PROCESS OF COMBUSTION OF SOLID, LIQUID OR GASEOUS HYDROCARBON (HC) RAW MATERIALS IN A HEAT ENGINE, HEAT ENGINE AND SYSTEM FOR PRODUCING ENERGY FROM HYDROCARBON (HC) MATERIALS
The invention relates to a process of combustion of solid, liquid or gaseous hydrocarbon (HC) raw materials in a heat engine comprising at least one combustion chamber, said process comprising at least one iteration of the following steps, which constitute/form a combustion cycle, wherein a load of hydrocarbon (HC) materials and an oxidizing gas are added to said combustion chamber, combustion of said load of hydrocarbon materials being triggered by said oxidizing gas; characterized in that said oxidizing gas comprises: trioxygen (O3) and carbon dioxide (CO2) and/or carbon trioxide (CO3). The invention likewise relates to a heat engine for carrying out and conducting the process according to the invention, and to a system for producing energy from hydrocarbon materials by implementing and operating such engine.
This application is a 35 USC §371 national stage application of PCT/BR2014/000435, which was filed Dec. 10, 2014 and claimed priority to French Patent Application No. 1362395, filed Dec. 11, 2013, both of which are incorporated herein by reference as if fully set forth.
FIELD OF INVENTIONThe invention refers to a combustion process for hydrocarbon materials in a thermal engine. The invention also refers to a thermal engine implementing and operating said process and system for producing energy from hydrocarbon materials comprising such engine.
The field of invention is the field of treatment of solid, liquid and/or gaseous hydrocarbon materials, particularly diesel. The invention specifically relates to diesel combustion and generally to hydrocarbon materials in a thermal engine.
BACKGROUNDThe large majority of the systems of the state of the art performs combustion of said hydrocarbon materials with atmospheric air as oxidizing agent. We know that atmospheric air is constituted by 21% oxygen and 78% nitrogen, the balance being rare gases, and only oxygen (O2) is the reactive element of combustion. Nitrogen is a neutral gas, which serves as ballast gas fluid, a thermal fluid and/or work volume expansion in current systems. Said systems are dedicated to the production of thermal energy (boiler shells, etc.) or to a conversion into mechanical energy (thermal engines, turbines, etc.).
To perform a complete combustion with atmospheric air, the oxidizing agent should be supplied in excess relative to the quantity of reactive oxygen. This equation results in the generation of disproportionate combustion gas volumes over the gases effectively produced by complete combustion. Further, considerable combustion gas volumes generate large inconveniences, considerable atmospheric pollution and effects (heat, organic pollutants, CO2, various oxides, aerosols, etc.) which neutralization is extremely difficult.
On the other hand, said large volumes of combustion gases become extremely costly means to be implemented to neutralize the generated pollution, especially the capture of CO2, which is one of the main causes of global warming.
These excessive oxidizing agents also reduce the transfer efficiency of energy of fuel energy to the system, and they usually do not perform complete combustion.
On the other hand, incomplete combustion of hydrocarbon materials in the current systems causes dirt deposition of non-burnt material, thus reducing yield of the current systems over time.
The sum of these inconveniences reduces the thermodynamic yield of current thermal engines, rarely surpassing 50% of the heating power of the fuel used, thus meaning waste of more than half of the available energy. Furthermore, a large part of the thermal energy is dissipated by the cooling systems of the engines and exhaust gases. Usually, the “global” yield of thermal engines is lower than 45% of the Lower Heating Power (PCI) of the fuel used.
Other processes promote a combustion of hydrocarbon materials with pure or eventually mixed dioxygen with a neutral gas such as CO2, e.g., like the process as disclosed by the document EP 2,383,450 A1. These proceedings enable to increase yield, reduce the quantity of pollutant particles and facilitate the capture of CO2 from the combustion gas generated by the combustion.
However, it is still possible to increase combustion yield and improve combustion conditions to achieve a more respectful way of combustion, particularly the thermal engine wherein the combustion is performed.
One of the objects of the invention is to provide a combustion process of hydrocarbon materials in a thermal engine, so to allow for a better yield.
Another object of the present invention is to provide a combustion process of hydrocarbon materials in a thermal engine, which is more respectful than the thermal engine of the current processes.
Other advantages and characteristics will emerge after examining the detailed description of non-limitative embodiments and the attached drawings, wherein:
The invention enables to reach at least one of the objects as already explained, by means of a combustion process of solid, liquid or gaseous hydrocarbon materials in a thermal engine comprising at least one combustion chamber, said process comprising at least one interaction of the following steps constituting a combustion cycle:
introduction in said combustion chamber of a load of hydrocarbon materials and a oxidizing gaseous mixture; and
triggering of combustion of said load of hydrocarbon materials with said oxidizing gaseous mixture;
wherein said oxidizing agent comprises:
trioxygen (O3); and
carbon dioxide (CO2) and/or carbon trioxide (CO3).
As “hydrocarbon materials,” we understand petroleum, petroleum derivatives, natural and synthetic petroleum gases, coals and/or biomass, as well as all residues containing carbon and/or hydrocarbon, and synthesis gases from decomposition and gasification of said hydrocarbon materials.
As oxygen, we understand the oxygen atom (O) which, in current formulations, composes the dioxygen molecule (O2) and the trioxygen molecule (O3), usually called “ozone.”
As “thermal engine,” we understand every device performing the combustion of hydrocarbon materials and producing mechanical or electric energy.
The process of the invention provides a combustion of hydrocarbon materials with an oxidizing gaseous mixture comprising trioxygen (O3) and more particularly negative trioxygen (O3−).
The use of trioxygen in the oxidizing gas allows for a better use of each oxygen (O) element and consequently a more complete combustion of hydrocarbon material.
In fact, as will be disclosed below, the use of trioxygen increases the flammability of hydrocarbon materials by destabilizing the cohesion of their molecules and by speeding up the oxidization of the atoms in their compositions.
Furthermore, due to the increase in the flammability of the hydrocarbon material by using trioxygen, the combustion of hydrocarbon material is facilitated in terms of temperature and/or pressure, preserving the thermal engine or means operating combustion.
According to a first embodiment of the process of the invention, the oxidizing gas can solely comprise trioxygen (O3) and carbon dioxide (CO2) and/or carbon trioxide (CO3).
According to a second embodiment of the process of the invention, the oxidizing gas can also comprise dioxygen (O2).
Whichever is the embodiment of the process of the invention, trioxygen is dosed for each atom of fuel organic material (C and H) to have the number of oxygen (O) atoms as required for a stoichiometric combustion. Trioxygen present in the oxidizing gas (alone or mixed with dioxygen O2), thermo-chemically interacts with fuel organic materials of multiple form.
Trioxygen reacts firstly with CO2 in the oxidizing gaseous mixture according to the reaction:
CO2+O3CO3+O2 (1).
Subsequently, trioxygen reacts with the organic materials, which act with catalysts according to the reaction:
O3+catalyst→catalyst+O catalyst+O2 (2).
Said interactive bonds are unstable and kept in the order of milliseconds during combustion.
If the oxidizing gas comprises carbon trioxide (CO3), generated by the reaction (1), the latter instantaneously loses (during the combustion) its third O atom in the form of negative ion (O−), which is also immediately captured by a hydrocarbon fuel molecule. The same happens with trioxygen (O3), from which the surplus oxygen atom is extracted and immediately fixed by an organic catalyst (C or H) of the hydrocarbon molecule, thus creating a free pathway for its parent molecule of O2.
Said instantaneous and simultaneous interactions increase the flammability of catalyst fuels by destabilizing the cohesion of their molecules and speeding up the oxidization of atoms of their composition.
The integrity of oxygen available is the heart and the reaction agents. The combustion is complete, with maximum yield with the right measurement of oxygen.
With the process according to the invention, the lower flammability limit is optimized by factor 5 (five) and the speed of deflagration is doubled relative to atmospheric combustion. Oxidizing conditions make flammability conditions become instantaneous, as well as the thermal generation, thermal transmission and the expansion of the gas volume.
Providing for a complete combustion of hydrocarbon materials, thermal yield as obtained from the process according to the invention is better than that of the processes and/or engines of the state of the art. Furthermore, the thermal engine is not subject to the dirt deposition of non-burnt material, thus considerably increasing the working life of the system in comparison with the processes of the state of the art.
The combustion gas, as a result of the combustion, is composed only by CO2 and H2O, with eventual residual O2 molecules. The CO2 is the complete combustion carbon molecule, stable at high temperatures, above 800° C. H2O is the molecule resulting from the complete combustion of hydrogen from the molecular composition of the hydrocarbon material, said H2O is easily recoverable by condensation, even at atmospheric pressure and temperature. Said two molecules are recyclable and allow recovering most of the dissipated energy of the combustion and reduce the ecological impact on the environment, thus eliminating gaseous pollutants, notably nitrogen oxides, which cannot exist in the absence of nitrogen.
On the other hand, the oxidizing gas has constant characteristics for any geographic or atmospheric variations (air humidity and altitude). Therefore, quantities can be precise and constant under any circumstances, so to provide for linear and permanently regulated combustion.
According to the invention, the load of hydrocarbon materials as required for the combustion can be mixed with at least one component of the oxidizing gas before being introduced into the combustion chamber, e.g., with CO2 and/or CO3, or even with pure O3 or eventually with O2.
The oxidizing gas can be injected in the combustion chamber before, after or simultaneously with the introduction of the load of hydrocarbon material into the combustion chamber.
CO2 and/or CO3 and pure O3 or eventually mixed with O2 can be separately injected in the combustion chamber, or all of them can be mixed together before the injection in the combustion chamber.
In the process according to the invention, the combustion can be performed with:
applying a pressure in the combustion chamber; and/or
supplying electrical energy to said combustion chamber;
e.g., with a spark plug as known by the expert in the art.
The process according to the invention can also comprise the injection of a quantity of liquid water in the combustion chamber before, after or simultaneously with the oxidizing gas. Therefore, up to 20% of water relative to the oxidizing gas and preferably between 5% and 20% of water relative to the oxidizing gas can be introduced into the combustion chamber as a function of the thermal regulation as scheduled or desired and the water expansion capacity into steam, which will replace its equivalent into CO2 and/or CO3.
The injection of water allows regulating the combustion temperature, since it absorbs a large quantity of energy from combustion into latent heat, thus reducing thermal losses caused by the dissipation in the cooling and combustion exhaust gas circuits. The injected liquid water represents a negligible volume ratio with the oxidizing gaseous mixture of less than 20% as a function of the size of the thermal system at issue. Once amidst the combustion medium, said water evaporates into overheated steam. The expansion of the volume of liquid water as converted into steam is more than 10 times to hundreds of times the value introduced as a function of the dynamic pressure as impinged.
Therefore, latent heat of evaporation is completely and immediately transformed into useful thermodynamic energy, instead of having a considerable part of it dissipated by the cooling and combustion gas exhaust circuits. The portion of injected water is limited by lowering the temperature caused by its evaporation and which should not be lower than the optimal operating temperature of the thermal system at issue. The volume of the portion of evaporated water replaces the equivalent volume of CO2/CO3.
The oxidizing gas can comprise between 15 and 25% of oxygen, in the form of pure O3 or in the form of a mixture of O3 and O2, and between 85 and 75% of CO2 and/or CO3.
More particularly, the oxidizing gas can comprise between 18 and 22%, preferably 21% of oxygen in the form of pure O3 or in the form of a mixture of O3 and O2, and between 82 and 78%, preferably 79%, of CO2 and/or CO3.
The oxidizing gas advantageously comprises, for a mole of carbon of hydrocarbon material, at least one mole of CO2 and/or CO3, and a maximum of 17 moles of CO2 and/or CO3.
The oxidizing gaseous mixture advantageously comprises, for one carbon atom of the hydrocarbon material, at least the equivalent to two oxygen atoms and a maximum of the equivalent to 102% of oxygen, in the form of pure O3 or in the form of a mixture of O3 and O2.
The oxidizing gas can advantageously comprise for a hydrogen (H) atom in the hydrocarbon material, at least one oxygen atom in the form of pure O3 or in the form of a mixture of O3 and O2, and a maximum of the equivalent to 102% of oxygen in the form of pure O3 or in the form of a gas mixture of O3 and O2.
When the oxidizing gas comprises pure trioxygen, the latter may be obtained from a pure O3 reservoir/tank. When the oxidizing gas comprises trioxygen mixed with dioxygen, the mixture can be obtained either from a reservoir/tank containing a mixture of O3 and O2, or from a reservoir containing pure O3 and a reservoir containing pure O2.
Alternatively, the process according to the invention can also comprise a step of generation of trioxide from oxygen molecules, more particularly from dioxygen molecules (O2), e.g., by the “CORONA” effect applied to the oxygen molecules, more particularly to dioxygen molecules.
For that purpose, the process according to the invention can implement a production mean of trioxygen (O3).
Trioxide generating means can comprise a “CORONA” effect device, installed, e.g., on a conduit in which oxygen (O2) flows, such as the injection tube of dioxygen O2 into the combustion chamber, to induce electric conversion discharges according to the formula:
O2+hv→O2*(3Σu−);
(170 to 210 nm);
O2*+O2→O3+O, O+O2→O3.
The ratio of oxygen to be converted is defined by the intensity of the induced Corona effect, and the portion of O3 can vary between 10 and 100% of the oxidizing oxygen as included in the gaseous oxidizing mixture.
Furthermore, the process according to the invention can comprise a step of generation of carbon trioxide CO3 from CO or CO2 molecules, and preferably from CO2 molecules, e.g., by means of the “CORONA” effect applied to the CO2 molecules in the presence of O3/O2.
According to a preferred embodiment, the oxidizing gas is obtained from a gaseous mixture of O2 and CO2, to which Corona effect is applied to generate O3 and CO3 molecules, the oxidizing gas therefore, obtained comprises:
O3; and
CO2 or CO3 or a mixture of CO2 and CO3; and
eventually O2, as a function of the energy of the electric discharges applied for the Corona effect.
As disclosed above, the combustion gas obtained after the combustion essentially comprises CO2 and H2Osteam.
The process according to the invention can also comprise a recovery of CO2 included in the combustion gas, by cooling said combustion gas.
When the combustion gas comprises H2O molecules, steam can be previously removed from the combustion gas by condensation, and then, CO2 and the latent heat from condensation can be recovered.
Advantageously, CO2 can be condensed by any/all process known by the expert in the art. Therefore, all non-condensable material originated from the fuel and/or from the oxidizing gaseous mixture (metals, metalloids, sulfur, oxygen) are isolated from CO2, which is pure in liquid stage, and can be stored and recycled in the process. CO2 can be evaporated during the cooling process of the combustion gas before being re-injected into the combustion chamber for a new cycle.
Thermal energy (thermal capacity/sensitive and latent heat) of the combustion gas can also be recovered, by means of heat exchange with a thermal fluid with one or more heat exchangers, e.g., aiming to produce electricity with a turbine.
A part of CO2 recovered from the combustion gas of a combustion cycle can be advantageously re-used in the oxidizing gas and/or to generate carbon trioxide as disclosed above, to perform a new combustion cycle.
A part of CO2 recovered from the combustion gas can be re-used in a microalgae culture, e.g., in a microalgae reactor, wherein the microalgae culture provides O2 by means of photosynthesis.
At least a part of O2 provided by microalgae can be used in the oxidizing gas and/or to generate trioxygen as disclosed above, for a new combustion cycle.
According to another aspect of the invention, it is provided a thermal engine performing a combustion of hydrocarbon materials, and particularly organized means to operate all the steps of the combustion process according to the invention. The thermal engine according to the invention can comprise trioxygen generating means from oxygen atoms, more particularly from a gaseous flow of O2.
Said carbon trioxide generating means can comprise means applying Corona effect with oxygen atoms, more particularly with a gaseous flow of O2, e.g., a Corona effect tube disposed on a duct in which O2 flows.
The thermal engine according to the invention can also comprise means to generate carbon trioxide from CO molecules or preferably from CO2 molecules.
Said carbon trioxide generating means can comprise means to apply Corona effect on CO molecules or preferably on CO2 molecules, e.g., a Corona effect tube disposed on the duct in which CO2 flows in the presence of O3/O2.
The thermal engine according to the invention can further comprise at least one adjustment module for the:
quantity of CO2 and/or CO3; and/or
quantity of oxygen in the form of pure O3 or a mixture of O3 and O2;
used in the oxidizing gas.
The thermal engine can also comprise at least one adjustment module of the quantity of liquid water introduced into the combustion chamber and eventually an adjustment module of the quantity of hydrocarbon materials for each combustion cycle.
According to another aspect of the invention, it is provided a vehicle with a thermal engine according to the invention to move the vehicle. Said vehicle can be, e.g., a boat or a train.
According to another aspect of the invention, it is provided a system for producing mechanical or electrical energy from hydrocarbon materials, comprising:
a thermal engine according to the invention, supplying a combustion gas comprising CO2; and
at least one microalgae reactor producing O2 by photosynthesis;
at least one means for feeding said reactor with at least a part of CO2 present in said combustion gas; and
at least one means for recovering at least a part of said O2 produced by said microalgae reactor and reusing said recovered O2 to generate trioxygen.
It is understood that the embodiments described below will not be limitative. We can notably imagine variations of the invention comprising only a selection of the characteristics described below, isolated from the other characteristics as described, if this selection of characteristics is sufficient to confer a technical advantage or to show the difference between the present invention over the state of previous art. This selection comprises at least one preferable functional characteristic with no structural details, or only with a part of the structural details if this part is sufficient only to confer a technical advantage or to distinguish the invention unique enough over the state of the prior art.
In the drawings, the elements common to several figures keep the same reference.
The engine 100 as represented by
The engine 100 comprises, for each cylinder 102 and for each combustion cycle:
a first module 110i, adjusting the quantity of hydrocarbon materials HC introduced into the combustion chamber 106, from a reservoir 112 of hydrocarbon materials;
a second module 1141, dosing the quantity of oxygen introduced into the combustion chamber 106, in the form of pure O3 or a mixture of O3 and O2;
a third module 116, dosing the quantity of pure CO2, pure CO3 or also CO2 mixed with CO3, introduced in the combustion chamber 106;
a forth module 118, dosing the quantity of liquid H2O as introduced into the combustion chamber 106 from a H2O reservoir 120.
The engine 100 also comprises a corona effect tube 122, located at the outlet of a reservoir of O2 124, allowing generating a gas flow constituted by pure O3 or by a mixture of O3 and O2, from O2 provided by the reservoir 124. The gas flow obtained downstream from the corona effect tube 124 (and constituted by pure O3 or a mixture of O3 and O2) feeds the module 114i to regulate the quantity of oxygen, and then its injection into the combustion chamber 106i.
The engine 100 also comprises a corona effect tube 126, located at the outlet of a reservoir of CO2 128, allowing generating a gas flow composed by pure CO3 or a mixture of CO3 and CO2, from a part of CO2 provided by the reservoir 128 and from the O2 provided by the reservoir 124. The gas flow obtained downstream from the corona effect tube 126 feeds the module 1161 to regulate the quantity of CO3 and CO2, followed by its injection into the combustion chamber 1061.
Combustion of the mixture formed by the load of materials (hydrocarbons+oxidizing gas) is activated by the combustion chamber 106 or by pressure applied by the piston or by a spark plug (not shown), producing an electric spark in the combustion chamber.
The combustion gas obtained from the complete combustion of the load of hydrocarbon materials with oxygen entering the combustion chamber 106 is evacuated by an evacuation tube/conduit 130. The combustion gas GC is mainly constituted by CO2. On one hand, the CO2 admitted into the combustion chamber 106 through the module 116 and, on the other hand, CO2 formed by the oxidization of carbon elements C present in hydrocarbon compounds by the O3 compounds (and possibly O2), and H2O, on one side H2O eventually admitted in the combustion chamber 106 by the module 118 and, on the other side, H2O formed by the oxidization of the di-hydrogen elements H2 present in the hydrocarbon compounds.
It is possible that the combustion gas GC includes residual compounds of O2, e.g., in a ratio of 1 or 2% of combustion gas, excessively admitted in the combustion chamber 106 to assure complete combustion of the load of hydrocarbon materials HC in the combustion chamber 106.
The engine 200 as represented by
Besides the engine 100 of
The treatment module comprises a thermal exchanger (not shown) performing a thermal exchange between the combustion gas GC to take the combustion gas GC to a temperature lower than 100° C. so to condensate H2O steam contained in the combustion gas GC. Therefore, the steam found in the combustion gas GC is isolated and feeds the water reservoir 120 to be re-used in the next combustion cycle.
When the combustion gas GC includes residual O2, the latter one, which is not condensable at the condensation temperature of CO2, is isolated by means of CO2 condensation and feeds the reservoir of O2 124 to be re-used in the next combustion cycle.
Finally, after separating steam from O2, the combustion gas GC only contains CO2 feeding the reservoir 128 of CO2 to be re-used in the next combustion cycle.
The system 300 for producing energy of
Besides the thermal engine of
In all the examples disclosed, the invention allows to produce mechanical energy by rotating the shaft 108.
Said mechanical energy can, for instance, be used to move a vehicle on the ground, in the air or water, such as a boat. In this case, the thermal engine can be, as a non-limitative example, a diesel engine fed by a petroleum derivative such as heavy fuel oil.
Mechanical energy can also be used to generate electric energy, e.g., with an electric generator moved by an engine and/or gas turbine and/or liquid hydrocarbons and in combination with a steam turbine alternator.
In all the examples disclosed, modules 110, 114, 116 and 118 can be configured to introduce in the combustion chamber 106, respectively, a pre-determined quantity of hydrocarbon materials HC, oxygen in the form of pure O3 or mixed with O2, CO2/CO3 and liquid water, said quantities being determined in accordance to, on one hand the quantity of carbon C and hydrogen H molecules present in the load of hydrocarbon materials admitted into the combustion chamber, so that the load of hydrocarbon materials suffers a complete combustion, i. e. a complete oxidization, and on the other hand, the size of the cylinder 102 and piston 104 and the desired power at the engine output.
Each one of the modules 110, 114-118 can be an electronic module controlled by computer.
In all the examples disclosed, each combustion element is separately admitted into the combustion chamber 106. Consequently, it is also possible to mix at least two elements of combustion before admission into the combustion chamber 106 and submit them to thermal and/or mechanical treatment, e.g., compression.
In all disclosed cases, each combustion element can suffer thermal treatment or compression before being admitted into the combustion chamber.
In the examples described, the corona effect tube 126 is optional and the oxidizing gas may not contain CO3.
Alternatively, one single corona effect tube can be used instead of tubes 122 and 126. In this case, the O2 provided by the reservoir 124 is mixed with the CO2 provided by the reservoir 128, after the gaseous mixture O2+CO2 is transported by one single corona effect tube.
We now describe a combustion of hydrocarbon materials according to the invention, when the hydrocarbon material is solely constituted of hexadecane with the formula C16H34, in comparison with a combustion under atmospheric air.
The table below shows the characteristics of hexadecane C16H34:
Wherein it describes that:
1 kg of hexadecane has a higher heating value (PCS) of 12.78 kWh and a lower heating power (PCI) of 11.48 kWh≈˜9%;
The complete oxidization of 1 mole of carbon in 1 mole of CO2 generates an exothermic reaction of 394 kilojoules, while the incomplete oxidization of 1 mole of carbon into 1 mole of CO only generates an exothermic reaction of 111 kilojoules, i.e., 3.55 times less;
Each particle is carbon and each gram of carbon can generate 32.83 kilojoules of thermal energy with 1 mole of carbon=12 g.
The “thermodynamic” yield of an explosion engine, with controlled ignition or compression Otto or Diesel is relative to the combustion yield and the transfer from thermal energy to mechanical energy.
The present invention optimizes combustion yield and, consequently to reduce fuel consumption, for identical energetic product.
Combustion at “atmospheric” air depends on atmospheric (humidity) and geographic factors (altitude, oxygen-poor air). In Diesel engines, at constant volumes, the quantity of oxidizing air is constant and must be oversized to offer the best combustion. The quantity of interactive oxygen in air is not higher than 65% of 21% of oxygen existent in the air, at sea level. To reach the oxygen of the stoichiometric combustion, we need to double the volume of oxidizing air. The volume of combustion air interacts with the combustion providing active oxygen, but, on the other hand, increasing the volume of neutral gas (nitrogen), which acts in the opposite direction reducing the combustion zones since it takes space.
One of the advantages of the process, according to the invention is that the trioxygen molecule can be produced on the site of its use with several possibilities of quantitative and qualitative regulation.
Another advantage of the process, according to the invention is that the trioxygen molecule is unstable and it immediately interacts with its medium, provided that it contains “catalyst” organic materials or that its electric polarity (negative/positive) is opposed to that applied to the ozone. The prime interaction between trioxygen with the carbon dioxide molecule in the gaseous oxidizing mixture, before its injection in the combustion chamber, generates carbon trioxide (CO3). The binding of the third oxygen atom and the CO2 molecule is very unstable. Any proximity with an organic material causes the catalytic reaction of transferring said atom to the organic material; the capture of said oxygen atom, actives the destabilization of the catalyst molecule. Said partial oxidization makes the compounds of the organic molecule more oxidative and more flammable.
The gaseous oxidizing mixture (O2/O3+CO2/CO3) interacts directly with the fuel.
The instability of the trioxygen bindings and their immediate capture by the organic catalysts create an “autogenous” pre-combustion of the fuel materials, oxygen then interacts directly with fuel under more favorable conditions than the usual combustion/oxidization, without the fact that being mixed with CO2/CO3 hampers this reaction, which is exothermal.
Another advantage of the process according to the invention is that the injection of water into the combustion chamber with the oxidizing gaseous mixture favors the distribution of the fuel front flame. In that highly exothermic medium and under temperatures above 1000° C., CO2/CO3 and H2O also interact directly with the fuel by means of a “redox” reaction, which helps distribute and speed up combustion.
In atmospheric combustion, numerous carbon particles are not burned, thus hydrocarbon molecules, which have not been oxidized by the mixture of combustion air.
In the process, according to the invention, atomic and molecular oxygen reacts directly with the fuel and decomposes the hydrocarbon molecule in oxidizing C and H. At the same time, a “redox” reaction is activated by CO2 and H2O of the mixture, which also react with C and H of the decomposed molecules of the following redox reactions:
C+CO22CO+172 kJ/mol;
H2+CO2H2O+CO+41 kJ/mol.
These reactions are endothermal; they take part in the regulation of the temperature of the medium and reduce thermal dissipation. The reaction (C+CO2 2CO) gasifies carbon structures and amorphous carbon elements (particles, soot) which would not be directly oxidized by O2. Therefore, they are converted into gaseous molecules (CO) that are more reactive to complete oxidation (eminently more flammable because of their gaseous state, which causes CO molecules to have a better distribution in front of the flame(s) of the thermal system and by of the thermochemical conditions of the medium) in the presence of free oxygen:
CO+OCO2−283 kJ/mol.
Therefore, completion of combustion is progressive during the thrust (work) period of the engine pistons, which increases thermodynamic capacity for a same unit of fuel, improves the linear efficiency by distributing thermal effects throughout the course of said piston, and thus reduces wear due to thermal differentials, reducing global thermal dissipation.
The same thing happens to the H2O molecule that react with CO according to:
H2O+COH2+CO2−41 kJ/mol; and
H2+OH2O−242 kJ/mol.
Therefore, completion of combustion is progressive during the thrust (work) period of the engine pistons, increasing thermodynamic efficiency by homogenization of thermal distributions by these sequences of simultaneous exothermal reactions.
Another advantage of the process according to the invention is that the mixture of CO2/oxygen does not generate pollution by nitrogen oxide, since nitrogen molecules are not present in the combustion.
In the present example, the fuel is hexadecane, of formula C16H34, the average density of this fuel is ≦1.
As disclosed on the table, to perform the stoichiometric combustion of 1 liter of hexadecane, 3.46 kg of oxygen (O2) (2.425 Nm3) are required.
For atmospheric combustion with 50% efficiency yield with the characteristics of the current processes and engines, one must consider the volume of air as a function of the efficiency coefficient of separation O2 from the nitrogen mixture, approximately 60/65%.
To reach the combustion yield of said engines, an excess of oxygen of at least 15% is required, i.e.:
3.98 kg or 2.79 Nm3 of O2.
Considering an efficiency coefficient of separation of O2 of 65%:
2.79/65%=4.29 Nm3 of O2.
Considering a 21% percentage of O2 per m3 of air:
20.43 Nm3 of air per liter of hexadecane.
This combustion has only 50% of efficiency.
An engine is designed then in function of these parameters. Current engines work with a proportion of ⅕ of oxygen in the oxidizing mixture (the same ratio as in air).
The process according to the invention only requires an excess of O2 between 2 and 5% for a combustion yield higher than 93%, i.e.:
3.57 kg or 2.50 Nm3 of O2.
Since there is no constraint linked to the separation of the gaseous mixture, oxygen is totally active. Combustion yield is maximized.
Complete combustion of carbon generates CO2 and 3.6 times more energy than that produced by incomplete combustion in CO:
C+O=CO 111 kJ/mol;
C+O2═CO2 394 kJ/mol.
This state of fact provides energy from a better expansion of the combustion gas.
CO2 substitutes nitrogen as ballast gas for thermal gaseous expansion that supplies mechanical work pushing the piston.
At 800° C., CO2 has a dilatation coefficient 30% higher than air, thus requiring 23% less of the thermal capacity (heat sensitive).
From this, if we compare “atmospheric” values, transposed to O2/CO2, we have:
20.43 Nm3 of air per liter of hexadecane less oxidizing oxygen “2.425 Nm3 of O2” (see table)=18 Nm3 of ballast gas (nitrogen+rare gases).
At 800° C., said 18 Nm3 of ballast gas represent 48.021 m3 for a thermal capacity of 9.283 kWh. 1 kg of hexadecane has a lower heating power (PCI) of 11.48 kWh, thus representing combustion yield of 80.86%.
18 Nm3 of ballast gas CO2:
At 800° C., said 18 Nm3 substituted by CO2 expand into 62.654 m3 for a thermal capacity of 7.174 kWh.
About 15 m3 of exceeding “work” capacity.
1 kg of hexadecane has a lower heating power (PCI) of 11.48 kWh, which leave more than 4 kWh of exceeding thermal energy, i.e.:
The capacity to generate about 35 m3 of CO2 at 800° C., i.e., cumulated an exceeding total of 50 m3 of CO2 at 800° C.
Alternatively:
1 kg of hexadecane+2.425 Nm3 of O2+18 Nm3 of CO2 produce two times more work capacity than 1 kg of hexadecane in atmospheric combustion.
Or also:
½ kg of hexadecane+1.213 Nm3 of O2+9 Nm3 of CO2 produce the same work as 1 kg of hexadecane in atmospheric combustion.
Another example, 1 kg of hexadecane contains 70.66 moles of carbon (see table). The minimum CO2 (to justify an ideal Boudouard reaction homogenizing the combustion) is 70.66 moles of CO2, i.e., at least 1.6 Nm3 of CO2 (approximately) and maximum of 27 m3 of CO2 to exploit 95% of the lower heating power (PCI) of 1 kg of hexadecane: the value for a given engine depends on the type of engine, i. e. the engine cubic capacity, piston course, etc., this value being between these two numbers.
Additionally, a small part of the CO2 ballast may be substituted by “liquid” water injected at the same time as O2 and CO2 of the gaseous oxidizing mixture.
This addition may happen in order to:
regulate the combustion temperature absorbing a large quantity of energy in latent heat to transform it into dynamic energy by volume expansion of steam; and
homogenize the combustion by the redox reaction which can occur during the change of state (liquid/steam) if the H2O molecule of steam is near a CO molecule. Said exothermal reaction releases a di-hydrogen (H2) molecule in the medium that will react in any way with the oxygen of said medium, either with a free (O) atom or with an (O) atom of a trioxidized molecule;
reduce thermal loss by dissipation, latent heat is recovered during steam condensation by the cold heat carrier (liquid and/or gaseous CO2, oxygen, liquid water).
The process according to the invention reduces the wear of the equipment, maintenance; the whole combustion gas produced is recyclable:
H2O is condensable into distilled water;
CO2 is partially recycled for re-use in the process according to the invention; and
excess CO2 and H2O can be recycled in a microalgae culture plant, which will then produce hydrocarbon materials and oxygen.
Anyway, the invention is not limited to the examples disclosed above.
Claims
1. A process combustion raw material hydrocarbon (HC) solid, liquid or gaseous in heat engine comprising at least a combustion chamber, said process comprising at least one iteration of the following steps composing/amounting a combustion cycle by introducing, into said combustion chamber, a charge hydrocarbon substances and an oxidant gas, triggering combustion of said charge hydrocarbon material with said oxidant gas; characterized by the fact that the said oxidising gas comprises:
- trioxygen (O3), and
- carbon dioxide (CO2) and/or carbon trioxide (CO3).
2. A process according to claim 1, wherein the oxidizing gas comprises only one or more of trioxygen (O3) and carbon dioxide (CO2) or carbon trioxide (CO3).
3. A process according to claim 1, wherein the oxidizing gas further comprising dioxygen (O2).
4. A process according to claim 1, wherein the charge hydrocarbon material (HC) is mixed with at least one oxidant gas component before being introduced into the combustion chamber.
5. A process according to claim 1, wherein the trigger combustion is performed:
- by applying a pressure in the combustion chamber; and/or
- by an electric energy in said combustion chamber.
6. A process according to claim 1, further comprising an injection of a quantity of liquid water (H2O) and/or gas in the mixture.
7. A process according to claim 1, wherein the oxidising gas comprises between 15 and 25% of oxygen in form O3 neat or in the form of a mixture of O3 and O2, and 85 and 75% CO2 and/or CO3.
8. A process according to claim 1, wherein the oxidizing gas comprises to one mole of carbon in the hydrocarbon material, at least one mole of one or more of CO2 or CO3, and at most 17 moles of one or more of CO2 or CO3.
9. A process according to claim 1, further comprising a recovery CO2 present in the flue gas (CG) obtained after combustion by cooling said flue gas (CG), and a use of the CO2 least a portion recovered in the flue gas (CG) in the oxidizing gas to a new combustion cycle.
10. A process according to claim 9, further comprising a use of part of the CO2 recovered in the flue gas (CG) microaigas in culture, said culture providing microaigas O2 through photosynthesis, at least a portion said O2 being used for obtaining trioxide constituting the oxidizing gas to a new combustion cycle.
11. A process according to claim 1, further comprising a step trioxide generation (O3) and e respeti vãmente carbon trioxide (CO3), by means of corona discharge applied to the dioxygen molecules (O2) and, respectively, the carbon dioxide molecules (CO2).
12. A thermal engine carrying out combustion of hydrocarbon material according to claim 1.
13. A thermal engine according to claim 12, further comprising at least one module dosage:
- the amount of CO2 and/or CO3, and/or
- the amount of oxygen in the form O3 neat or in the form of a mixture of O3 and O2; used in the oxidising gas.
14. A system for energy production from hydrocarbon content (HC) comprising:
- a heat engine according to claim 12, providing a flue gas (CG) comprising CO2; and
- at least one reactor (302) producing microaigas O2 through photosynthesis;
- at least one means for feeding said reactor by at least a portion of the CO2 present in said flue gas (CG), and
- at least one means for recovering at least a portion of said reactor said O2 produced by microalgae reactor and reuse it to generate a portion of the oxidant gas.
Type: Application
Filed: Dec 10, 2014
Publication Date: Nov 10, 2016
Applicant: SEE - SOLUÇÕES, ENERGIA E MEIO AMBIENTE LTDA. (São Paulo)
Inventor: Raymond GUYOMARC'H (Negrepelisse)
Application Number: 15/103,722
