WO2008103063A1 - Process for reducing polluting emissions and greenhouse effect gas emissions, resulting from combustibles burning - Google Patents

Process for reducing polluting emissions and greenhouse effect gas emissions, resulting from combustibles burning Download PDF

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Publication number
WO2008103063A1
WO2008103063A1 PCT/RO2007/000009 RO2007000009W WO2008103063A1 WO 2008103063 A1 WO2008103063 A1 WO 2008103063A1 RO 2007000009 W RO2007000009 W RO 2007000009W WO 2008103063 A1 WO2008103063 A1 WO 2008103063A1
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Prior art keywords
combustible
alkaline
emissions
combustion
concentration
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PCT/RO2007/000009
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French (fr)
Inventor
Mihai Suta
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Mihai Suta
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Priority claimed from ROA200700422A external-priority patent/RO122782B1/en
Application filed by Mihai Suta filed Critical Mihai Suta
Publication of WO2008103063A1 publication Critical patent/WO2008103063A1/en

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J7/00—Arrangement of devices for supplying chemicals to fire
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/12—Inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/12—Inorganic compounds
    • C10L1/1233—Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/12—Inorganic compounds
    • C10L1/1233—Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof
    • C10L1/125—Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof water
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/12—Inorganic compounds
    • C10L1/1266—Inorganic compounds nitrogen containing compounds, (e.g. NH3)
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/12—Inorganic compounds
    • C10L1/1275—Inorganic compounds sulfur, tellurium, selenium containing compounds
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J2215/00—Preventing emissions

Definitions

  • the invention relates to a process for reducing the polluting emissions and the greenhouse effect gas emissions, resulted from the combustibles burning.
  • All combustibles used in industrial combustion plants cause the emission in atmosphere of greenhouse effect gases, mainly CO 2 .
  • atmosphere of greenhouse effect gases mainly CO 2 .
  • gaseous, liquid and solid, or combination of these the burning of all combustibles emit in the atmosphere volatile organic compounds, sulfur and nitrogen oxides, as well as combinations of these.
  • Liquid and solid combustibles emit a larger amount of greenhouse effect gases than the gaseous ones (mainly because of a larger specific quantity of released burned gases), but also larger amounts of volatile organic compounds, sulfur and nitrogen oxides, as well as important quantities of powders and heavy metals or their compounds.
  • Solid compounds mainly coals, emit the largest specific quantities of greenhouse effect gases, sulfur and nitrogen oxides, volatile organic compounds, but also the largest quantities of heavy metal compounds and powders.
  • US Patent 6258336 describes a process for reducing the concentrations of nitrogen oxides in the combustion gases, by injecting a relatively important quantity of ammonia or urea in the burner, after the end of the combustion reactions, treating thus the effects and not the causes of the formation of the respective pollutants,
  • a relatively important quantity of ammonia or urea in the burner, after the end of the combustion reactions, treating thus the effects and not the causes of the formation of the respective pollutants.
  • post-combustion injections with ammonium ions and amines are used, especially introduced as ammonia and urea.
  • the gases are subjected to a fairly complicated chemical purification process, in large installations.
  • Sulfur oxides are treated in a similar way, in large installations, vehiculating large quantities of consumables, mainly lime, used for trapping the sulfur oxides.
  • US Patents 7048779 and 6521021 describe a process and the respective installation for collecting mercury from the evacuated burned gases, in which combustion gases resulted in the combustion reactions are treated, collecting mercury on a consumable consisting of transitional metals with affinity for mercury.
  • KR20030072827 proposes a method and a device for treating volatile organic compounds (VOC) and the ash resulted from combustion, also on the
  • CA 3560678 proposes the reduction of greenhouse effect gas emission by marketing the emission rights, not affecting in fact the total amount of evacuated emissions.
  • the known processes have the disadvantage that they treat the reduction of emissions of sulfur and nitrogen oxides, volatile organic compounds and heavy metals which are found in the already evacuated gases from the combustion installation and not the causes of their apparition. These processes are applied in large installations consuming supplementary energetic resources, generating large quantities of infested consumables which, after their use in cleaning the combusted gases, become dangerous waste, difficult to manage.
  • Patent RO113489 discloses a composition, a process and an installation for treating the combustion in industrial and home combustion installations for activating the combustion and against the deposits and corrosion phenomena, by introducing in the burner, together with the combustion air, in a 0.01 % to 0,05% ratio, of a additivation composition consisting from a 95% solution of potassium bicromate or permanganate in demineralized water, ammonia and mineral oil 2-3% as vapors, resulting in a lowering of the greenhouse effect gases emission and a reduction of the SO x concentration in the evacuated gases.
  • Patent RU 2188329 discloses additives for reducing the combustible consumption and reduction of the toxicity of the combustion gases consisting of compositions based on copper, zirconium, aluminum, molibdene, sodium vanadate, aluminum molibdate.
  • Patent US 5380692 discloses a method for the catalytical reduction of the concentration of nitrogen oxide present in the combustion gases using as reducing agent oxygen containing organic compounds.
  • - RO113489 treats a reduced number of pollutants, focusing, from the point of view of pollutants emission, only on the removal of deposits and the reduction of sulfur oxides.
  • - RU2188329 regards the additivation of liquid combustibles, namely their pre- treatment, and the additivation process and especially stabilization of the resulting combustible is costly and rises the problem of antefabrication of the additives based in an organic binder.
  • US 5380692 concentrates on the reduction mainly of the emitted nitrogen oxides as a result of combustion, requiring energy intensive large installations and which treat the combustion products without dealing with the lowering of the production of these oxides by combustion.
  • the technical problem solved by the invention consists of establishing technical conditions for the activation of chemical processes of reduction of the oxidation state of the substances resulted from the combustion reactions, leading to the reduction of the pollutants resulted from the combustibles burning.
  • the process for reducing the pollutant emissions and of the greenhouse effect gas emissions according to the invention eliminates the above mentioned disadvantages by continuously introducing in the combustible and in the combustion air, highest oxidation state transitional metal salts, in quantities of only 0,001 - 1 ,00 ppm, without organic binders, these being conditioned exclusively in the water in which they are introduced, to form very dilute solutions.
  • the invention relates to a process for reducing polluting emissions and greenhouse effect gas emissions, by reducing the oxidation state of substances resulted from the combustion reactions by the peroxosulphuric and peroxodisulphuric acids created during * the combustion reaction, by introducing in the combustibles or in the combustible air maximum oxidation state transitional metal salts, containing in their molecule singlet oxygen.
  • the reaction initiators are peroxosulfuric and peroxodisulfuric acids, formed in the combustion reactions, as a result of introducing in the system of some maximum oxidation state transitional metal salts, which contain in the molecule singlet oxygen, for example ortovanadates (MeVO 4 ) and pyrovanadates (MeV 2 O 7 ) of alkaline and earth-alkaline metals, alkaline and earth-alkaline metal salts of isopolyacids of vanadium, molibden (MeMo 7 O 24 ) and wolfram (MeW 6 O 2 i), or peroxychromates (MeHCrO 6 ) of chromium, as potassium, lithium or ammonium salts.
  • ortovanadates MeVO 4
  • pyrovanadates MeV 2 O 7
  • transitional metal salts are introduced with the participants at the burning reaction, combustibles or combustion air, in infinitesimal quantities, of 0,001-1 ,00 ppm, their role being to cause the start of the reaction chains.
  • the reaction promoters are formed at temperatures above 400 0 C, as a result of reactions between the reaction initiators and the polynuclear aromatic organic substances from the combustibles.
  • the compounds resulted in these reactions are generally organic peroxides and superoxides of alkaline and earth-alkaline metals, which constitute promoters of the subsequent reactions, becoming in turn, initiators for the subsequent reactions.
  • the main common characteristic of these promoters is the existence in the molecule of the singlet oxygen, which has a maximum affinity for singlet carbon atoms from the polynuclear aromatics.
  • the hydride ion by trimolecular collisions, gives electrons to the central atoms from the oxygenated compounds of metals and nonmetals (for example: SO x , NO x , MeO x ) resulting protons and oxygen which form mainly water.
  • metals and nonmetals for example: SO x , NO x , MeO x
  • These trimolecular collisions occur in the heterogeneous gas medium, in the combustion enclosure and between two molecules and the wall of the combustion enclosure.
  • Most of the metal and nonmetal ions in minimal oxidation states, do not have oxidation conditions anymore, as the temperature of the heterogeneous medium they are in drops with the move toward the evacuation zone of the combusted gases.
  • Example 1 In the combustion air is dosed by injection at a ratio of 10 "4 ⁇ 10 "2 of the quantity of vanadium in the combustible or in the solid combustible is mixed in an identical proportion, a composition made of, in %(weight percentage):
  • Example 4 In the combustion air is dosed by injection at a ratio of 10 '4 ⁇ 10 "2 of the quantity of vanadium in the combustible or in the solid combustible is mixed in an identical proportion, a composition made of, in %(weight percentage):
  • Example 9 In the combustion air is dosed by injection at a ratio of 10 "6 ⁇ 10 "3 of the quantity of wolfram in the combustible or in the solid combustible is mixed in an identical proportion, a composition made of alkaline and earth-alkaline metal salts of isopolyacids as:

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to a process for reducing the polluting emissions of greenhouse effect gases resulted from the combustibles burning. The process consists of injecting in the combustible or in the combustion air of inorganic salts of transitional metals.

Description

PROCESS FOR REDUCING POLLUTING EMISSIONS AND
GREENHOUSE EFFECT GAS EMISSIONS, RESULTING FROM
COMBUSTIBLES BURNING
The invention relates to a process for reducing the polluting emissions and the greenhouse effect gas emissions, resulted from the combustibles burning.
It is known that the main source of pollution, both with greenhouse effect gases and with sulfur and nitrogen oxides, partially oxidized organic compounds, as well as with heavy metals and powders is the production of thermal energy.
All combustibles used in industrial combustion plants, cause the emission in atmosphere of greenhouse effect gases, mainly CO2. To this category belong all combustibles: gaseous, liquid and solid, or combination of these. Also, the burning of all combustibles emit in the atmosphere volatile organic compounds, sulfur and nitrogen oxides, as well as combinations of these. Liquid and solid combustibles emit a larger amount of greenhouse effect gases than the gaseous ones (mainly because of a larger specific quantity of released burned gases), but also larger amounts of volatile organic compounds, sulfur and nitrogen oxides, as well as important quantities of powders and heavy metals or their compounds.
Solid compounds, mainly coals, emit the largest specific quantities of greenhouse effect gases, sulfur and nitrogen oxides, volatile organic compounds, but also the largest quantities of heavy metal compounds and powders.
Technologies for the reduction of pollutants from the combustion gases resulted from combustion of combustibles are known.
US Patent 6258336 describes a process for reducing the concentrations of nitrogen oxides in the combustion gases, by injecting a relatively important quantity of ammonia or urea in the burner, after the end of the combustion reactions, treating thus the effects and not the causes of the formation of the respective pollutants, Thus, for the nitrogen oxides, already produced in the combustion reaction, post-combustion injections with ammonium ions and amines are used, especially introduced as ammonia and urea. At the exit of the combustion installation, the gases are subjected to a fairly complicated chemical purification process, in large installations. Sulfur oxides are treated in a similar way, in large installations, vehiculating large quantities of consumables, mainly lime, used for trapping the sulfur oxides.
The US Patents 7048779 and 6521021 , describe a process and the respective installation for collecting mercury from the evacuated burned gases, in which combustion gases resulted in the combustion reactions are treated, collecting mercury on a consumable consisting of transitional metals with affinity for mercury.
Technological installations, similar as principle and dimensions are used also for other pollutants from the volatile organic series and the heavy metals compounds, contained in the combustion products.
International publication WO2005113115 describes a method for treating evacuated combusted gases with hydrogen peroxide, for reducing the concentration of sulfur and nitrogen oxides and heavy metals.
KR20030072827 proposes a method and a device for treating volatile organic compounds (VOC) and the ash resulted from combustion, also on the
• * basis of comsumables based on transitional metals and organic binders, in large scale treatment installation.
CA 3560678 proposes the reduction of greenhouse effect gas emission by marketing the emission rights, not affecting in fact the total amount of evacuated emissions.
The known processes have the disadvantage that they treat the reduction of emissions of sulfur and nitrogen oxides, volatile organic compounds and heavy metals which are found in the already evacuated gases from the combustion installation and not the causes of their apparition. These processes are applied in large installations consuming supplementary energetic resources, generating large quantities of infested consumables which, after their use in cleaning the combusted gases, become dangerous waste, difficult to manage.
Also known are processes for reducing some pollutants contained in the combustion gases mainly NOx and SOx by introducing in the burning enclosure of some compounds which contribute to reducing the pollutants concentration at the evacuation of gases.
Patent RO113489 discloses a composition, a process and an installation for treating the combustion in industrial and home combustion installations for activating the combustion and against the deposits and corrosion phenomena, by introducing in the burner, together with the combustion air, in a 0.01 % to 0,05% ratio, of a additivation composition consisting from a 95% solution of potassium bicromate or permanganate in demineralized water, ammonia and mineral oil 2-3% as vapors, resulting in a lowering of the greenhouse effect gases emission and a reduction of the SOx concentration in the evacuated gases.
Patent RU 2188329 discloses additives for reducing the combustible consumption and reduction of the toxicity of the combustion gases consisting of compositions based on copper, zirconium, aluminum, molibdene, sodium vanadate, aluminum molibdate. Patent US 5380692 discloses a method for the catalytical reduction of the concentration of nitrogen oxide present in the combustion gases using as reducing agent oxygen containing organic compounds.
International publication WO 2004065529 discloses the use of additives based on cerium oxide loaded with transitional metals for eliminating noxes from the emission gases by incorporating them in the combustibles.
These technical solutions for reducing the pollutants from the combustion gases have the following disadvantages:
- RO113489 treats a reduced number of pollutants, focusing, from the point of view of pollutants emission, only on the removal of deposits and the reduction of sulfur oxides. - RU2188329 regards the additivation of liquid combustibles, namely their pre- treatment, and the additivation process and especially stabilization of the resulting combustible is costly and rises the problem of antefabrication of the additives based in an organic binder. - US 5380692 concentrates on the reduction mainly of the emitted nitrogen oxides as a result of combustion, requiring energy intensive large installations and which treat the combustion products without dealing with the lowering of the production of these oxides by combustion.
- WO 2004065529 proposes a class of expensive additives (cerium based) requiring a supplemental technology for their preparation.
The technical problem solved by the invention consists of establishing technical conditions for the activation of chemical processes of reduction of the oxidation state of the substances resulted from the combustion reactions, leading to the reduction of the pollutants resulted from the combustibles burning.
The process for reducing the pollutant emissions and of the greenhouse effect gas emissions according to the invention, eliminates the above mentioned disadvantages by continuously introducing in the combustible and in the combustion air, highest oxidation state transitional metal salts, in quantities of only 0,001 - 1 ,00 ppm, without organic binders, these being conditioned exclusively in the water in which they are introduced, to form very dilute solutions.
By applying the process the following advantages are obtained:
- the operation costs and the capital invested are reduced, and the problem of managing the waste of infested consumables practically disappears;
- the radiation in the combustion enclosure is increased; - the flame grows short and is concentrated;
- the formation of deposits on the heat exchange surfaces is prevented; - the existent deposits are destroyed;
- the emission of SOx (mainly SO3), NOx and volatile organic compounds is reduced;
- the combustible specific consumption is reduced and, proportionally, the greenhouse effect gas emission is reduced;
- the acid attack on the masonry and refractory concrete is reduced;
- the corrosion of heat exchange metallic surfaces is reduced;
- the specific quantity of ash and slag is reduced;
- the emission of polluting compounds of transitional metals resulted from the burning of combustibles is reduced;
- the emission of nonmetallic chlorinated organic substances is reduced;
- aromatic compounds emissions are reduced;
- environment protection costs are reduced (taxes on emissions evacuated in the atmosphere, soil and water); - the work of combustion installations is allowed with very small excess of air, the combusted compounds having almost a neutral pH.
The invention relates to a process for reducing polluting emissions and greenhouse effect gas emissions, by reducing the oxidation state of substances resulted from the combustion reactions by the peroxosulphuric and peroxodisulphuric acids created during* the combustion reaction, by introducing in the combustibles or in the combustible air maximum oxidation state transitional metal salts, containing in their molecule singlet oxygen.
In the combustion reaction, as the temperature rises, the oxidation state of the participants in the reaction increases, resulting in compounds which will also have high oxidation states. As the temperature continues to rise, a large part of these compounds will decompose, part of them participating at the reformation of some pollutants, when the temperature decreases in the second part of the trajectory of burned gases. The process concerns the burning reactions of the combustibles, at temperatures above 4000C, initiating new reaction chains, developed and propagated then by reaction promoters produced in the heterogenous medium of the gases from the combustion enclosure. The reaction initiators are peroxosulfuric and peroxodisulfuric acids, formed in the combustion reactions, as a result of introducing in the system of some maximum oxidation state transitional metal salts, which contain in the molecule singlet oxygen, for example ortovanadates (MeVO4) and pyrovanadates (MeV2O7) of alkaline and earth-alkaline metals, alkaline and earth-alkaline metal salts of isopolyacids of vanadium, molibden (MeMo7O24) and wolfram (MeW6O2i), or peroxychromates (MeHCrO6) of chromium, as potassium, lithium or ammonium salts.
These transitional metal salts are introduced with the participants at the burning reaction, combustibles or combustion air, in infinitesimal quantities, of 0,001-1 ,00 ppm, their role being to cause the start of the reaction chains.
The reaction promoters are formed at temperatures above 4000C, as a result of reactions between the reaction initiators and the polynuclear aromatic organic substances from the combustibles. The compounds resulted in these reactions are generally organic peroxides and superoxides of alkaline and earth-alkaline metals, which constitute promoters of the subsequent reactions, becoming in turn, initiators for the subsequent reactions. The main common characteristic of these promoters is the existence in the molecule of the singlet oxygen, which has a maximum affinity for singlet carbon atoms from the polynuclear aromatics.
From the reaction between the singlet oxygen of the promoters and the singlet carbon of the polynuclear aromatic molecules, result carbocations and hydride ions. The hydride ion is rejected by the flame front, and the carbocations form intermediate combinations with carbanions of transitional metals, in higher oxidation states. The carbanions give electrons and reduce their oxidation state. The carbocation molecules are broken, in turn by oxidative degradation. The reactions are repeated, till the oxidation state of the transitional metals becomes minimal. The hydride ion, by trimolecular collisions, gives electrons to the central atoms from the oxygenated compounds of metals and nonmetals (for example: SOx, NOx, MeOx) resulting protons and oxygen which form mainly water. These trimolecular collisions occur in the heterogeneous gas medium, in the combustion enclosure and between two molecules and the wall of the combustion enclosure. Most of the metal and nonmetal ions, in minimal oxidation states, do not have oxidation conditions anymore, as the temperature of the heterogeneous medium they are in drops with the move toward the evacuation zone of the combusted gases. At the drop of temperature, the reformation .of organic and inorganic substances will be more difficult, because of the decrease in the concentration of specific catalysts and because of the minimal oxidation state of metals and nonmetals in the combusted gases. The following embodiments are given.
Example 1 In the combustion air is dosed by injection at a ratio of 10"4 ÷ 10"2 of the quantity of vanadium in the combustible or in the solid combustible is mixed in an identical proportion, a composition made of, in %(weight percentage):
- Potassium orthovanadate 0.5 ÷ 2.0 %
- Demineralised water 98 ÷ 99.5 % Sulfuric acid is added for a pH between 5.5 and 6.6
Example 2
In the combustion air is dosed by injection at a ratio of 10~4 ÷ 10"2 of the quantity of vanadium in the combustible or in the solid combustible is mixed in an identical proportion, a composition made of, in %(weight percentage): - Barium orthovanadate 0.5 ÷ 2.0 %
- Demineralised water 98 ÷ 99.5 % Sulfuric acid is added for a pH between 5.5 ÷ 6.5
Example 3
In the combustion air is dosed by injection at a ratio of 10"4÷ 10'2 of the quantity of vanadium in the combustible or in the solid combustible is mixed in an identical proportion, a composition made of, in %(weight percentage): - potassium pyrovanadate 1.0 ÷ 2.0 %
- demineralised water 98 ÷ 99 % Sulfuric acid is added for a pH between 6.0 ÷ 6.5
Example 4 In the combustion air is dosed by injection at a ratio of 10'4÷ 10"2 of the quantity of vanadium in the combustible or in the solid combustible is mixed in an identical proportion, a composition made of, in %(weight percentage):
- barium pyrovanadate 1.0 ÷ 2.0 %
- demineralised water 98 ÷ 99 % Sulfuric acid is added for a pH between 6.0 ÷ 6.5
Example 5
In the combustion air is dosed by injection at a ratio of 10"6÷ 10"3 of the quantity of chromium in the combustible or in the solid combustible is mixed in an identical proportion, a composition made of: - Potassium peroxychromate 2.0 ÷ 4.0 %
- Demineralised water 96 ÷ 98.5 % Potassium hydroxide is added for a pH between 7.5 ÷ 9.0
Example 5
In the combustion air is dosed by injection at a ratio of 10"6÷ 10"3 of the quantity of chromium in trie combustible or in the solid combustible is mixed in an identical proportion, a composition made of:
- Lithium peroxychromate 2.0 ÷ 4.0 %
- Demineralised water 97 ÷ 98 % Potassium hydroxide is added for a pH between 7.5 ÷ 9.0 Example 7
In the combustion air is dosed by injection at a ratio of 10"6÷ 10"3 of the quantity of chromium in the combustible or in the solid combustible is mixed in an identical proportion, a composition made of:
- Ammonium peroxychromate 2.0 ÷ 4.0 % - Demineralised water 96 ÷ 98 % Potassium hydroxide is added for a pH between 7.5 ÷ 9.0
Example 8
In the combustion air is dosed by injection at a ratio of 10"6÷ 10"3 of the quantity of wolfram in the combustible or in the solid combustible is mixed in an identical proportion, a composition made of alkaline and earth-alkaline metal salts of isopolyacids as:
- Potassium metawolframate 2.0 ÷ 4.0 %
- Demineralised water 96 ÷ 98 % Example 9 In the combustion air is dosed by injection at a ratio of 10"6÷ 10"3 of the quantity of wolfram in the combustible or in the solid combustible is mixed in an identical proportion, a composition made of alkaline and earth-alkaline metal salts of isopolyacids as:
- barium metawolframate 2.0 ÷ 4.0 % - demineralised water 96 ÷ 98 %
Example 10
In the combustion air is dosed by injection at a ratio of 10"6÷ 10"3 of the quantity of molibden in the combustible or in the solid combustible is mixed in an identical proportion, a composition made of: - Potassium paramolibdate 2,.O ÷ 4.0 %'
- Demineralised water 96 ÷ 98 % Example 11
In the combustion air is dosed by injection at a ratio of 10"6÷ 10"3 of the quantity of molibden in the combustible or in the solid combustible is mixed in an identical proportion, a composition made of:
- Barium paramolibdate 2.0 ÷ 4.0 %
- Demineralised water 96 ÷ 98 %

Claims

1. Process for reducing the polluting emissions and the emissions of greenhouse effect gases by activating the combustibles burning, wherein in the combustible or in the combustion air are continuously injected aqueous solutions of inorganic salts of transitional metals, in 4% maximum concentration, salts representing 0,001 - 1 ,00 ppm with respect to the combustible mass entered in the system.
2. Process according to claim 1 wherein the inorganic salts of transitional metals are chosen among alkaline and earth-alkaline metal orthovanadates, in 0.5 - 2.0% concentration, in the dilute sulfuric acid solution in demineralized water, with a pH between 5.5 - 6.5, the orthovanadates representing between 10"4 and 10'2 of the vanadium quantity of the combustible.
3. Process according to claim 1 wherein the inorganic salts of transitional metals are chosen among alkaline and earth-alkaline metal pyrovanadates, in 1.0 - 2.0% concentration, in the dilute sulfuric acid solution in demineralized water, with a pH between 6.0 - 6.5, the pyrovanadates representing between 10"4 and 10"2 of the vanadium quantity of the combustible.
4. Process according to claim 1 wherein the inorganic salt of transitional metals are chosen among alkaline and earth-alkaline metal peroxychromates, in 2.0 - 4.0% concentration, in the dilute sulfuric acid solution in demineraiized water, with a pH between 7.5 - 9.0, the peroxychromates representing between 10"6 and 10"3 of the chromium quantity of the combustible.
5. Process according to claim 1 wherein the inorganic salt of transitional metals are chosen among alkaline and earth-alkaline metal salts of isopolyacids, as barium or potassium metawolframates, dissolved in 2.0 - 4.0% concentration in demineralized water, the metawolframates representing between 10"6 and 10"3 of the wolfram quantity of the combustible.
PCT/RO2007/000009 2007-02-22 2007-07-20 Process for reducing polluting emissions and greenhouse effect gas emissions, resulting from combustibles burning WO2008103063A1 (en)

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GB1438352A (en) * 1973-08-23 1976-06-03 Svenska Utvecklings Ab Fuel composition with increased octane number
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