Classifications

• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L9/00—Treating solid fuels to improve their combustion
  • C10L9/10—Treating solid fuels to improve their combustion by using additives
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L9/00—Treating solid fuels to improve their combustion
  • C10L9/10—Treating solid fuels to improve their combustion by using additives
  • C10L9/12—Oxidation means, e.g. oxygen-generating 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L2200/00—Components of fuel compositions
  • C10L2200/02—Inorganic or organic compounds containing atoms other than C, H or O, e.g. organic compounds containing heteroatoms or metal organic complexes
  • C10L2200/0204—Metals or alloys
  • C10L2200/0209—Group I metals: Li, Na, K, Rb, Cs, Fr, Cu, Ag, Au
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L2200/00—Components of fuel compositions
  • C10L2200/02—Inorganic or organic compounds containing atoms other than C, H or O, e.g. organic compounds containing heteroatoms or metal organic complexes
  • C10L2200/0204—Metals or alloys
  • C10L2200/024—Group VIII metals: Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L2200/00—Components of fuel compositions
  • C10L2200/02—Inorganic or organic compounds containing atoms other than C, H or O, e.g. organic compounds containing heteroatoms or metal organic complexes
  • C10L2200/0272—Silicon containing 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L2200/00—Components of fuel compositions
  • C10L2200/02—Inorganic or organic compounds containing atoms other than C, H or O, e.g. organic compounds containing heteroatoms or metal organic complexes
  • C10L2200/029—Salts, such as carbonates, oxides, hydroxides, percompounds, e.g. peroxides, perborates, nitrates, nitrites, sulfates, and silicates

Definitions

• the subject-matter of the invention is the ecological solid fuel additive, reducing soot formation.
• the fuel additive for soot combustion applied in operations of hard coal, lignite, fine coal, coke, anthracite, peat, pellets, coal briquettes and wood-burning furnaces as well as low, medium and high efficiency furnaces and boilers.
• the effective fuel additive allowing for reduction by deposit volume at the exchanger by 45- 55% is known from the Chinese patent CN 1010483.
• the fuel additive is a mixture of potassium nitrate (60-80%), ammonium nitrate, triiron tetroxide (0.1-1.0%), charcoal, borax, trisodium phosphate as chelating agent, magnesium, aluminum, sodium chloride and powdered sulphur.
• the additive is used in household and industrial installations and industrial coal-burning boilers.
• the additive modifies chemical and physical soot properties improving at the same time heating efficiency of the heat exchanger.
• the fuel additive is decomposable in 485°C, forming a coating on the heat exchanger surface and protecting it against corrosion.
• Coal additive to coal of low calorific value known from the Chinese CN 103305313 patent description contains 20-100% of active substance.
• Mixture of active substances contains 30- 80% in weight of calcium cobaltite (Ca 3 Co 4 0 9 ), 0-30% in weight of triiron tetroxide (Fe 3 0 4 ) and cerium dioxide (Ce0 2 ) and potassium oxide of several percents in weight.
• the fuel additive revealed in this invention decreases the fuel ignition temperature by 3-15°C, enhancing the combustion effectiveness and making coal combustion with fuel additive less polluting to the air comparing to fuel combustion without the fuel additive.
• soot combustion catalysts containing copper sulphate, sodium chloride and ammonium chloride are known from PL 207482 and PL 165406 patent description. Despite its advantages in combustion of lesser quantities of coal and lower risk of carbon deposities ignition in the flue pipes, this is not environmentally safe operation.
• the solid biomass additive containing among others the carboxylic acid salts and one or more metals from among the alkaline earth, lanthanide and ferrous metals; fatty acid esters and fatty acids or acidic resins, is known from the EP 0 725 128 B l patent.
• the fatty acid esters are, advantageously, methyl esters, in particulars of rape oil esters.
• the described additive enhances mechanical properties of biomass in the course of processing and reduces production of toxic fumes.
• the disadvantage of the described solution is no opportunity to apply the additive to any other fuels than pulverized one.
• Known fuel additives may be harmful to the environment (copper and chlorine compounds), cause excessive corrosion of boiler and flue pipes (chloride and sulphur compounds, fatty acid oxy-degradation products) and have pathogenic effect (cerium compounds).
• the subject-matter of the invention is the ecological solid fuel additive, composed of triiron tetroxide, nitrates, most frequently potassium nitrate(V) containing 30-60% in weight of triiron tetroxide (Fe 3 0 4 ), 10-30% in weight of potassium nitrate(V) (KN0 3 ), sodium nitrate(V) (NaN0 3 ), ammonium nitrate(V) (NH 4 N0 3 ), or mixture of the abovementioned nitrates(V), 5-30% in weight of sodium percarbonate (Na 2 C0 3 - 1,5H 2 0 2 ) and 10% in weight of anti-caking agent.
• the anti-caking agent is powdered burnt clay.
• Fe 3 0 4 used for fuel additive production is free from FeS0 4.
• soot production and toxic compounds present in soot is limited.
• Ecological solid fuel additive reducing soot production presented in the invention is a proposal for environment-friendly solid fuel combustion, preventing environmental contamination with soot accompanying pollutants such as: polyaromatic hydrocarbons (PAH), persistent organic radicals and heavy metals, whereas reduction of carbon black production prevents additionally the excessive fuel consumption (carbon black decreases the heating efficiency of a boiler) and increases combustion effectiveness.
• PHA polyaromatic hydrocarbons
• carbon black decreases the heating efficiency of a boiler
• Solid fuel additive according to the invention is characterized by that it contains 30-60% in weight of triiron tetroxide (Fe 3 0 4 ), 10-30% in weight of potassium nitrate(V) (KN0 3 ), sodium nitrate(V) (NaN0 3 ), ammonium nitrate(V) (NH 4 N0 3 ), or mixture of the abovementioned nitrates(V), 5-30% in weight of sodium percarbonate (Na 2 C0 3 - 1,5H 2 0 2 ) and 10% in weight of anti-caking agent e.g. powdered burnt clay.
• Triiron tetroxide Fe 3 0 4
• KN0 3 potassium nitrate(V)
• NaN0 3 sodium nitrate(V)
• NH 4 N0 3 ammonium nitrate(V)
• anti-caking agent e.g. powdered burnt clay.
• FeS0 4 may act as the raw material for Fe 3 0 4 production, which explains its presence). FeS0 4 presence in small quantities does not change the activity of fuel additive towards reducing the carbon black production, however carbon black obtained in presence of even small quantities of FeS0 4 is significantly less biodegradable (negative environmental impact).
• the additive according to the invention introduced to the combustion chamber with fuel or at the surface of the combusted fuel, is subject to partial thermal decomposition and releases the larg volume of gaseous products.
• Fuel additive components are activated in the temperature range of 80-650°C.
• Gaseous products of nitrates and sodium percarbonate decomposition reaction transport part of Fe 3 0 4 quantity onto the carbonaceous deposite surface covering the heat exchanger.
• Fe 3 0 4 particles in contact with heated fuel reach high temperature and then are transported on the carbonaceous deposite surface along with flue gas, where using its energy and catalytic oxidation properties catalyze the reaction of complete and total fuel combustion for hours.
• Decomposition of sodium percarbonate produces the peroxide and hydroxyl radicals, which, by means of chain reactions, are able to initiate the carbon black oxidation reaction.
• the chemical composition of the produced carbon black changes advantageously, in effect of which it contains less harmful substances. Modification of the composition in result of application of the ecological fuel additive facilitates biodegradation of substances contained in the carbon black, including cancerogenic polyaromatic hydrocarbons (PAH).
• PAH cancerogenic polyaromatic hydrocarbons
• the additive according to the invention should be used in quantity of 0.5-2 kg per 1000 kg of fuel, advantageously 1.2 kg per 1000 kg of fuel in the case of application of additive in mixture with fuel.
• Chemical composition of the additive is decisive for its value, however its dose i.e. weight proportion of the additive to fuel unit (1000 kg) is almost of equal importance.
• the sufficient quantity is 50 g of additive in weekly intervals. In the cases of tendency of the heat exchanger to intensive covering with deposite resulting from quality of combusted fuel or the structure of heating installation, it is necessary to increase the fuel additive dose or its more frequent application.
• the additive and produced carbon black is more environment- friendly. Combustion is more complete and produces less waste and smaller quantities of carbon black, which is additionally less toxic. There is also more energy produced.
• Solid fuel additive (coal, briquettes, etc.) according to the invention is a better ecological product than the additives in the composition, containing also: copper, chlorine, sulphur or fatty acids.
• the most significant pro-ecological effect of the fuel additive according to the invention is reduced carbon black production i.e. cancerogenic substance causing a greenhouse effect, carrier of polyaromatic hydrocarbons, stable organic radicals and heavy metals. Carbon black is also a pathogenic agent (circulatory and respiratory system diseases).
• Carbon black is a chemical and physical pollutant of air, water and soils, therefore its reduction constitutes a significant component of air protection programmes as well as the low emission reduction programmes (LERP).
• LEP low emission reduction programmes
• soot is a powerful absorbent of sunlight and contributes to climate warming and melting of glaciers covered with so called dry deposition (particulates) causing the greenhouse effect.
• Ecological effect of the additive according to the invention results also in lowering the combustion temperature and quantity of produced combustion gases, whereas the limited amount of produced soot is both less toxic and its components are biodegradable, and demonstrates the properties stimulating plant growth, including biomass increase.
• Figure 1 presents comparison of the content of the total of 4 components of soot sample determined using the HS-GC-MS method in the soot biodegradtion studies of two carbon black types
• Figure 2 presents the impact of carbon black (5% v/v) on the rate of occurrence of visible cotyledons of A. thaliana.
• NM carbon black - carbon black without fuel additive B carbon black - carbon black with added commercially available additive containing significant quantities of NaCl and copper, A carbon black - carbon black with fuel additive according to the invention;
• Figure 3 presents the impact of carbon black (5% v/v) on the rate of occurrence of the first leaf pair of A. thaliana. NM carbon black - carbon black without fuel additive, B carbon black - carbon black with added commercially available additive containing significant quantities of NaCl and copper, A carbon black - carbon black with fuel additive according to the invention;
• Figure 4 presents the impact of the studied types of carbon black (5% v/v) on mass increase of A. thaliana upon 2 and 4 weeks of cultivation.
• NM carbon black - carbon black without fuel additive B carbon black - carbon black with added commercially available additive containing significant quantities of NaCl and copper, A soot - carbon black with fuel additive according to the invention;
• Figure 5 presents the impact of the tested soot types (5% v/v) on pigment content in A. thaliana upon 4 weeks of cultivation.
• NM carbon black - carbon black without fuel additive B carbon black - carbon black with added commercially available additive containing significant quantities of NaCl and copper, A carbon black - carbon black with fuel additive according to the invention;
• Figure 6 presents the graph of A. thaliana superoxide dismutases (SOD) activity upon native electrophoresis and histochemical staining of control plant homogenates (NM carbon black - carbon black without fuel additive, A carbon black -with newly-invented fuel additive, B carbon black - carbon black with added commercially available additive containing significant quantities of NaCl and Cu compounds);
• SOD superoxide dismutases
• Figure 7 presents the graph of fuel additive composition optimization - cubic model verification
• Figure 8 presents TGA and DSC thermograms of carbon black and carbon black with fuel additive samples
• Figure 9 presents the DP thermogram (red line - DSC, black line - TGA);
• Figure 10 presents the thermovision image of Hercules auxiliary furnace (upon 8h from ignitron), whereas Figure 11 presents the thermovision image of SAS MI fine-coal auxiliary furnace (upon 10 hours from ignition).
• the subject-matter of the invention is presented by the following examples of embodiment. Example 1.
• the fuel additive Upon mixing the components the fuel additive was obtained.
• the additive was introduced onto the surface of combusted fuel in coal boiler of 29 kW capacity. Quantity of carbon black covering the heat exchanger decreased 8 times, comparing to analogous combustion conditions without the additive. Thanks to this the chimney heat losses were reduced and fuel consumption was decreased. Soot deposited on the heat exchanger has lower carbon content and higher mineral component content (fly ash), comparing to carbon black produced during fuel consumption without the fuel additive.
• Application of fuel additive enables easier removal of deposits from heat exchanger. In addition it was observed that application of fuel additive reduces emission of nitrogen oxides in the flue gas.
• Carbon black composition on the basis of elementary analysis was as follows:
• Carbon black produced upon combustion of coal with no additives 50.54% in weight of coal
• Carbon black upon application of fuel additive coal 39.60% in weight, hydrogen 10.92% in weight, nitrogen 5.39% in weight.
• Carbon black composition upon application of commercially available fuel additive based on CuS0 4 and NaCl coal 44.66%, hydrogen 7.47%, nitrogen 5.01% (in weight).
• the remaining components include non-organic matter ( fly ash).
• the fuel additive was obtained.
• the additive was introduced onto the surface of combusted fuel in coal boiler of 29 kW capacity.
• Quantity of carbon black covering the heat exchanger decreased 8 times, thanks to which the chimney heat losses were reduced and fuel consumption was decreased.
• Soot deposited on the heat exchanger has lower carbon content and higher mineral component content ( fly ash), comparing to carbon black produced during fuel consumption without the fuel additive, which enabled easier removal of deposits from heat exchanger.
• application of fuel additive reduces emission of nitrogen oxides in the fumes.
• the fuel additive was obtained.
• the additive was introduced onto the surface of combusted fuel in coal boiler of 29 kW capacity. Quantity of carbon black covering the heat exchanger decreased 5 times.
• the fuel additive was obtained.
• the additive was introduced onto the surface of combusted fuel in coal boiler of 29 kW capacity. Quantity of carbon black covering the heat exchanger decreased 5 times.
• the other types of carbon black used in the description include:
• carbon black with fuel additive available on the market is based on NaCl and copper (name not provided on purpose).
• the additive according to the invention in contrary to the other additives available on the market, is based on iron compounds, more environmental friendly comparing to copper compounds demonstrating specific toxicity to environmental microflora.
• the flasks with BSM nutrient medium and relevant type of carbon black were placed in the batch retort. After sterilization one of each type of the flasks with relevant type of carbon were left as control sample (no bacteria), whereas the remaining two containing the same type of carbon black were filled with the same amount of cells of one of two bacterial strains (A or B, the principle of standardization of the number of cells in inoculum was described in Example 6). The cultures were kept in darkness to prevent possible photolysis of sample components and incubated for 4 weeks (30 2 C, RPM 150). The test was repeated 10 times.
• control samples i.e. containing the relevant type of carbon black however with no bacteria added, were filtered. All residues on the filters and weighted portions of carbon black were analyzed using the Headspace Gas Chromatography/Mas s Spectrometry (HS-GC-MS) after app. 15 minutes of vials thermostating in temperature 150 2 C directly before inoculation (50 ⁇ ).
• the dispenser temperature was set to 250 2 C, carrier gas stream proportion (helium) was 10: 1, column flow was 1 ml/min, whereas linear speed amounted to 36 cm/sec.
• the analysis used the programmable temperature change method: 60 2 C for 1 minute, temperature increase by 10 2 C/minute until the maximum temperature of 250 2 C (maintained for 1 minute) was reached.
• the tested plant was thale cress (Arabidopsis thaliana).
• Arabidopsis thaliana is a model plant commonly used in genetic tests (known genome) as well as biochemical, physiological and toxicological tests (certain standards in the area of assessment of different pollutants' phytotoxicity, including PAH recommend this species).
• genetic tests known genome
• biochemical, physiological and toxicological tests certain standards in the area of assessment of different pollutants' phytotoxicity, including PAH recommend this species.
• the plant was subject to the activity of three types of carbon black:
• Arabidopsis thaliana seeds were sterilized as follows in the eppendorf test-tube:
• the plants cultivated on the nutrient medium with B carbon black featured weaker growth among the plants treated with three types of carbon blacks.
• average height of A. thaliana cultivated in presence of this carbon black decreased along with its increasing concentration in the nutrient medium, in effect of which upon 14 days, at the highest concentration of carbon black, the plant height exceeded the control plants only by 5%.
• composition of the most important group of photosynthetic pigments i.e. chlorophyll a, b and carotenoids. These pigments are necessary for proper course of photosynthesis and condition the effective conversion of luminous energy into hydrocarbons. Pigments deficiencies or irregularities in their proportion decrease the photosynthetic efficiency and therefore widely-understood plant production.
• Pigment content was measured in four-week leaves of A. thaliana by sampling 4 leaves from each plant, homogenization and extraction of pigments with 80% (v/v) acetone solution.
• absorbance of the obtained extract was measured using the Jasco V-650 spectrophotometer at the following wavelengths: 662nm, 645nm and 470nm (Lichtenthaler method, 1987):
• the additive according to the invention stimulates plant photosynthetic pigment production, including valuable for health carotenoids, which is advantageous in context of plant growth, productivity and nutritive values.
• e) impact of carbon black on anti-oxidative enzymes activity Impact of A, B and NM carbon blacks on the activity of anti-oxidative enzymes was studied on 8-week plants.
• the tested enzymes were superoxide dismutases (SOD), being the metalloproteins protecting the cellular structures against oxidative stress. Depending on the bonded co-factor, they may have the form of copper/zinc, iron or manganese dismutases.
• SOD superoxide dismutases
• A. thaliana contains the genes of all the above-mentioned forms.
• Copper/zinc dismutases CuZnSOD are localized primarily in the chloroplasts, peroxisomes and cytosol, whereas Iron dismutases (FeSOD) are present in chloroplasts and manganese dismutases (MnSOD) in mitochondria and peroxisomes (K Kunststoffenstein et al. 1998, Malecka & Tomaszewska 2005). Enzyme activity was tested using the native electrophoresis with histochemical staining method. Electrophoresis was carried out on polyacrylamide gels (11.6% (bottom) and 0.8% (upper)) at 180V in 4°C. Upon electrophoresis, the gels were subject to 30-minute staining to detect SOD activity (Miszalski et al. 1998).
• the additive according to the invention applied in the production of carbon black A does not increase the oxidative stress in plant cells, both in plants not treated with carbon black (control) and growing in presence of carbon black produced with no additive.
• Experiments #1-10 result from the experiment plan (simplex plan, grade 3 ⁇ 3;3 ⁇ ).
• Experiments #11 and 12 were used to develop a mathematical model and optimize the experiment towards the extreme (minimum) of the objective function, physical sense of which corresponds to the lowest coverage of heat exchanger with deposited soot.
• Fig. 7 presents the graph illustrating that the lowest coverage of heat exchanger is obtained when the chemical composition of the additive ranges between points #4, 5, 10 and 11.
• f ( ) 48.90x+37.76y+36.13z-82.40xy-89.06xz-42.61yz+27.38xyz-81.30xy(x-y)- -93.15xz(x-z)+90.22yz(y-z) (formula 1)
• Fig. 8 features the thermogravimetric analysis curves and differential scanning calorimetry (DSC) analysis curves, performed for the carbon black samples (black line) and carbon black with fuel additive (red line).
• DSC differential scanning calorimetry

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• Combustion & Propulsion (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Chemistry (AREA)
• Solid Fuels And Fuel-Associated Substances (AREA)

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Citations (8)

• 2015
  • 2015-07-23 PL PL413233A patent/PL231237B1/pl unknown
  • 2015-09-23 WO PCT/IB2015/057335 patent/WO2017013476A1/en not_active Ceased
  • 2015-09-23 EP EP15787013.0A patent/EP3325581B1/en active Active

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