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WO2023141686A1 - High energy environmentally friendly fuel as an additive for coal-fired power plants - Google Patents

High energy environmentally friendly fuel as an additive for coal-fired power plants Download PDF

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Publication number
WO2023141686A1
WO2023141686A1 PCT/BA2022/000001 BA2022000001W WO2023141686A1 WO 2023141686 A1 WO2023141686 A1 WO 2023141686A1 BA 2022000001 W BA2022000001 W BA 2022000001W WO 2023141686 A1 WO2023141686 A1 WO 2023141686A1
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Prior art keywords
fuel
coal
combustible mixture
thermoelectric power
liquid
Prior art date
Application number
PCT/BA2022/000001
Other languages
French (fr)
Inventor
Drago ĆOSIĆ
Original Assignee
Cosic Drago
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Publication date
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Priority to CN202280001683.5A priority Critical patent/CN116829497A/en
Publication of WO2023141686A1 publication Critical patent/WO2023141686A1/en

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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00Halogens; Halogen acids
    • C01B7/01Chlorine; Hydrogen chloride
    • C01B7/03Preparation from chlorides
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00Halogens; Halogen acids
    • C01B7/09Bromine; Hydrogen bromide
    • C01B7/093Hydrogen bromide
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00Halogens; Halogen acids
    • C01B7/09Bromine; Hydrogen bromide
    • C01B7/096Bromine

Definitions

  • the Invention relates to the fuel and combustible mixture based on the production of hydrogen that can be used as a substitute to fossil fuels in thermoelectric power plants.
  • the fact that the Invention replaces fossil fuels implies that the emissions of harmful gases, like CO2, are reduced.
  • the Invention has an additional property: it binds the CO2 made from the combusted coal.
  • the Invention makes it possible to reduce the amount of dust generated as a by-product of the combustion process.
  • the Invention is a combustible fuel that requires an airtight container with or without an added insulator.
  • the characteristics of the container tank and the relationship between the solid and liquid phases during the combustion within the tank will be explained later.
  • the tank is considered part of the fuel, because it has to be made of a flammable material and it takes the role of the burning trigger inside the furnace. Through chemical reactions of the combustible mixture, hydrogen is generated and collected in the tank. The tank bums in the furnace and triggers the combustion of the hydrogen. If an insulator is used, it has to be flammable as well and is also part of the fuel. The insulator helps to keep the hydrogen inside the tank and triggers the combustion process.
  • This Invention represents the new combustible fuels which release 15 times more energy than lignite and 4-5 times than coke. To allow that, fuel has to be sealed in an impermeable container.
  • the inside of the tank was coated in an insulator and the hydrogen was bound to prevent leaking of the gas. During the combustion process, the tank and insulator bum and ignite the hydrogen while inside the furnace. Examples of such insulators are tar based adhesives or similar materials.
  • the tank is made of a polymer, preferably polyvinyl chloride (PVC) due to its very flammable properties.
  • the Invention is primarily aimed at preparing an alternative fuel which could replace coal while providing the same amount of electricity, which would reduce the costs of exploitation and transportation of coal to thermoelectric power plants. Secondarily, it is aimed at reducing the mass emission of greenhouse gases as a consequence of incomplete coal combustion.
  • the technical requirements have been solved by preparing a flammable mixture consisting of a solid and liquid part.
  • the mixture is in a sealed polyethylene hose (container) with a barrier separating the liquid and solid parts, where the barrier gradually disintegrates when in contact with the liquid, allowing the liquid and solid to combine. This results in the chemical reactions which produce hydrogen.
  • Emission permits or Greenhouse Gas Emission Verifications (GHGV) in the European Union have increased in prices and are at a record 43.14 Euros per ton.
  • the price of emission permits has increased by as much as 32.4% in 2021, 16 times the amount they were on the 17 th of April 2013.
  • the high prices of permits exist to pressure emitters of greenhouse gases in the EU by increasing their costs. By doing that, coal power plants, along with industrial facilities are becoming less competitive or even closing down.
  • thermochemical decomposition gasification
  • the Invention includes all of these reactions, especially relying on the fact that in the thermoelectric power plant furnace water comes into contact with coal at a high temperature, so these reactions are inevitable. However, this process is only a segment of the entire process which enables the hydrogen production and its usage in situ (without transport and storage).
  • quicklime is added during reactions where CO2 is extracted.
  • the Invention provides for a polyvalent role of quicklime, not only for binding the CO2 to lower emissions, but also for creating H2 and other reactions which improve flammability of the combustible mixture.
  • Flammable mixture refers to a mixture of solid and liquid states. Both of these states include multiple components. All the components will be listed below.
  • the synthetic fuel is a flammable mixture hermetically sealed in an 8x4 centimeter polyvinyl chloride tank with or without an insulator, welded after the chemical components are added.
  • the characteristics of the container tank and the relationship between the solid and liquid phases during the combustion within the tank will be explained later.
  • the tank is considered part of the fuel because it is used as a trigger in the furnace and it must be flammable.
  • the H-I fuel has a presupposed heat value of 94 M3/kg with pmupposed PE lower heat value of 42, 193 MJ/kg and measured bituminous coat ted value nf 2O90 MPkg,
  • the Invention unearths a new flammable mixture that, during combustion, releases energy 15 times greater than the energy released by lignite and 4-5 times greater than that of coke.
  • the combustible mixture must be closed in an airtight container.
  • the container has a barrier preventing direct contact between the solid and liquid matter, but the barrier, in contact with the acid component of the liquid matter, gradually disintegrates and allows contact between the solids and liquids. That is, in fact, the main trigger of chemical reactions that leads to hydrogen generation. Because the container is hermetically sealed, the hydrogen remains inside. In a previous version of the Invention, the inside of the container would be coated by an insulator, which bound the hydrogen to prevent hydrogen leaking while in the furnace.
  • the container is made of a polymer, preferably polyvinyl chloride (PVC) due to its very flammable properties.
  • the Invention also implies the methods of using this fuel in thermoelectric power plant furnaces, industrial furnaces or district heating furnaces.
  • the mentioned flammable mixture which can be used as substitute for a portion of the required coal in thermoelectric power plants, is made of solid and liquid matter, where the solid matter phase consists of:
  • Aluminium powder at least one M 1 X 2 , where M 1 can be any metal in the oxidation state +2 and X can be any halogen; M 2 CO 3 , where M 2 can be any divalent metal; zinc ammonium chloride; SiO2 in the form of quartz sand; and quicklime.
  • the presence of water is clear to any expert in the field as the liquid matter consists of aqueous solutions of previously mentioned chemicals. Because of this, the water percentage is self-explanatory and won’t be mentioned again.
  • the percentage of solids can vary from 32% w/w to 46% w/w, and the liquid varies from 54% w/w to 68% w/w.
  • the solid state varied between 36% w/w and 42% w/w, and the percentage of liquid was 58% w/w to 64% w/w.
  • the share of solids was 39% w/w, and the liquids 61% w/w.
  • Aluminium powder 5% to 8%
  • the components are present in the following weight percentages:
  • At least one carboxylic acid, or at least one anhydride of mentioned carboxylic acids, or at least one of its esters or amides can be present in an interval of 10% to 27%;
  • Methylcellulose can be present in an interval of 20% to 40%;
  • Formaldehyde, or its commercially accessible solution - formalin can be present in an interval of 1% to 10%;
  • Remaining part consists of water, as is self-explanatory.
  • the components of the liquid matter were present in the following weight percentages:
  • At least one carboxylic acid, or at least one anhydride of mentioned carboxylic acids, or at least one of its esters or amides can be present in an interval of 5% to 22%;
  • Methylcellulose can be present in an interval of 25% to 35%
  • Formaldehyde, or its commercially accessible solution - formalin can be present in an interval of 3% to 7%; Remaining part consists of water.
  • liquid components are in the following weight percentages:
  • At least one carboxylic acid, or at least one anhydride of mentioned carboxylic acids, or at least one of its esters or amides had a presence of 17%;
  • Methylcellulose had a presence of 29%
  • Formaldehyde, or its commercially accessible solution - formalin had a presence of 5%
  • Remaining part consists of water.
  • M 1 and M 2 from the description of the mixture above, or more accurately, the description of the solid matter, in one version, are selected between Fe (iron), Cu (copper) and Zn (zinc).
  • at least one carboxylic acid, or at least one of its derivatives is selected from a group made up of Ci - C3 carboxylic acids; while the methylcellulose is selected between gelatine and tylose.
  • M 1 and M 2 are Zn, where M 'X represents a mixture of ZnCh and ZnBn
  • the methylcellulose used is tylose, while the liquid contains two carboxylic acids, those being: Ci carboxylic acid - also known as formic acid; and C2 carboxylic acid - known as acetic acid.
  • additives like coke or ethanol may be added to the combustible mixture, where coke is added to the solid phase and ethanol to the liquid phase.
  • Another property of the Invention is the proposed method of generating energy in thermoelectric power plants including replacing a portion of coal using the previously described fuel.
  • the invented fuel can already replace more than 50% of the required coal.
  • up to 60% of required coal can be replaced, even up to 100% with some modifications, primarily in the materials that the furnaces are made of. Percentages in this paragraph relate to volume or other shares.
  • 1 kg of the invented fuel replaces 15 kg of lignite or 4-5 kg of coke.
  • CO2 emissions can be reduced up to 75%
  • the next subject of the Invention is the usage as a substitute/alternative fuel in thermoelectric power plants.
  • the combustible mixture or its components bind harmful exhaust gases generated by the burning of coal in the thermoelectric power plants. Above all, this refers to the binding of CO2.
  • the task of insulator which coats the inside of the container is collecting and activating the combustion of hydrogen in the process.
  • Methylcellulose makes the insulator prevent hydrogen outflow from the container.
  • Methylcellulose can be either gelatine or tylose, or another industrially accessible methylcellulose.
  • the Invention can be used in all solid fuel furnaces, including, besides thermoelectric power plants, industrial and central heating furnaces of varying capacities, given that the minimal working temperature of the furnace is no less than 350°C.
  • Aluminum is present in the solid matter of the combustible mixture in the form of aluminium powder of high purity.
  • High purity means that it contains at least 90% aluminium.
  • the best results are achieved with aluminum with the specific surface area of 7000 cm 2 /g.
  • the volume density of aluminium powder is desired to be around 0.15 kg/dm 3 .
  • Fuel combustion occurs in 4 phases: a) In the first phase hydrogen is generated by reactions between solid and liquid components of the combustible mixture. Hydrogen is contained within the fuel because the airtight container is keeping it inside. Hydrogen is ignited inside the container by the flammable insulator and container inside the furnace. b) Combustion of pure hydrogen in close proximity of the mixture from which hydrogen is coming out from the extremely hot furnace of a thermoelectric power plant (1000°C) causes an accelerated extrusion of hydrogen from water in the mixture. c) The separation of hydrogen is followed by the burning of aluminate salts and other flammable silicate components in the mixture.
  • thermoelectric power plant Regardless of how the fuel is used, the incombustible part of the mixture, calcium oxide or quicklime, while travelling with other gases through thermoelectric power plant’s chimney or of other plants, further purifies harmful exhaust gases by binding to them. This way up to 75% of exhaust gases are purified, making them environmentally acceptable.
  • the polyethylene container production in accordance with Invention evolve as follows: a) Two touching rollers have 2 mm wide, 1 mm deep interlocking grooves. If the lower roller has grooves lengthwise, the top roller grooves are placed so that by means of power, when they cut a double foil, rectangles/squares are cut out containing generated hydrogen. The space inside the container needs to be larger than two-thirds of the granulated combustible mixture volume to make room for hydrogen that will be generated inside the container. b) After certain time, more precisely, after a few hours, the combustible mixture will generate enough hydrogen that the granules look inflated. In this phase it is ready for combustion.
  • the PVC container bums and allows uniform separation of hydrogen as well as its combustion, while oxygen from the water binds to the mixture. This then creates calcium hydrosilicate, which prevents the formation of explosive gas.
  • zinc carbonate As for zinc carbonate (ZnCCh), as dehydrated it occurs in the form of white powder that doesn’t dissolve in water. However, as a commercial product, it is sold in a hydrated form as basic zinc carbonate (2ZnCOs x 3Zn(OH)2). Basic zinc carbonate is used in the Invention.
  • CaO is made from Ca(OH)2 which has lost water due to heat and C is the carbon from coal. Therefore, with this Invention, hydrogen isn’t just formed inside the fuel, but also in the reaction of water vapor gasification. Water in the liquid part of fuel is responsible for gasification, along with any moisture from the coal.
  • the lower heating value of coal varies from 29,310 kJ/kg for anthracite to 12,250 kJ/kg for lignite.
  • 1,250 Nm 3 of hydrogen is needed for lignite and 521 Nm 3 for anthracite. Converting this to mass, that is 110 kg of hydrogen for anthracite and 42.7 kg of hydrogen for lignite. Therefore, 1,000 kg of anthracite give off as much heat as 500 kg of anthracite enriched with 110 kg of hydrogen, or, in the other case, 500 kg of lignite enriched with 42.7 kg of hydrogen.
  • eight mass percentages of this fuel substitutes around 50 mass percentages of coal.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)

Abstract

Hydrogen Industrial is a new fuel on a basis of hydrogen and other chemical compounds as an environmental contribution to the effects of coal burning in thermoelectric power plants by replacing more than half of coal-based fuel. It is fact that the coal in thermoelectric power plants is considered the largest polluter and this fuel eliminates, not just CO2, but also other contents of aggressive gases released in the atmosphere. The use of a new alternate fuel, as an supplement to coal, replacing it by 45-60% so that the new fuel purifies the rest of the coal and turn it into a pile of ash. This mineral enriched ash can be further processed in production of agricultural fertilizers. The very fact that the Invention replaces fossil fuels means that emission of harmful exhaust gases is reduced, as well as the amount of dust as a by-product of coal burning in thermoelectric power plants.

Description

HIGH ENERGY ENVIRONMENTALLY FRIENDLY FUEL AS AN ADDITIVE FOR COAL-FIRED POWER PLANTS
A SUMMARY OF THE INVENTION
Climate change is occurring globally and much faster than scientists have predicted. Global warming as a result of industrial development causes droughts, floods and extreme weather disturbances. The preservation of our planet is necessary for future generations and that is why we must act now.
Several actions have been taken, especially after the signing of the Kyoto Protocol in late 1997 in Japan, with the goal of stabilizing the amount of greenhouse gases in the atmosphere in order to prevent severe changes to our climate. One consensus is that new technologies need to be invented and put into commercial use as to mitigate the negative impact of the prevalent traditional forms of energy production based on fossil fuels. Among other efforts to reduce the use of fossil fuels, like renewable and biomass energy, the inventor (of HI) has opted to explore a safe and affordable method of hydrogen production which can replace 50% of coal usage. Many other scientists, researchers and experts worldwide have explored hydrogen production, but what makes HI unique is that it is produced and burned in the thermoelectric power plant itself.
The Invention relates to the fuel and combustible mixture based on the production of hydrogen that can be used as a substitute to fossil fuels in thermoelectric power plants. The fact that the Invention replaces fossil fuels implies that the emissions of harmful gases, like CO2, are reduced. However, the Invention has an additional property: it binds the CO2 made from the combusted coal. Moreover, the Invention makes it possible to reduce the amount of dust generated as a by-product of the combustion process.
TECHNICAL BACKGOUND
The Invention is a combustible fuel that requires an airtight container with or without an added insulator. The characteristics of the container tank and the relationship between the solid and liquid phases during the combustion within the tank will be explained later. The tank is considered part of the fuel, because it has to be made of a flammable material and it takes the role of the burning trigger inside the furnace. Through chemical reactions of the combustible mixture, hydrogen is generated and collected in the tank. The tank bums in the furnace and triggers the combustion of the hydrogen. If an insulator is used, it has to be flammable as well and is also part of the fuel. The insulator helps to keep the hydrogen inside the tank and triggers the combustion process.
This Invention represents the new combustible fuels which release 15 times more energy than lignite and 4-5 times than coke. To allow that, fuel has to be sealed in an impermeable container. In another version of this Invention, the inside of the tank was coated in an insulator and the hydrogen was bound to prevent leaking of the gas. During the combustion process, the tank and insulator bum and ignite the hydrogen while inside the furnace. Examples of such insulators are tar based adhesives or similar materials. The tank is made of a polymer, preferably polyvinyl chloride (PVC) due to its very flammable properties.
The Invention is primarily aimed at preparing an alternative fuel which could replace coal while providing the same amount of electricity, which would reduce the costs of exploitation and transportation of coal to thermoelectric power plants. Secondarily, it is aimed at reducing the mass emission of greenhouse gases as a consequence of incomplete coal combustion.
The technical requirements have been solved by preparing a flammable mixture consisting of a solid and liquid part. The mixture is in a sealed polyethylene hose (container) with a barrier separating the liquid and solid parts, where the barrier gradually disintegrates when in contact with the liquid, allowing the liquid and solid to combine. This results in the chemical reactions which produce hydrogen. This ignites the synthetic fuel made by mixing the liquid and solid fuel with the large amount of energy that hydrogen releases when burning. This all occurs in the 8x4 centimeter polyethylene tank.
STATE OF THE ART
Emission permits or Greenhouse Gas Emission Verifications (GHGV) in the European Union have increased in prices and are at a record 43.14 Euros per ton. The price of emission permits has increased by as much as 32.4% in 2021, 16 times the amount they were on the 17th of April 2013. The high prices of permits exist to pressure emitters of greenhouse gases in the EU by increasing their costs. By doing that, coal power plants, along with industrial facilities are becoming less competitive or even closing down.
As far as known to the applicant, there aren’t similar fuels which could replace fossil fuels. A lot of effort is invested into hydrogen production, where hydrogen is produced and stored in a special plant which cogenerates electricity along thermoelectric power plant. Most of these efforts have led to the principle of thermochemical decomposition (gasification) of water, where water vapor is brought into a furnace where the following reactions take place in solid and liquid phases:
Solid phase:
Partial oxidation C + V2O2 = CO
Burning C + O2 = CO2
Gasification C + H2O = CO + H2
Boudouard reaction CO + V2 O2 = CO2
Hydrogenation C + 2H2 = CH4
Liquid phase:
Partial oxidation CO + V2 O2 = CO2
Hydration CO + H2O = CO2 + H2 Methanation CO + 3H2 = CH4 + H2O
Hydrogen oxidation 2O2 + H2 = H2O
The Invention includes all of these reactions, especially relying on the fact that in the thermoelectric power plant furnace water comes into contact with coal at a high temperature, so these reactions are inevitable. However, this process is only a segment of the entire process which enables the hydrogen production and its usage in situ (without transport and storage).
On the other side, document US7014834 describes the usage of quicklime (CaO, calcium oxide) to absorb CO2 emissions from thermoelectric power plants. The basic chemical reactions that demonstrate the chemism of CO2 absorption according to aforementioned documents are the following:
C + H2O = co + H2
H2O + co = co2 + H2
CaO + CO2 = CaCO3
Combined: C + 2 H2O + CaO = CaCO3 + 2 H2
While it is in the solid phase, quicklime is added during reactions where CO2 is extracted. However, the Invention provides for a polyvalent role of quicklime, not only for binding the CO2 to lower emissions, but also for creating H2 and other reactions which improve flammability of the combustible mixture.
SUMMARY OF THE INVENTION
Before describing the basis of Invention, it would be appropriate to define the terms, which will be used here in their specific meanings, unless otherwise specified.
Flammable mixture refers to a mixture of solid and liquid states. Both of these states include multiple components. All the components will be listed below.
The synthetic fuel is a flammable mixture hermetically sealed in an 8x4 centimeter polyvinyl chloride tank with or without an insulator, welded after the chemical components are added. The characteristics of the container tank and the relationship between the solid and liquid phases during the combustion within the tank will be explained later. The tank is considered part of the fuel because it is used as a trigger in the furnace and it must be flammable.
Through the reactions of the combustible mixture, hydrogen is generated and accumulates in the 8x4 centimeter polyvinyl chloride container, which burns in the furnace and ignites the hydrogen. If an insulator is used, it has to be flammable as well. The insulator helps keep the hydrogen molecules inside the PVC tank by binding the hydrogen. On the other hand, the insulator stimulates combustion and helps the container burn, along with igniting the hydrogen and is therefore considered part of the fuel. Energy Content of The HI Fuel
♦ Mix 0 pure coal
♦ Mix I ~ 0,44 kg of c oal with 10 packages of H4 fuel
♦ Mix 2 0,54 kg of coal with 8 packages of H4 fuel
Comparison of the planned energy input into the holler is shown in Figure 3 J ,
100,008
Figure imgf000005_0001
Conclusion
1. Using the pure coal and the mixtures of coal and HI fuel the following values were obtained by measurements and calculation
Figure imgf000006_0001
2. Heat transfers to the water are nearly the same
3. EfBciency (calculated, based on flue gases)
4. Amount of sulphur (with 0% Gs in Sue gases) decreases with the increase of the H-l &el content
It can be concluded that the H-I fuel has a presupposed heat value of 94 M3/kg with pmupposed PE lower heat value of 42, 193 MJ/kg and measured bituminous coat ted value nf 2O90 MPkg,
The analysis of the sulphur in th e .fee gases shows decrease with an Increase of H~I fuel content in the fuel mixture, e,g., for foe fuel mixture 2 (0.44 kg of coal + 10 packages of H-I fuel) the amount of sulphur in flue gases is almost 50H lower.
Figure imgf000006_0002
Energy Dispersive X-Ray Fluorescence Analysis (ED-XRF) on Coal Ash The analysis of the composition of ash from coal is carried out according to standard ASTM d 4326 with the energy dispersive X-ray fluorescence spectrometer (EDXRF). Samples that were analyzed were the ashes after the annealing process (the analysis of inorganic ash). The following results are obtained:
Figure imgf000007_0001
One can observe the reduction in the amount of iron oxides, silicon dioxide and an increase of calcium oxide in the composition of the ash.
Figure imgf000007_0002
Figure imgf000008_0001
Hence, the Invention unearths a new flammable mixture that, during combustion, releases energy 15 times greater than the energy released by lignite and 4-5 times greater than that of coke. To make that possible, the combustible mixture must be closed in an airtight container. The container has a barrier preventing direct contact between the solid and liquid matter, but the barrier, in contact with the acid component of the liquid matter, gradually disintegrates and allows contact between the solids and liquids. That is, in fact, the main trigger of chemical reactions that leads to hydrogen generation. Because the container is hermetically sealed, the hydrogen remains inside. In a previous version of the Invention, the inside of the container would be coated by an insulator, which bound the hydrogen to prevent hydrogen leaking while in the furnace. As both insulator and container are flammable, they ignite the oxygen in the oxidation atmosphere of the boiler furnace. Examples of such insulators are tar based adhesives or similar materials. The container is made of a polymer, preferably polyvinyl chloride (PVC) due to its very flammable properties.
Besides the flammable mixture, the Invention also implies the methods of using this fuel in thermoelectric power plant furnaces, industrial furnaces or district heating furnaces.
DETAILED DESTRIPTION OF THE INVENTION
The mentioned flammable mixture, which can be used as substitute for a portion of the required coal in thermoelectric power plants, is made of solid and liquid matter, where the solid matter phase consists of:
Aluminium powder; at least one M 1 X2, where M1 can be any metal in the oxidation state +2 and X can be any halogen; M2CO3, where M2 can be any divalent metal; zinc ammonium chloride; SiO2 in the form of quartz sand; and quicklime.
While the liquid matter phase consists of:
At least one Ci - Ce carboxylic acid, or at least one anhydride of mentioned carboxylic acids, or at least one of its esters or amides; methylcellulose; formaldehyde, or its commercially accessible solution - formalin; ammonium and water. The presence of water is clear to any expert in the field as the liquid matter consists of aqueous solutions of previously mentioned chemicals. Because of this, the water percentage is self-explanatory and won’t be mentioned again. As for the weight percentages of solid and liquid matter in the combustible mixture, the percentage of solids can vary from 32% w/w to 46% w/w, and the liquid varies from 54% w/w to 68% w/w. In one version of the Invention, the solid state varied between 36% w/w and 42% w/w, and the percentage of liquid was 58% w/w to 64% w/w. In another version of implementing the Invention given in this patent application, the share of solids was 39% w/w, and the liquids 61% w/w.
In the above specified weight percentages, these components take up the following percentage of the solid matter:
Aluminium powder 3% to 10%
MXX2 1% to 4%
M2CO3 1% to 3%
Zinc ammonia chloride 2% to 5%
SiO2 3% to 8%
Quicklime 70% to 90% According to a more desirable version of the Invention, the solid components are present in the following weight percentages:
Aluminium powder 5% to 8%
MXX2 2% to 4%
M2CO3 1% to 2%
Zinc ammonia chloride 3% to 5%
SiO2 4% to 7%
Quicklime 74% to 85%
For the needs of the invented fuel as a fuel that substitutes coal in thermoelectric power plants, the components are present in the following weight percentages:
Aluminium powder 7%
MXX2 3%
M2CO3 1.5%
Zinc ammonia chloride 3.5%
SiO2 6%
Quicklime 79%
When it comes to the liquid matter and its components, they are present in the following percentages:
At least one carboxylic acid, or at least one anhydride of mentioned carboxylic acids, or at least one of its esters or amides can be present in an interval of 10% to 27%;
Methylcellulose can be present in an interval of 20% to 40%;
Formaldehyde, or its commercially accessible solution - formalin can be present in an interval of 1% to 10%;
Remaining part consists of water, as is self-explanatory.
According to one version of the Invention, the components of the liquid matter were present in the following weight percentages:
At least one carboxylic acid, or at least one anhydride of mentioned carboxylic acids, or at least one of its esters or amides can be present in an interval of 5% to 22%;
Methylcellulose can be present in an interval of 25% to 35%;
Formaldehyde, or its commercially accessible solution - formalin can be present in an interval of 3% to 7%; Remaining part consists of water.
In the described example of implementing the Invention, the liquid components are in the following weight percentages:
At least one carboxylic acid, or at least one anhydride of mentioned carboxylic acids, or at least one of its esters or amides had a presence of 17%;
Methylcellulose had a presence of 29%;
Formaldehyde, or its commercially accessible solution - formalin had a presence of 5%;
Remaining part consists of water.
M1 and M2 from the description of the mixture above, or more accurately, the description of the solid matter, in one version, are selected between Fe (iron), Cu (copper) and Zn (zinc). On the other hand, in the same version, at least one carboxylic acid, or at least one of its derivatives is selected from a group made up of Ci - C3 carboxylic acids; while the methylcellulose is selected between gelatine and tylose.
During the use of this fuel in a thermoelectric power plant as a substitute for coal, which should by no means be considered a limiting factor and does not narrow the scope and subject protected by patent claims, M1 and M2 are Zn, where M 'X represents a mixture of ZnCh and ZnBn During the same use of the invented fuel - the methylcellulose used is tylose, while the liquid contains two carboxylic acids, those being: Ci carboxylic acid - also known as formic acid; and C2 carboxylic acid - known as acetic acid.
To improve the flammable properties of the fuel, additives like coke or ethanol may be added to the combustible mixture, where coke is added to the solid phase and ethanol to the liquid phase.
Another property of the Invention is the proposed method of generating energy in thermoelectric power plants including replacing a portion of coal using the previously described fuel. The invented fuel can already replace more than 50% of the required coal. According to the Invention, up to 60% of required coal can be replaced, even up to 100% with some modifications, primarily in the materials that the furnaces are made of. Percentages in this paragraph relate to volume or other shares. By its caloric value, 1 kg of the invented fuel replaces 15 kg of lignite or 4-5 kg of coke. Besides that, using the requested method of use, CO2 emissions can be reduced up to 75%
The next subject of the Invention is the usage as a substitute/alternative fuel in thermoelectric power plants. During the use of the fuel, the combustible mixture or its components bind harmful exhaust gases generated by the burning of coal in the thermoelectric power plants. Above all, this refers to the binding of CO2.
The task of insulator which coats the inside of the container is collecting and activating the combustion of hydrogen in the process. Methylcellulose makes the insulator prevent hydrogen outflow from the container. Methylcellulose can be either gelatine or tylose, or another industrially accessible methylcellulose. The Invention can be used in all solid fuel furnaces, including, besides thermoelectric power plants, industrial and central heating furnaces of varying capacities, given that the minimal working temperature of the furnace is no less than 350°C.
When the fuel enters the furnace, calcium aluminate salts 3CaO x AI2O3 are formed as a product of combustion, along with the release of three hydrogen molecules in the form of bubbles. Reactions between quartz sand, quicklime and water form calcium hydrosilicate. The Sulphur necessary to form calcium hydrosilicate is found in coal as an impurity. The airtight container has the function of collecting hydrogen in these reactions, acting like a “fuse” the moment the fuel enters a furnace. As hydrogen can burn in an oxygen atmosphere, oxygen can burn in a hydrogen atmosphere. If two volumes of hydrogen and one volume of oxygen mix together (explosive gas), the mixture will explode if ignited. Accordingly, this Invention provides the formation of calcium hydrosilicate from quartz sand, lime, water and Sulphur from coal which extracts oxygen during combustion that prevents the creating of explosive gas.
Aluminum is present in the solid matter of the combustible mixture in the form of aluminium powder of high purity. High purity means that it contains at least 90% aluminium. The best results are achieved with aluminum with the specific surface area of 7000 cm2/g. The volume density of aluminium powder is desired to be around 0.15 kg/dm3.
One kilogram of hydrogen, during combustion, releases 143,146 kJ/kg of energy, while the newly invented fuel releases 95,690 kJ/kg, i.e., 67% of the combustion energy of pure hydrogen. That usability comes from the fact that the hydrogen burns in fuel - in other words, the hydrogen is burning inside the container, where components of the combustible mixture create an oxidizing atmosphere which generate more hydrogen.
Fuel combustion occurs in 4 phases: a) In the first phase hydrogen is generated by reactions between solid and liquid components of the combustible mixture. Hydrogen is contained within the fuel because the airtight container is keeping it inside. Hydrogen is ignited inside the container by the flammable insulator and container inside the furnace. b) Combustion of pure hydrogen in close proximity of the mixture from which hydrogen is coming out from the extremely hot furnace of a thermoelectric power plant (1000°C) causes an accelerated extrusion of hydrogen from water in the mixture. c) The separation of hydrogen is followed by the burning of aluminate salts and other flammable silicate components in the mixture. d) Regardless of how the fuel is used, the incombustible part of the mixture, calcium oxide or quicklime, while travelling with other gases through thermoelectric power plant’s chimney or of other plants, further purifies harmful exhaust gases by binding to them. This way up to 75% of exhaust gases are purified, making them environmentally acceptable.
The polyethylene container production in accordance with Invention evolve as follows: a) Two touching rollers have 2 mm wide, 1 mm deep interlocking grooves. If the lower roller has grooves lengthwise, the top roller grooves are placed so that by means of power, when they cut a double foil, rectangles/squares are cut out containing generated hydrogen. The space inside the container needs to be larger than two-thirds of the granulated combustible mixture volume to make room for hydrogen that will be generated inside the container. b) After certain time, more precisely, after a few hours, the combustible mixture will generate enough hydrogen that the granules look inflated. In this phase it is ready for combustion.
At temperatures higher than 300 degrees Celsius, the PVC container bums and allows uniform separation of hydrogen as well as its combustion, while oxygen from the water binds to the mixture. This then creates calcium hydrosilicate, which prevents the formation of explosive gas.
As for zinc carbonate (ZnCCh), as dehydrated it occurs in the form of white powder that doesn’t dissolve in water. However, as a commercial product, it is sold in a hydrated form as basic zinc carbonate (2ZnCOs x 3Zn(OH)2). Basic zinc carbonate is used in the Invention.
Main reactions of the solid matter occur with caustic or slack lime (Ca(OH)2), which is produced when quick lime (CaO) comes into contact with water from the liquid part of the mixture. It is the basis of hydrogen generation. These reactions are the following:
1. 2A1 + 3Ca(OH)2 = 3CaO x AI2O3 + 3H2
2. 2A1 + Ca(OH)2 + 6H2O = 3CaO x AI2O3 + 3H2
3. 7ZnBr2+ Ca(OH)2 + 6H2O = 7ZnO + 7Br2 + 7H2 or 14HBr
4. 2ZnCO3 + 3Ca(OH)2 + = 2ZnO2 +2CaCO3 +2CaO + 3H2
5. (2ZnCO3 x 3Zn(OH)2 + 2Ca(OH)2 = 6ZnO2 + CaCO3+CaO + 5H2
6. 2ZnCl2 x 2NH4CI + 2Ca(OH)2 +2H2O = 2ZnO + 2NH4OH +2CaO + 3H2 + 2C12
It should be noted that the other part of CaO in contact with water turns into hydrated lime - Ca(OH2) + 6H2O which along with aluminium starts the reaction listed as 2.
On the other hand, reactions between the liquid components and Ca(OH)2, which produce hydrogen are the following:
7. 2HCOOH +2Ca(OH)2 + 2H2O =3CaO + 2CO2 +6H2
8. CH3OH + Ca(OH)2 = CaCO3 + 3H2
9. HCHO + Ca(OH)2 + = CaCO3 + 3H2
When the polyvinyl chloride container has burned, the following reactions occur:
10. C + H2O = co + H2
11. H2O + CO = CO2 + H2
12. CaO + CO2 = CaCO3
Combined: C + 2H2O + CaO = CaCO3 + 2H2
Generally, CaO is made from Ca(OH)2 which has lost water due to heat and C is the carbon from coal. Therefore, with this Invention, hydrogen isn’t just formed inside the fuel, but also in the reaction of water vapor gasification. Water in the liquid part of fuel is responsible for gasification, along with any moisture from the coal.
The lower heating value of coal varies from 29,310 kJ/kg for anthracite to 12,250 kJ/kg for lignite. In terms of heating value, when replacing 50% of coal mass, calculated on a 1,000 kg base, 1,250 Nm3 of hydrogen is needed for lignite and 521 Nm3 for anthracite. Converting this to mass, that is 110 kg of hydrogen for anthracite and 42.7 kg of hydrogen for lignite. Therefore, 1,000 kg of anthracite give off as much heat as 500 kg of anthracite enriched with 110 kg of hydrogen, or, in the other case, 500 kg of lignite enriched with 42.7 kg of hydrogen. In other words, eight mass percentages of this fuel substitutes around 50 mass percentages of coal. Furthermore, assuming that anthracite is 100% coal, the coal and hydrogen ratio in 500kg of coal and 110 kg of hydrogen is C:H = 1:1.32. The ratio of coal to hydrogen is one of the key energy and environmental indexes. Natural gas has a ratio of C:H = 1:4, petrol C:H = 1:2. With that in mind, the higher the percentage of carbon, the more harmful the environmental impact, because more carbon dioxide is generated. That is why the combustible mixture, the fuel, is prepared in a way to reduce the environmental risks based on reaction 12 above.
Inventor Drago COSIC

Claims

PATENT CLAIMS The combustible mixture, consisting of a solid and liquid part, is characterized in that the solid part comprises:
Aluminium powder; at least one M 1 X2, where M1 can be any metal in oxidation state +2 and X can be any halogen;
M2COS, where M2 can be any metal in oxidation state +2; zinc ammonia chloride;
SiO2; and quicklime.
The liquid part comprises:
At least one Ci to Cf> carboxylic acid, or at least one anhydride of the said carboxylic acids, or at least one of its esters or amides; methylcellulose; formaldehyde, or its commercially accessible solution - formalin; water. The combustible mixture according to Claim 1, is characterized in that the share of solid matter in the mixture varies between 32% w/w and 46% w/w, and that of liquid matter between 54% w/w and 68% w/w. The combustible mixture according to Claim 2, is characterized in that the share of solid matter in the mixture varies between 36% w/w and 42% w/w, and that of liquid matter between 58% w/w and 64% w/w. The combustible mixture according to Claim 2, is characterized in that the share of solid matter in the mixture 39% w/w and that of liquid 61% w/w The combustible mixture according to Claim 1, is characterized in that the components of solid matter are present in the following weight percentages:
Aluminium powder 3% to 10%
MXX2 1% to 4%
M2CO3 1% to 3% zinc ammonia chloride 2% to 5%
SiO2 3% to 8% quicklime 70% to 90% The combustible mixture according to Claim 5, is characterized in that the components of solid matter are present in the following weight percentages: Aluminium powder 5% to 8%
MXX2 2% to 4%
M2CO3 1% to 2% zinc ammonia chloride 3% to 5%
SiO2 4% to 7% quicklime 74% to 85% The combustible mixture according to Claim 5, is characterized in that the components of solid matter are present in the following weight percentages:
Aluminium powder 7%
MXX2 3%
M2CO3 1.5% zinc ammonia chloride 3. 5%
SiO2 6% quicklime 79% The combustible mixture according to Claim 1, is characterized in that the components of liquid matter are present in the following weight percentages:
At least one carboxylic acid, or at least one anhydride of carboxylic acids, or at least one of its esters or amides can be present in an interval of 10% to 27%;
Methylcellulose can be present in an interval of 20% to 40%;
Formaldehyde, or its commercially accessible solution - formalin can be present in an interval of 1% to 10%;
Remaining part consists of water. The combustible mixture according to Claim 8, is characterized in that the components of liquid matter are present in the following weight percentages:
At least one carboxylic acid, or at least one anhydride of carboxylic acids, or at least one of its esters or amides can be present in an interval of 5% to 22%;
Methylcellulose can be present in an interval of 25% to 35%;
Formaldehyde, or its commercially accessible solution - formalin can be present in an interval of 3% to 7%;
Remaining part consists of water. The combustible mixture according to Claim 8, is characterized in that the components of liquid matter are present in the following weight percentages:
At least one carboxylic acid, or at least one anhydride of carboxylic acids, or at least one of its esters or amides had a presence of 17% Methylcellulose had a presence of 29%
Formaldehyde, or its commercially accessible solution - formalin had a presence of 5%
Remaining part consists of water. The combustible mixture according to any of the preceding claims, is characterized in that M1 and M2 are selected among Fe (iron), Cu (copper) and Zn (zinc); that and at least one carboxylic acid, or at least one of its derivatives is selected from a group made up of Ci - C3 carboxylic acids; while the methylcellulose is selected between gelatine and tylose. The combustible mixture according to Claim 11, is characterized in that M1 and M2 are Zn; and methylcellulose is tylose. The combustible mixture according to Claims 1, 8-10 and 11, is characterized in that the liquid phase two carboxylic acids are present: Ci carboxylic acid and C2 carboxylic acid. The combustible mixture according to Claims 1, 5-7 and 11, is characterized in that in the solid matter the M 1 X2 is a mixture of ZnCh and ZnBn. The combustible mixture, according to any of the preceding claims, is characterized in that it contains coke and ethanol as additives. The fuel, is characterized in that it contains the combustible mixture according to any of the preceding claims is hermetically sealed in a container. The fuel according to Claim 16, is characterized in that the hermetically sealed container is made of a polymer material. The fuel according to Claim 17, is characterized in that the hermetically sealed container is made of a polyvinyl chloride. The fuel according to Claim 16, is characterized in that the hermetically sealed container has a barrier that separates the solid and liquid matter and that barrier, when in contact with the acids in the liquid, slowly dissolves and allows mixing of solid and liquid matter and thereby gradual generation of hydrogen inside the container. The fuel according to Claim 16, is characterized in that the hermetically sealed container is coated on the inside with an insulator. The fuel according to Claim 16, is characterized in that the heat insulator is a tar-based adhesive. The fuel according to Claim 16, is characterized in that one third of the hermetically sealed polyvinyl chloride container is filled with liquid and solid matter, while the remaining two-thirds are for receiving generated hydrogen. The energy production method in the thermoelectric power plant furnace is characterized in that the fuel according to claims 16-22 is brought into the thermoelectric power plant furnace. The energy production method in the thermoelectric power plant furnace according to Claim 23, is characterized in that the fuel according to claims 16-21 replaces up to 50% of required coal. The energy production method in the thermoelectric power plant furnace according to Claim 23, is characterized in that the fuel according to claims 16-21 replaces up to 60% of required coal. The energy production method in the thermoelectric power plant furnace according to Claim 23, is characterized in that the fuel according to claims 16-21 replaces up to 70% of required coal. The energy production method in the thermoelectric power plant furnace according to Claim 23, is characterized in that the fuel according to claims 16-21 replaces all of the required coal. The energy production method in the thermoelectric power plant furnace according to Claim 23, is characterized in that 1kg of the fuel according to claims 16-21 replaces 15 kg of lignite or 4-5 kg of coke. The energy production method in the thermoelectric power plant furnace according to Claim 23, is characterized in that the fuel according to claims 16-21 reduces CO2 emissions by up to 75%. The use of fuel according to claims 16-22, is characterized in that the said fuel is used as a substitute for coal in thermoelectric power plants. The use of fuel according to Claim 30, is characterized in that the said fuel binds harmful exhaust gases made as a result of incomplete coal burning in the thermoelectric power plant furnace. The use of fuel according to Claim 31, is characterized in that the said fuel binds CO2. The use of fuel according to any of the claims 16-22, is characterized in that the said fuel is used for energy production in industrial and central heating furnaces.
Inventor COSIC, Drago
PCT/BA2022/000001 2022-01-28 2022-02-21 High energy environmentally friendly fuel as an additive for coal-fired power plants WO2023141686A1 (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7014834B2 (en) 2002-07-30 2006-03-21 Center For Coal Utilization, Japan Process for preparing hydrogen through thermochemical decomposition of water
US20130167761A1 (en) * 2010-09-08 2013-07-04 Cor Brevis D.O.O. Fuel and combustible mixture used as a substitute for fossil fuels in thermoelectric power plants, industrial and central heating furnaces

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7014834B2 (en) 2002-07-30 2006-03-21 Center For Coal Utilization, Japan Process for preparing hydrogen through thermochemical decomposition of water
US20130167761A1 (en) * 2010-09-08 2013-07-04 Cor Brevis D.O.O. Fuel and combustible mixture used as a substitute for fossil fuels in thermoelectric power plants, industrial and central heating furnaces

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