PL249246B1 - Biomass fuel additive package - Google Patents

Abstract

The subject of the application is a package of additives for biomass fuels subjected to the agglomeration process, limiting the level of emission of toxic exhaust components, containing urea and magnesium carbonate, characterized in that it contains, based on the total mass of the additive package: from 49.0% to 51.0% (m/m) of urea, and from 49.0% to 51.0% (m/m) of magnesium carbonate, where components I and II are mixed and thoroughly homogenized.

Description

The subject of the invention is a package of additives for biomass fuels subjected to the agglomeration process, reducing the level of toxic exhaust gas components emitted during the combustion of these fuels.

STATE OF THE ART

Since the second half of the 1980s, regulations limiting the emission of harmful exhaust components into the atmosphere have been introduced and systematically tightened worldwide. The amount and type of exhaust components emitted from biomass-fired power plants depend primarily on the fuel composition, the combustion process used, and the exhaust gas treatment method. Emissions of toxic exhaust components can also be reduced by using substances added to the fuel during its production.

Patent description KR 102171528 describes a method for producing a fuel additive, in the form of hard coal mixed with other fuels, to reduce the concentration of nitrogen oxides in exhaust gases, improve the combustion process of this fuel, and improve the quality of combustion residues. Using the additive reduces the amount of fuel consumed and the amount of clinker produced, limits the formation of carbon monoxide, nitrogen oxides, sulfur oxides, and unburned substances, enables the combustion of resulting ash, and reduces the production of waste that must then be disposed of in hazardous waste landfills.

The proposed additive is used in the co-combustion of various types of pellets with hard coal: animal manure, food waste, household waste, wood pellets, in waste incineration plants, combined heat and power plants, power plants, and other energy plants. The additive consists of: 100 parts by weight of sodium silicate, 5-15 parts by weight of urea, 5-15 parts by weight of ammonium hydroxide, 5-15 parts by weight of hydrogen peroxide, 30-45 parts by weight of sodium hydroxide, 15-35 parts by weight of borax, 5-10 parts by weight of manganese urea hydroxide, 2-5 parts by weight of glycerol, 1-3 parts by weight of fatty acid ester, 2-5 parts by weight of surfactant. Analysis of the additive shows that it contains: SiO2 60 to 80 wt.%, Al2O3 5 to 15 wt.%, Fe2O3 1 to 5 wt.%, CaO 1 to 5 wt.%, Na2O 1 to 5 wt.%, K2O 1 to 5 wt.%, MgO 0.1 to 1 wt.% and Ag2O 0.5 to 10 wt.%. The mixture prepared by mixing 5 to 10 parts by weight of urea, 5 to 10 parts by weight of metal oxide and 0.5 to 1 part by weight of dispersant and 100 parts by weight of water, which were stirred for 2 hours, is responsible for reducing the concentration of nitrogen oxides in the exhaust gases. The dispersing agent used in the described additive is a water-soluble dispersion of linseed oil, polyacrylate, acrylic polymer emulsion and sulfonated polystyrene.

Patent description CN 103194292 presents a composition of additives reducing the emission of sulfur oxides and nitrogen oxides and improving the hard coal combustion process. The proprietary additive composition contains the following raw materials: 2-7 parts by weight of sodium carbonate, 1-3 parts by weight of alumina, 2-8 parts by weight of aluminum hydroxide, 2-5 parts by weight of ferric chloride, 2-6 parts by weight of iron oxide, 3-10 parts by weight of potassium permanganate, 3-10 parts by weight of potassium chlorate, 10-35 parts by weight of activated attapulgite clay, 15-30 parts by weight of urea, 2-4 parts by weight of ammonium formate, 2-4 parts by weight of ammonium chloride, 6-23 parts by weight of ammonium acetate, 3-9 parts by weight of manganese oxide, 9-12 parts by weight of copper chloride, 1-3 parts by weight of copper oxide, 2-4 parts by weight of zinc sulfate, 1-3 parts by weight Zinc nitrate, 7-18 parts by weight potassium dichromate, 1.0-1.5 parts by weight titanium dioxide, 0.5-1.0 parts by weight barium molybdate, 0.5-1.5 parts by weight cobalt sulfate, 0.5-1.5 parts by weight vanadium pentoxide, 0.3-0.7 parts by weight cerium oxide, 0.1-0.2 parts by weight sodium dodecylbenzenesulfonate, 0.1-0.2 parts by weight alkyl glyceryl ether. The composition is easy to use, has stable properties, improves the coal combustion process, leading to fuel savings of 8 to 25%, and reduces the amount of emitted sulfur and nitrogen oxides.

Patent description CN 106861431 presents the composition of a quadruple-action nitrogen compound emission-reducing additive and a method for reducing these compounds. The additive consists of the following components (in weight percent): reducing agent 50% - 78%, catalyst

15% - 30%, adsorbent 1% - 10%, accelerator 1% - 10%, dispersant 1% - 10%, activator 1% - 10%, deaeration agent 1% - 10%, sustained-release agent 1% - 10% and initiator 1% - 10%. The denitrification additive consists of the following components:

1. a reducing agent containing one or more of the following: A. an acid amide;

B. hexamethylene amide; C. alkylamine; D. cyanic acid and/or isocyanic acid or cyanic acid melamine; E. ammonium carbonate, ammonium hydrogen carbonate, urea

2. a catalyst containing one or more of the following: A. vanadic anhydride and titanium dioxide and a mixture thereof; B. manganese dioxide; C. carbon black, activated carbon, activated coke, carbon fiber and a mixture thereof

3. an adsorbent containing diatomaceous earth, a mixture of sepiolite or diatomite and sepiolite

4. the accelerator consists of a mixture of iron oxides Fe2O3 and Fe3O4

5. dispersant contains fly ash

6. the activator contains rare earth elements

7. the release extender contains kaolin

8. an initiator containing one or more of the following: A. sodium oxide, molybdenum oxide, sodium hydroxide, sodium carbonate, sodium bicarbonate; B. potassium oxide, potassium hydroxide, potassium carbonate; C. magnesium oxide, magnesium hydroxide, magnesium carbonate, magnesium bicarbonate.

Patent description US10465137 claims a process for reducing nitrogen oxide emissions from hard coal combustion.

This process, in the first version, consists of: mixing fuel with an additive containing nitrogen compounds and burning the fuel prepared in this way, producing exhaust gas containing nitrogen oxides and derivatives of nitrogen compounds, where these derivatives reduce the amount of nitrogen oxides in the exhaust gases.

In the second version, the process of reducing nitrogen oxide emissions claimed in this patent description includes: mixing fuel with an additive that produces ammonia during combustion and mixing fuel with a halogen-containing additive that produces halogen in the gas phase during combustion.

In the third version, this process includes the stages of combustion of fuel causing nitrogen oxide emissions and the introduction of nitrogen-containing substances into the combustion zone to reduce nitrogen oxides.

A nitrogen compound in this description is a substance containing amine and/or amide groups that thermally decompose into ammonia. Most often, this compound is urea or polymerized methylene urea. It can be dosed in powdered form with a mesh size of about 6 to about 20, or less than 60. It can also be dosed in combination with other compounds such as zeolites, metal silicates, clay, activated carbon, graphite, and fly ash. The fuel contains from about 0.05 to about 1 wt.%, most often from about 0.05 to about 0.75 wt.%, of an additive containing a nitrogen compound, and the mass ratio of nitrogen to halogen in the fuel is in the range of about 1.1 to about 2400:1.

US20200332213 patent discloses an additive composition and a method for controlling nitrogen oxide emissions by adding the composition to fuel prior to combustion in a pulverized coal boiler system. The process comprises: mixing fuel with an additive composition containing a heat-stable agent to produce an upgraded fuel, wherein the fuel, in the absence of the heat-stabilizing agent, is unstable when burned; and burning the upgraded fuel to produce a contaminated gas stream containing the additive composition or derivatives thereof, wherein the additives or derivatives thereof remove or cause the removal of pollutants from the exhaust gas. The additive composition that reduces nitrogen oxide emissions is one or more halogen compounds, nitrogen, and activated carbon; the nitrogen compound may be ammonia, an amine, an amide, cyanuric acid, urea, or mixtures thereof. The heat-stabilizing agent may be a metal hydroxide, a metal carbonate, a metal bicarbonate, ash, or mixtures thereof. Additionally, the additive composition may contain a dispersing and/or stabilizing and/or binding substance.

Patent description CN102517120 discloses the composition of a coal additive that contains the following ingredients: 10-15 wt.% sulfur-binding substances, 20-40 wt.% oxidizers, 10-15 wt.% catalysts, and 30-50 wt.% leavening substances. The leavening substances may be sodium chloride and/or perlite powder. The described additive improves boiler thermal efficiency by over 22%, reduces coal consumption by over 23%, and has a positive effect on the reduction of sulfur and nitrogen oxides emissions. The fuel coal additive contains the following substances: 10-15 wt.% sulfur-binding substance, which is calcium oxide; 20-40 wt.% an oxidizer consisting of a mixture of potassium permanganate, potassium chlorate and potassium perchlorate, and the mass ratio of potassium permanganate, potassium chlorate and potassium perchlorate is (5-10) : (5-10) : (10-15); 10-15 wt.% of a catalyst which is ferrocene; 30-50 wt.% of a raising agent consisting of sodium chloride and perlite, and the mass ratio of sodium chloride and perlite is (15-20) : (15-30).

Patent description KR101697716 discloses the composition of an additive composition for solid fuels such as coal or coke, which increases the efficiency of fuel combustion, effectively prevents slagging, ensures easy removal of by-products such as clinker, and at the same time effectively reduces the formation of solid particles, nitrogen oxides, and sulfur oxides. The composition includes the following substances: magnesium oxide in an amount of 2 to 10% by weight of the total composition; a petroleum-based mineral oil, which may be a paraffin oil modified by hydrotreating and/or dewaxing; nanoparticles of aluminum, vanadium, and tin hydroxides with a particle size of 10 to 500 nm; at least one inorganic peroxide selected from the group consisting of metal salts and borates and metal salts and carbonates, which may be an ammonium salt of an organic acid with 5 to 10 carbon atoms. The composition of additives for solid fuel is characterized by the fact that its use allows for the reduction of NOx emissions by 40% or more, and the degree of SOx reduction is 20% or more.

Patent description CN 104845697 presents the composition and method for producing briquettes from municipal waste. Biomass briquettes consist of municipal waste residues and additives, the additives including a combustion modifier containing caustic soda, lime, and bentonite, wherein the weight proportion of caustic soda, lime, and bentonite is 0.5:4.5:5.0; a combustion enhancer containing powdered iron ore, powdered bauxite, magnesia, ammonium perchlorate, and powdered feldspar, wherein the weight proportion of iron ore, bauxite, magnesia, ammonium perchlorate, and feldspar is 5.0:1.0:3.5:0.1-0.2:0.5; auxiliary materials that increase the calorific value of the briquettes, e.g., coal. The described fuel from municipal waste has the advantage of being composed of solid particles and can be processed into briquettes of various specifications and shapes according to market and user requirements. The fuel particles have a uniform size, large contact surface area, good permeability, and high flammability, and can replace raw coal. The soot produced by burning this fuel is better than that of coal fuel, and the ash can be used for the production of construction materials or for landfill.

Patent KR 101586430 describes a composition of additives that improve the combustion process of biomass pellet fuel, coal fuel, or waste fuel. The purpose of using the additive composition is to improve combustion efficiency and prevent environmental pollution. This is achieved by optimizing combustion time and reducing the amount of clinker produced during incomplete combustion, which reduces waste treatment costs and prevents environmental pollution. The additive can be used with fuel derived from farm animal manure, food waste, household sewage sludge, wood waste, and recycled waste. According to the above-mentioned invention, the composition of fuel additives improving the burning rate of pellets contains: 5-15 parts by weight of hydrogen peroxide, 30-45 parts by weight of sodium hydroxide, 1-10 parts by weight of borax, 10-50 parts by weight of hydrogen peroxide, 2-5 parts by weight of glycerol, 1-3 parts by weight of fatty acid ester, 2-5 parts by weight of surfactant, 10-30 parts by weight of sodium silicate ceramic balls.

The aim of the present invention is to obtain a package of additives for biomass fuels subjected to the agglomeration process, reducing the level of emission of toxic exhaust components emitted during the combustion of these fuels, which package of additives is characterized by high efficiency in reducing emissions generated during the combustion of biomass fuels: nitrogen oxides, organic carbon compounds, carbon monoxide (II) and sulfur oxides.

It was unexpectedly found that the package of additives for biomass fuels subjected to the agglomeration process, in accordance with the present invention, has such properties, limiting the level of emission of toxic exhaust components emitted during the combustion of these fuels.

THE ESSENCE OF THE INVENTION

A package of additives for biomass fuels subjected to the agglomeration process, limiting the level of emission of toxic exhaust components emitted during the combustion of these fuels, according to the present invention, containing urea and magnesium carbonate, is characterized in that it contains, calculated on the total mass of the additive package:

PL 249246 Β1

I. from 49.0 to 51.0% (m/m) of urea, and

II. from 49.0 to 51.0% (m/m) of magnesium carbonate.

Components I and II are mixed together and thoroughly homogenized.

For the purposes of this invention, agglomeration should be understood as the process of densification or compaction in order to obtain pellets or briquettes.

It turned out during the tests that adding a package of additives to biomass fuels subjected to the agglomeration process allows for reducing emissions into the atmosphere from their combustion: nitrogen oxides by about 83%, organic carbon compounds by about 90%, carbon monoxide (II) by about 91% and sulfur oxides by about 94% compared to the level of emissions of the above-mentioned compounds from the combustion of biomass fuels without the additive package; moreover, the additive package is more effective in reducing emissions into the atmosphere of nitrogen oxides by about 21% and sulfur oxides by about 39% than urea used as an individual additive.

The present invention is presented in Examples 1 to 4, illustrating the composition, method of production, and effectiveness of reducing toxic exhaust emissions by using an additive package in the combustion process of agglomerated biomass fuels in test trials. Therefore, they cannot be considered as limiting the scope of the invention, as they are illustrative only. Examples 1 and 2 are comparative examples.

EXAMPLES

Example 1 - comparative example

6000 g of coniferous sawdust with the properties given in Table 1, 3000 g of sunflower husks with the properties given in Table 2, and 1000 g of dry sewage sludge with the properties given in Table 3 were weighed, then all ingredients were thoroughly mixed and granulated in a ZLSP-150B pelletizing machine from Haven Polska Sp. z o.o. using a matrix with a mesh diameter of 6 mm.

Table 1. Characteristics of coniferous wood sawdust used for testing

Name of the marking, test method Unit Value Appearance — characteristic Moisture content % 11.2 Ash content % 0.3 Calorific value MJ/kg 21.54

Table 2. Characteristics of sunflower husks used for research

Name of the marking, test method Unit Value Appearance — characteristic Moisture content % 12.6 Ash content % 3.6 Calorific value MJ/kg 16.09

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Table 3. Characteristics of dry sewage sludge used for testing

Name of the marking, test method Unit Value Appearance — dark gray powder Moisture content % 11.0 Ash content % 35.1 Calorific value MJ/kg 12.1

Example 2 - comparative example

6000 g of coniferous sawdust with properties in Table 1, 3000 g of sunflower husks with properties in Table 2, 1000 g of dry sewage sludge with properties in Table 3, and 100 g of urea with properties in Table 4 were weighed. All ingredients were thoroughly mixed. The resulting sample was granulated in a ZLSP-150B pelletizing machine from Haven Polska Sp. z o.o. using a matrix with a mesh diameter of 6 mm.

Table 4. Characteristics of urea used for testing

Name of the marking, test method Unit Value Appearance — white powder pH (10% solution), 20 ^uC — 8, ,5 Density kg/ ^dm3 1,335 Bulk density kg/ ^dm3 0.75

Example 3

6000 g of coniferous sawdust with properties given in Table 1, 3000 g of sunflower husks with properties given in Table 2, and 1000 g of dry sewage sludge with properties given in Table 3 were weighed and thoroughly mixed. 50 g of urea with properties given in Table 4 and 50 g of magnesium carbonate with properties given in Table 5 were weighed and thoroughly mixed. The components were combined with a prepared additive package containing urea and magnesium carbonate. All ingredients were thoroughly mixed. The resulting sample was granulated in a ZLSP-150B pelletizing machine from Haven Polska Sp. z o.o. using a matrix with a mesh diameter of 6 mm.

Table 5. Characteristics of magnesium carbonate used for testing

Name of the marking, test method Unit Value Appearance — white powder pH (5% suspension), 20°C — 10.5 Density kg/ ^dm3 2.16 Bulk density kg/ ^dm3 0.29

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Example 4

Combustion tests of the products from examples 1 to 3 were carried out in a pellet stove model AIRPELL 8 by Defro with a nominal thermal power of 8 kW.

During the tests, the following exhaust gases were measured: oxygen, carbon monoxide, carbon dioxide, nitrogen oxides, sulfur dioxide, and organic carbon compounds. Exhaust gases for analysis of harmful substances were collected from nozzles installed in the measuring section connecting the heater to the chimney. An MRU ECU 3000 gas analyzer was used to measure carbon monoxide and sulfur dioxide in accordance with the PN-EN 14785:2009 standard, as well as nitrogen oxides in accordance with the PN-EN 303-5:2012 standard. A Thermo-FID TG gas analyzer was used to measure organic carbon compounds in accordance with the PN-EN 303-5:2012 standard.

The determined results of the composition of exhaust gases emitted during the combustion of products from examples 1 to 3 are presented in Table 6.

In accordance with the requirements of the PN-EN 14785:2009 standard and the COMMISSION REGULATION (EU) 2015/1185 of 24 April 2015 implementing Directive 2009/125/EC of the European Parliament and of the Council with regard to requirements for solid fuel local space heaters, the measured substance values in the flue gases were converted to 13% oxygen content.

Table 6. Composition of exhaust gases emitted from the combustion process of products from examples 1 to 3

Exhaust gas component Iunit Product from example 1 Product from example 2 Product from example 3 N0x converted Lpplllj 408.4 90.0 71.2 CO converted [ppm] 1434.9 136.6 124.2 SO2 converted to ippm 158.6 16.0 9.8 organic carbon compounds converted [lii g/ηΐθ] 93.3 7.4 9.5

The above examples present the composition of a package of additives for biomass fuels subjected to the agglomeration process according to the invention and demonstrate its effectiveness in reducing the emission of toxic exhaust gas components in the combustion process of biomass fuels refined with the additive package in test samples, proving its industrial applicability.

Emissions of toxic exhaust gas components from the combustion of biomass fuels subjected to the agglomeration process and refined with the additive package according to the invention were compared with emissions from the combustion of biomass fuels not containing the additive package.

Claims (1)

1. A package of additives for biomass fuels, limiting the level of emission of toxic exhaust components, containing urea and magnesium carbonate, characterized in that it contains, calculated on the total mass of the additive package: I. from 49.0 to 51.0% (m/m) of urea, and II. from 49.0 to 51.0% (m/m) of magnesium carbonate.