small amount of fixed carbon and can be mechanically extracted and used as a carbon-based material in R1. -Sub-stage (s): The water from gas washing accumulates by precipitation at the bottom of at least one tank arranged in the lower section below. This water has 95% of the previously recovered tar removed and 95% of the recovered ash removed, and is reused for gas washing. The remaining trace amount of floating tar is also separated and mechanically extracted, and can be re-introduced into R1 together with the carbon-based material.

[0034] 6.-Sixth stage of the reuse of fine ash and coarse ash: The equipment (mixing container and drying device) mentioned in item I optionally uses its own dried coarse ash and fine ash to produce multifunctional additives such as foaming agents, heat insulation and sound insulation agents, and flame retardants, by mixing with at least one of the following products: a) sodium bicarbonate or potassium bicarbonate, b) ammonium sulfate or calcium sulfate, together with a dispersant such as polyethylene wax, ethylene vinyl acetate (EVA), or paraffin. This sixth stage includes the following sub-stages to easily produce and use this additive in plastics, clay, mortar, or cement: Sub-stage 1 of the sixth stage: In the mixing tank, heat the dispersant wax to a temperature sufficient for the dispersant wax to melt and become completely liquefied. -Add sodium bicarbonate or potassium bicarbonate, or ammonium sulfate or calcium sulfate to the liquid wax and continue stirring until the components are dispersed. -Cool until a viscous state is reached. - Once this viscous state is reached, stop stirring and let it cool until solidification occurs. Finally, cut it in the solid state for potential use, such as the production of pellets or granules. - In the above mixture, the amount of sodium bicarbonate or potassium bicarbonate, or ammonium sulfate or calcium sulfate, must be not less than the amount of coarse ash and fine ash produced in the SID. - Sodium bicarbonate or potassium bicarbonate obtained from other processes unrelated to the present invention, or alternatively ammonium sulfate or calcium sulfate, may be added to the mixture described in the previous item.

[0035] The importance of the previous stage is to convert the hydrogen production system into a clean process without an increase in the carbon footprint. Furthermore, the utilization of CO2 emissions and ash from this process strengthens the circular economy. Ash, which was generally considered to have little or no value as it was commonly used as a substitute for sand in the production of cement and mortar products, now has added value by being sold as part of a foaming additive. CO2, which was also regarded as a low-value product, is used in the production of carbonated beverages near the location where it is generated. According to the present invention, CO2 now provides an opportunity to enter a more attractive market through the production of sodium carbonate or potassium carbonate, or sodium bicarbonate or potassium bicarbonate. These are sold in large quantities in agriculture to neutralize soil acidity, and are also sold as foaming agents for food, plastics, concrete, cement, ceramics, and clay. In addition, sodium carbonate or potassium carbonate is also used in the manufacturing industries of paper, fibers, soaps, and glass.

[0036] When used in the plastics industry, sodium bicarbonate or potassium bicarbonate incorporated into a foaming additive is environmentally advantageous. This is because when the foaming additive is heated within the plastic resin during the manufacturing process of the final product, CO2 is released by decomposition and encapsulated, remaining trapped in the independent air bubbles within the material, i.e., the small microbubbles that significantly reduce the density of the product, thus preventing its migration into the environment. That is, the foaming additive serves as an alternative to raw materials derived from fossil sources and prevents CO2 emissions into the environment.

[0037] 7. The seventh stage of process control: It is the control equipment mentioned in item J, equipped with sensors installed at different locations of different devices, suitable for measuring temperature, pressure, pH, H2 / CO ratio, level, and flow rate, and for automatically controlling the normal operation of the system. According to the instructions of these sensors, the system itself automatically performs the necessary operations and preferably maintains the control of the preset parameters according to the ratio of the expected operating range according to the preset limits. Thereby, if any ratio exceeds the preset value, the sensor makes corrections and issues commands acting on each component as shown below. a) A range is defined for the following ratio: actual volume of hydrogen / actual volume of carbon monoxide: H2 / CO - When it is greater than the specified value, reduce the steam supply until the ratio reaches within the specified range. - When it is less than the specified value, increase the steam supply until the ratio reaches within the specified range. b) A range is defined for the following ratio: ratio of the actual temperature of reactor 1 / preset limit temperature: (T1) / (T limit) - When the temperature is higher than the specified value, increase the supply of raw materials until the temperature reaches within the specified range. - When the temperature is lower than the specified value, activate the oxygen supply at R1 until the temperature reaches within the specified range. c) A range is defined for the following ratio: actual pressure of reactor 1 / preset limit pressure 1: (PR1) / (PR limit 1) - If the pressure is higher than the specified range, reduce the supply of raw materials and / or oxygen until the pressure is within the specified range. This instruction takes precedence over (b). - If the pressure is lower than the specified range, increase the supply of raw materials and / or oxygen until the pressure is within the specified range. If the ratio is higher than 1, the safety valve opens. d) A range is defined for the following ratio: actual pressure of reactor 2 / pre-set limit pressure 2: (PR2) / (PR limit 2) - If the pressure exceeds the specified range, the suction of the blower mentioned in the equipment of item E increases until the pressure reaches the level of the specified range. - If the pressure is below the specified range, the suction of the blower decreases until the pressure returns within the specified range and may reach zero. e) A range is defined for the following ratio: level in any of the tanks for individually discharging each of the following materials: dry ash, tar, water, and wet ash / limit level: (N) / (N limit). - If it is larger than expected, operate the valves and pumps. - If it is smaller than expected, stop the valves and pumps.

[0038] The fifth and sixth steps are optional in that they provide additional advantages to the proposed system, but they do not themselves change the way the final gas is produced. Rather, they complement the system by removing waste. However, it is also possible to implement other methods of reducing or eliminating waste.

Brief Description of the Drawings

[0039]

Figure 1

Modes for Carrying Out the Invention

[0040] Figure 1 shows the state in which the carbon-based material (22) enters from the supply port (16) in the inner container of R1(1), and calcium carbonate, sodium carbonate, or potassium carbonate is also introduced as an optional additive. This additive is an alkaline element that functions to capture acidic substances, reacts with acidic substances to form compounds such as calcium chloride or calcium sulfate, and these are later discharged from the system as part of the ash. This R1(1) is composed of an external chamber and an internal chamber. The internal chamber is composed of a container that houses a granular metal oxide equipped with an electric stirrer (18), and at least one reaction fluid preheated by a heat exchanger (9) is added thereto. When the carbon-based material is gasified, it generates solid waste consisting of ash in the form of sand, and this solid waste is removed by gravity through a shaft (3) and a duct (17) arranged at the bottom of R1(1).

[0041] A space that preferably functions as a combustion chamber (12) for oxygen combustion is formed between the wall of the inner container of R1(1) and the jacket surrounding it. Inside this chamber, there is at least one burner (2) for burning hydrocarbons or the final gas (FG) in order to heat both walls of the inner container of R1 and to reheat at least one reaction fluid (26) arranged in a coil or a heat exchanger (20) arranged in the combustion chamber (12). Then, this already high-temperature reaction fluid is injected into the inner part where the carbon-based material (22) flows.

[0042] The final gas burner (2) using oxygen can be replaced with a G / WV torch generated by an electric plasma or a torch generated by the combustion of oxygen and hydrogen obtained by the electrolysis of water.

[0043] When the combustion gas is generated from oxygen combustion, after exiting R1, it passes through at least one heat exchanger (9) to transfer its heat to at least one of the reaction fluids, and then the reaction fluid is reheated by a heat exchanger arranged in R1 in the combustion gas chamber.

[0044] When combustion gas is generated from oxy-fuel combustion, after transferring its heat to the reaction fluid in the heat exchanger (9), the combustion gas then passes through a closed-loop cooler (10) to cause condensation of steam, thereby separating CO2 gas. This gas can optionally be used in the production of sodium carbonate or potassium carbonate, or sodium bicarbonate or potassium bicarbonate, in a container (11) or tank, where it is dissolved in an aqueous solution of sodium hydroxide or potassium hydroxide, or sodium carbonate or potassium carbonate. Optionally, hydrogen peroxide can be incorporated to obtain oxygen as a by-product in the production of sodium carbonate or potassium carbonate, or sodium bicarbonate or potassium bicarbonate. Depending on the molar relationship with CO2, optional hydrogen peroxide, and sodium hydroxide or potassium hydroxide, sodium carbonate or potassium carbonate, or sodium bicarbonate or potassium bicarbonate are produced. These products are then dried in a container or equipment designed for this purpose to obtain the corresponding powder or flakes.

[0045] The raw material gas exiting from the carbon-based material produced in R1 is led to R2(4) containing a metal cyclone (27) with a catalyst attached or embedded, and the fine ash carried by the final gas flowing through R2(4) is separated by gravity. When the raw material gas is exposed to BL / UV light at 600 °C and atmospheric pressure, a hydrogen photocatalytic reaction occurs, converting it into the final gas, thereby converting almost all the tar into carbon monoxide and hydrogen. The hydrogen photocatalytic reaction (HFC) is generated by at least one G / WV torch produced by an electric plasma (EP), or by the intense BL / UV light rays emitted from a torch (19). At the same time, in this cyclone housed in R2, ultrafine ash is separated by gravity.

[0046] Thereafter, the final gas is sent to a container (5), where it undergoes a water bath (21) doped with an alkaline agent to store the leaked trace amounts of acidic gas, and another water bath doped with an acid agent to capture trace amounts of ammonia and other basic gases.

[0047] After being cleaned, the final gas (FG) passes through the outlet (28) and is directed to the condenser (6), where most of the heat is transferred and it is cooled, and excess moisture is removed. The condensed water exiting the condenser (6) accumulates in the container (15) and is then used. After passing through the condenser (6) and the container (15), the final gas (FG) is directed to a commercially available gas filter (7) and optionally sent to a gas analyzer or an on-line chromatograph, where the composition of the final gas is measured and recorded to function as a data source for monitoring the gas quality. This, together with the sensors, enables automatic control of the entire process. This represents the final stage of the process to obtain the final gas. The blower (23) serves to create a vacuum within the system to send the final gas (FG) through the above-described system.

[0048] The CO2 obtained from the condensed combustion gas is bubbled into a container (11) containing an aqueous solution of sodium hydroxide or potassium hydroxide, or sodium carbonate or potassium carbonate, and reacts with it to produce sodium bicarbonate or potassium bicarbonate. After centrifugation and drying (25), a product in the form of a powder or flakes is obtained.

[0049] A portion of the sodium bicarbonate or potassium bicarbonate can optionally be used to mix with a dispersing agent and ash. The three products are mixed in equal amounts in a mixing tank (24), and heat is applied at a temperature slightly higher than the melting point of the dispersing agent, reaching a viscous state in the liquid state and under stirring, and a homogeneous paste is formed upon cooling.

[0050] The dry solid waste is ash generated from two sources. The first source is the coarse ash generated at R1 and discharged from the outlet (17), and the second source is the fine ash generated from the cyclone housing R2 and discharged from its outlet (13).

[0051] The third source of generation is the wet ultrafine ash that exits from the water recovery tank (8). The ash from the first two sources of generation is dry and, depending on its composition, can be used by mixing it with a dispersant and sodium bicarbonate or potassium bicarbonate, or ammonium sulfate or calcium sulfate to produce a foaming agent.

[0052] The water generated by gas washing passes through the outlet (29), is stored in the tank (14), and then is sent to another tank (8). If tar remains, the tar floats on the water due to the difference in density and is pumped to the hopper (16) of R1(1) for recycling. At the bottom of this washing tank (8), wet ultrafine ash mainly composed of carbon particles precipitates and is pumped to the hopper (16) of R1(1) for recycling. The coarse ash and fine ash recovered from R1(1) and R2(4) are mechanically removed at the recovered locations, accumulated in the tanks (8) and (14), and then transferred to the container (24) for mixing. What remains in the tank (8) is only water, which is recycled and reused for gas washing in the container (5).

[0053] [Description of Embodiment] Here, one possible method of implementing an SID that first converts a carbon-based material into a combustion gas and then into a final gas will be described, along with options for recovering and utilizing its by-products.

[0054] First, the carbon-based material is introduced into the inner container of R1. This R1 has a double jacket, and a part of the final gas is burned between them to heat the inner container up to 600°C. A heat exchanger is also arranged in this double-jacket chamber to reheat the steam injected into the inner container of this R1, where there is also a granular metal oxide, while stirring at 600°C. In this example, the carbon-based material constitutes the raw material together with the steam as the reaction fluid. The raw material is introduced into R1, comes into contact with the high-temperature granular metal oxide, and is stirred to generate a combustion gas. This process generates solid waste in the form of ash, which is then discharged from the system through the ash outlet of R1.

[0055] In this example, metal oxides based on iron, nickel, and copper heated to 600 °C are used as a fluidized bed. The combustion gas generated in the inner container of R1 at a temperature of 600 °C is then sent to R2. Here, gas reforming is carried out using a G / WV torch generated by a non-transferred arc plasma that emits strong ultraviolet rays. This torch surrounded by a catalyst causes a hydrogen photocatalytic reaction that dissociates the long and heavy molecules of tar present in the combustion gas, producing hydrogen and carbon monoxide in a ratio of approximately 2:1 respectively. This is confirmed by an on-line gas analyzer. This reaction is carried out at atmospheric pressure and an average temperature of 600 °C.

[0056] This combustion gas is converted into the final gas obtained through a hydrogen photocatalytic reaction. That is, the carbon derived from tar present in the combustion gas recovers oxygen and releases hydrogen from the steam reactant, increasing the hydrogen content in the total amount of the final gas. The molar ratio of hydrogen to carbon monoxide (H2 / CO) obtained by SID according to the procedure outlined in this patent is 2, which is twice the molar ratio of conventional systems that use pure oxygen, air, or carbon dioxide as reactants.

[0057] Finally, CO2 emerging from the combustion gas that heats R1 is recovered. When water is condensed, CO2 is bubbled into an aqueous sodium carbonate solution, reacts with it to form sodium bicarbonate, and precipitates in the same tank. After extracting the sodium bicarbonate, it is centrifuged and dried for use or commercialization.

[0058] In this example, a part of sodium bicarbonate is used to mix with a dispersant, and in this case, the dispersant is paraffin. Both products are mixed in equal amounts in a mixing tank and heated to a temperature of 70 °C, which slightly exceeds the melting point of the dispersant (paraffin). As a result, the mixture gradually increases in viscosity while remaining in a homogeneous liquid state, and finally solidifies when cooled to below 30 °C. In this way, the solid is cut into cube pieces of about 1 × 1 × 1 centimeter, and it will be easily incorporated into plastic resins, mortars, or clay mixtures for ceramics in the future, similar to the process used for other granular foaming additives.

Claims

1. An integrated system of an apparatus for converting a raw material containing a carbon-based material into a hydrogen-rich gas, wherein the raw material includes a carbon-based material and one or more reaction fluids, and the integrated system of the apparatus includes: - Two different types of reactors, R1(1) and R2(4), interconnected with each other in series, parallel, or a combination of both, where R1 is a reactor having two separated walls that define an inner container and an outer chamber; - A circuit including two tanks suitable for washing the gas exiting from R2; - Two cooling and condensing devices, one for the final gas after gas washing and the other suitable for separating water and CO2 from the combustion gas exiting from R1; - A filtering device suitable for filtering the final gas, provided in this order; The integrated system includes: - A blower suitable for maintaining the pressure within the assembly; - An apparatus for recovering coarse ash and fine ash exiting from the process; - A mineralization tank suitable for the dissolution and reaction of CO2; - A centrifuge and / or a dewatering press, and a container equipped with a heat source for treating the product exiting from one of the tanks or the mineralization tank; - A control system, and further includes: Optionally, an integrated system further including an apparatus suitable for the production of a foaming additive.

2. The integrated system of an apparatus for converting a raw material containing a carbon-based material into a hydrogen-rich gas according to Claim 1, wherein R1 has a cylindrical shape.

3. The inner container of R1 includes a supply port and at least two outlets, one of the outlets is arranged at the upper part where the raw material gas is discharged, the other is arranged at the lower part suitable for discharging ash, and further includes an inlet suitable for introducing one or more reaction fluids into the container and another inlet suitable for introducing the tar that has not been gasified through the process. The integrated system of an apparatus for converting a raw material containing a carbon-based material into a hydrogen-rich gas according to Claim 1.

4. The inner container of R1 optionally includes another inlet for another high-temperature gas or fluid from at least one heat source of a chamber configured within the double wall of R1. The integrated system of an apparatus for converting a raw material containing a carbon-based material into a hydrogen-rich gas according to Claim 3.

5. The internal container of R1 is an integrated system of an apparatus for converting a raw material containing a carbon-based material according to claim 1 into a hydrogen-rich gas, which contains a catalyst fluidized bed mainly composed of granular metal oxide.

6. The integrated system of an apparatus for converting a raw material containing a carbon-based material according to claim 5 into a hydrogen-rich gas, wherein the granular metal oxide contains at least one metal among iron, nickel, or copper.

7. The internal container of R1 is an integrated system of an apparatus for converting a raw material containing a carbon-based material according to claim 1 into a hydrogen-rich gas, which includes a stirring system and optionally at least one heat source.

8. The outer chamber of R1 includes an inlet for gas, a heat source suitable for generating a high-temperature fluid with the gas, an outlet for the heated fluid generated by the heat source, and an outlet connecting the outer chamber and the internal container. The integrated system of an apparatus for converting a raw material containing a carbon-based material according to claim 1 into a hydrogen-rich gas.

9. R2 includes an inlet, an outlet, a cyclone with a catalyst accommodated in the inlet duct, on the walls, and inside, a heat source for generating a high-temperature fluid with light having a wavelength of 100 to 700 nm (nanometers), at least one heating zone having at least one heat source for generating a high-temperature fluid, and a fine ash outlet, and a fine ash outlet having a pair of valves arranged vertically and continuously together with an intermediate tank for each outlet. The integrated system of an apparatus for converting a raw material containing a carbon-based material according to claim 1 into a hydrogen-rich gas.

10. The substance affected by the catalyst accommodated in R2 is based on nickel, copper, and iron. The integrated system of an apparatus for converting a raw material containing a carbon-based material according to claim 9 into a hydrogen-rich gas.

11. Both R1 and R2 are composed of one or more reactors that can be interconnected in series, in parallel, or a combination of both arrangements. The integrated system of an apparatus for converting a raw material containing a carbon-based material according to claim 1 into a hydrogen-rich gas.

12. The circuit comprising two tanks suitable for gas cleaning comprises two gas cleaning sub-circuits containing desalted and doped water, one containing an alkaline substance and the other containing an acidic substance. Further, each of the gas cleaning sub-circuits comprises an inlet for the contaminated final gas, another inlet for the doped water, an outlet for the cleaned final gas, and another outlet for the doped water and reaction products. An integrated system of an apparatus for converting a raw material containing a carbon-based material according to claim 1 into a hydrogen-rich gas.

13. The cooling and condensing device comprises at least one condenser, and the condenser comprises a liquid-gas heat exchanger for condensing water from the water vapor of the final gas and at least one condenser for the water vapor containing the combustion gas from R1. In the liquid-gas heat exchanger, the liquid absorbs heat from the gas to condense water from the water vapor of the final gas. The heat exchanger has an inlet for the wet final gas, an outlet for the dry final gas, and another outlet for the water condensed with a trace amount of contaminants. The cooling and condensing device further comprises a tank at the outlet of the condenser, and the tank functions as a separator for the final gas and the water condensed together with a part of the impurities carried by the final gas. The condenser for the water vapor containing the combustion gas from R1 comprises at least two types of heat exchangers. An integrated system of an apparatus for converting a raw material containing a carbon-based material according to claim 1 into a hydrogen-rich gas.

14. The filtration device comprises an inlet and an outlet and houses at least one filter. An integrated system of an apparatus for converting a raw material containing a carbon-based material according to claim 1 into a hydrogen-rich gas.

15. The ash recovery device comprises two gas cleaning tanks for the final gas that recover water containing impurities such as ash and tar, each having at least two inlets and three outlets. The two inlets allow access to water contaminated with ultrafine ash and tar. For the outlets, one is for returning the tar floating in the water to R1, another is for sending the precipitated wet ultrafine ash to the supply port of R1, and the third is for sending the water back to the gas cleaning process for recycling. An integrated system of an apparatus for converting a raw material containing a carbon-based material according to claim 1 into a hydrogen-rich gas.

16. The mineralization tank is suitable for dissolving and reacting CO2 with at least two of the following substances: i) sodium hydroxide or potassium hydroxide, ii) sodium sulfate or potassium sulfate, iii) sodium carbonate or potassium carbonate, iv) calcium hydroxide, v) sodium chloride, vi) methanol, vii) urea, viii) water, and ix) ammonia. Further, the mineralization tank is provided with a heat source and a cooling source, a control device for temperature, pressure, and pH, a stirring system, and optionally, at least one catalyst of zinc oxide or cerium dioxide. An integrated system of an apparatus for converting a raw material containing a carbon-based material according to claim 1 into a hydrogen-rich gas.

17. Following the centrifuge and / or the dewatering press, a container tank equipped with a heat source suitable for drying and / or calcining the product from the mineralization tank is installed. An integrated system of an apparatus for converting a raw material containing a carbon-based material according to claim 1 into a hydrogen-rich gas.

18. The control system is suitable for measuring temperature, pressure, pH, H2 / CO ratio, level, and flow rate and correcting them until they fall within a pre-set range. An integrated system of an apparatus for converting a raw material containing a carbon-based material according to claim 1 into a hydrogen-rich gas.

19. A procedure for converting a raw material containing a carbon-based material into a hydrogen-rich gas, The first stage of raw material gas generation: In this first stage, R1 starts the process by the physicochemical decomposition of the carbon-based material. The second stage of raw material gas reforming: In this stage, the process carried out in the first stage is continued in R2, and most of the tar present in the gas is removed by reforming the raw material gas. To perform this reforming, strong light irradiation with a wavelength of 100 to 700 nanometers (nm) is carried out on the surface covered with a catalyst in R2 using the heat carried by the raw material gas of R1. The third stage of gas cleaning is adopted. The cyclone of R2 is suitable for separating fine ash (diameter 0.5 - 0.1 millimeter) from the final gas. After this separation, the gas passes through at least two tanks containing water, one containing an alkali additive and the other containing an acid additive, thereby recovering residual ultra-fine ash (diameter less than 0.1 millimeter), trace amounts of tar, as well as both acidic and basic gases. This final gas then undergoes a cooling process to condense water along with any possible trace amounts of tar present. Finally, the final gas is made available for use after being filtered. Fourth stage of heat recycling or reuse: The heat generated by the combustion of a part of the final gas is utilized by R1 and R2. This heat acts on the raw materials and raw gas through granular metal oxides, raising and maintaining their temperatures. Execute the fifth stage of waste recovery and reuse. Sixth stage of the reuse of fine ash and coarse ash: At this stage, the dried coarse ash and fine ash are mixed with at least one of the following products: a) sodium bicarbonate or potassium bicarbonate, b) ammonium sulfate or calcium sulfate, along with a dispersant such as polyethylene wax, ethylene vinyl acetate (EVA), or paraffin to produce a multifunctional additive. The seventh stage of process control is distributed throughout the system and includes sensors that measure temperature, pressure, pH, H2 / CO ratio, level, and flow rate. When one or more measured values deviate from a pre-set range, the electronic system performs the actions necessary to correct the situation. The fifth and sixth stages are optional procedures.

20. The fifth stage of the recovery and reuse of the waste is a procedure for converting a raw material containing a carbon-based material according to claim 19 into a hydrogen-rich gas, including at least one of the following sub-stages: Sub-stage (a): CO₂ is recovered at the end of the exhaust stack of R1 from the burned final gas into a tank at the condenser outlet designed to separate water from the final gas, and sent to a mineralization tank. The burned final gas, which contains CO₂ and water vapor and is used to heat R1, has these two components separated by cooling in at least one condenser followed by a separator tank. The separated CO₂ is recovered by reacting it with at least two of the following substances: i) sodium hydroxide or potassium hydroxide, ii) sodium sulfate or potassium sulfate, iii) sodium carbonate or potassium carbonate, iv) calcium hydroxide, v) sodium chloride, vi) methanol, vii) urea, viii) water, and ix) ammonia. By this process, sodium carbonate or potassium carbonate, sodium bicarbonate or potassium bicarbonate, or dimethyl carbonate is produced. Then, in a centrifuge with a heat source tank installed later: a) in the case of sodium bicarbonate or potassium bicarbonate, when solids precipitate, they are centrifuged, dried and / or purified, or separated and commercialized; b) in the case of sodium carbonate or potassium carbonate, calcination of the previous product is required. Sub-stage (b): The dried coarse ash (with a diameter greater than 0.5 millimeters) is recovered at the lower part of R1. This sandy coarse ash is composed of more than 50% inert metal produced in at least one R1 and is sent to a mixing tank where a foaming additive is optionally produced. Sub-stage (c): The fine dried ash (with a water content of less than 4%) is recovered at the lower part of R2. The fine ash is produced by the cyclone contained in one R2 and is sent to the mixing tank where a foaming additive is optionally produced. Sub-stage (d): The ultra-fine (with a particle size smaller than that defined as cold ash) wet ash (with a water content of more than 50%) is recovered at the bottom of at least one gas washing tank. This ash is composed of a trace amount of fixed carbon and can be mechanically extracted and used as a carbon-based material in R1. Sub-stage (e): The water from the gas washing accumulates by settling at the bottom of at least one gas washing tank. This water has 95% of the recovered tar removed and 95% of the recovered ash removed. It is reused for gas washing, and the remaining trace amount of floating tar is also separated and mechanically extracted, and can be re-introduced into R1 together with the carbon-based material.

21. In the sixth stage of the reuse of the fine ash and coarse ash, the fine ash and coarse ash are mixed with at least one of the following products: a) sodium bicarbonate or potassium bicarbonate, b) ammonium sulfate or calcium sulfate, together with a dispersant such as polyethylene wax, ethylene vinyl acetate (EVA), or paraffin, to obtain a multifunctional additive. This sixth stage includes the following sub-stages for the production and use of this additive. A procedure for converting a raw material containing a carbon-based material according to claim 19 into a hydrogen-rich gas, a) In a mixing tank, heat until the dispersant wax is completely liquefied, b) Add sodium bicarbonate or potassium bicarbonate, or ammonium sulfate or calcium sulfate, to a liquid wax in an amount equal to or more than the amount of fine ash and coarse ash used, and continue stirring until the components are well dispersed, c) Cool until a viscous state is reached, d) Once this viscous state is reached, stop stirring and cool until solidification occurs, e) Finally, in a solid state, cut for potential use, such as the production of pellets or granules.

22. In the seventh stage, the correction operation is as follows. A procedure for converting a raw material containing a carbon-based material according to claim 19 into a hydrogen-rich gas, a) A range is defined for the actual volume of hydrogen / the actual volume of carbon monoxide H2 / CO, - When the sensor measurement shows a ratio higher than the specified value, reduce the steam supply until the ratio falls within the specified range, - When the sensor measurement shows a ratio lower than the specified value, increase the steam supply until the ratio reaches the specified range, b) A range is defined for the actual temperature of reactor 1 / the pre-set limit temperature: (T1) / (T limit), - When the sensor measurement shows a temperature higher than the specified value, increase the supply of raw material until the temperature reaches the specified range, - When the sensor measurement shows a temperature lower than the specified value, operate the oxygen supply in R1 until the temperature reaches within the specified range. - This operation is conditioned by the pressure ratio of R1, c) The range is defined as the actual pressure of reactor 1 / the pre-set limit pressure 1: (PR1) / (PR limit 1), - When the sensor measurement indicates a pressure higher than the defined range, the supply of raw materials and / or oxygen is decreased until the pressure is within the defined range, and this instruction takes precedence over operation (b). - When the sensor measurement indicates a pressure lower than the defined range, the supply of raw materials and / or oxygen is increased until the pressure is within the defined range. - When the ratio is higher than 1, the safety valve opens. d) The range is defined for the actual pressure of reactor 2 / the pre-set limit pressure 2: (PR2) / (PR limit 2). - When the sensor measurement indicates a pressure exceeding the defined range, the suction force of the blower is increased until the pressure reaches the level of the defined range. - When the sensor measurement indicates a pressure below the defined range, the suction force of the blower is decreased until the pressure returns within the defined range and may reach zero. e) The range is defined for the level / limit level: (N) / (N limit) in any of the tanks for individually discharging each of the following materials: dry ash, tar, water, and wet ash. - When the sensor measurement is higher than expected, the valves and pumps are actuated. - When the sensor measurement is lower than expected, the procedure to stop the valves and pumps.

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