SK287202B6 - Fuel mixture - Google Patents

Abstract

The object of the invention is a fuel mixture contains 9 to 99.97 weight. %. of glycerol, 0.01 to 90 weight %. of organic compounds with the calorific value in the range of 5 to 45 MJ.kg-1, 0.01 to 40 weight %. of inorganic compounds, which cation or anion in the compound is not bounded to the hydrocarbon chain or hydrocarbon cycle, and 0.01 to 40 weight %. of water H2O. The fuel mixture is liquid and has a total calorific value in the range of 5 to 42 MJ.kg-1.

Description

Technical field

The invention relates to a fuel mixture in particular for cement kilns, glass furnaces, glass and glass products, enamels, glazes, lime, gypsum and anhydrite binders, siderite decarbonisation, dehydration, dehydroxilization and aluminum hydroxide firing, calcination A1 ₂ O ₃ , magnesite clinker and products thereof, magnesium -ospinel, magnesium-chromium and other products based on MgO and its compounds, fireclay, sillimanite, mullite, corundum and dinas products, refractory materials and fittings, products of fused basalt, pottery products, pottery products, porcelain, earthenware, ceramics, ceramic coverings, wall and floor tiles, bricks and fittings and other products of the silicate and chemical industries, for heating plants of thermal power plants and heating plants, or of drying plants in the given sectors.

BACKGROUND OF THE INVENTION

To strengthen energy self-sufficiency, EU Member States are increasingly placing emphasis on the use of renewable energy sources. The EU's ambitious target for 2010 is to achieve a 12% share of renewable energy sources in total energy consumption in energy, transport and industrial production in line with the Sustainable Development Strategy.

Another EU objective is to reduce greenhouse gas emissions by 8% over the period 2008-2012 compared to 1990 under the commitment of the Kyoto Protocol to avoid climate change problems causing global warming of the Earth's atmosphere. Greenhouse gases include fluorinated hydrocarbons, N ₂ O, SF ₆ and especially CH ₄ and CO ₂ . Methane CH ₄ is formed and released in large quantities by the decomposition of organic biodegradable substances deposited in landfills for municipal and industrial waste. The source of much of the _CO2 is energy (thermal power plants, heating plants, domestic heating), transportation, industrial activity, production of building binders (cement and lime), ceramic and glass, metals, steel production.

One of the solutions to these global energy and environmental problems is to use biomass and waste containing it as a renewable energy source and CO ₂ neutral fuel in industry, energy and transport. The combustion of biomass as a renewable energy source is also supported by EU legislation - Directive 2001/77 / EC. Biofuel-based biofuels have a major contribution to reducing CO ₂ emissions, as CO ₂ emissions do not increase, but are consumed relatively quickly to generate and grow additional biomass. About 100 billion tons of CO ₂ are bound to organic matter on earth all year round, which is about 1/7 of the CO ₂ content in the air, and an additional 100 billion will only "pass" through the plants as an energy source to sustain their lives. However, all plant-bound CO ₂ is returned to the air sooner or later - to a lesser extent by burning, to a greater extent by rotting, thus maintaining the CO ₂ cycle. Biofuels can effectively replace natural non-renewable fossil fuels in both industry and energy, and now in transport. The use of biofuels in transport will promote a reduction in dependence on oil in the production of motor fuels. The promotion of the use of biofuels or other renewable fuels in transport is legally included in Directive. 2003/30 / EC. The indicative biofuel targets under the Directive are 2% at the end of 2005 and 5.75% at the end of 2010, calculated on the basis of the energy content of motor fuels, and it is expected that the share of biofuels will continue to increase after 2010. Energy legislation in the Slovak Republic already takes into account all currently valid EU legislation, which resulted in the implementation of the “National Program for the Development of Biofuels”. According to global forecasts, the role of agriculture as a producer of renewable energy sources will increase.

Such biofuels commonly used in transport abroad are methanol, ethanol, biodiesel methyl ester or ethyl ester of higher fatty acids from vegetable oils. Biogas consisting mainly of methane (60-70%) and carbon dioxide (30-40%) is a valuable fuel and is produced by the process of anaerobic extraction of organic residues, takes place in tanks without access to air, but biogas is of marginal importance in transport; potential is particularly useful in the energy sector. This production is promising especially for agricultural cooperatives, sewage treatment plants or municipal waste dumps, where so-called. sludge gas.

The production of alcohol (methanol and ethanol) from biomass for technical purposes has been known since the 1930s. Bioethanol is produced from starch and sugar rich cuttings, or from cellulose-containing biomass. More than 20 years of experience with ethanol in Brazil and the US have shown that its use has brought several benefits not only in transport but also in the industrial and social spheres. The production of biomethanol from wood has been known for a long time in the world. Methanol can be produced not only from biomass, but also from some fossil fuels such as. from natural gas or coal. They have experience with the frame in the US.

Biodiesel has the greatest potential for biofuels in the EU countries, especially considering that up to 90% of goods and passenger transport is currently carried out by means of diesel - fueled vehicles (trucks, buses, locomotives, ships, tractors, etc.) . In addition, there are a large number of diesel-powered passenger cars that could also use biodiesel. In the EU countries, their share in the total number of vehicles ranges from 15 to 40%.

Biodiesel - methyl ester of vegetable oils is produced by esterification of higher fatty acids derived from oilseeds. Significant oilseeds in the SR include oilseed rape, sunflower, soy, mustard and poppy, while the most important oilseed in the SR is clearly oilseed rape. Soybean, olive, oil palm and coconut are more important in the world. Oil production from plants is not less expensive compared to animal production, and health and dietary benefits such as e.g. the absence of cholesterol in vegetable oils, therefore the cultivation of oilseeds to date and will only show dynamic growth. In the SR, only oil from rapeseed is used for biodiesel production.

The content and composition of rapeseed oil makes it suitable for the production of biodiesel. Rape oil consists of approximately 97% triglycerides, the remainder being diglycerides and monoglycerides, free fatty acids, etc. Triglycerides (triacylglycerols) are compounds - esters of glycerin and saturated and unsaturated higher fatty carboxylic acids, which represent 95-98% of the lipid fraction. Fats and oils contain 7 - 13% glycerin. Rapeseed oil contains a high proportion of unsaturated fatty acids and is therefore liquid, unlike animal fats where saturated fatty acids predominate and are solid. The composition of the fatty acids determines the quality of fats and oils. Furthermore, sterols (0,3 - 0,5%), phospholipids (0,05 - 0,5%)

- 3.00%), pigments (24 - 50 ppm), free fatty acids (1-2%), tocopherols and other accompanying substances. The high content of pigments, especially chlorophyll, as well as the content of free fatty acids deteriorates fat quality and is therefore undesirable. Saturated are mainly palmitic acid (C16 _{: 0} ) and stearic acid ( _{C18: 0} ), unsaturated oleic acid (C18 _{; I} ), linoleic acid ( _{C18: 2} ), linolenic acid (C18 _{; 3} ), eicosene ( C ₂ o: (i) ^and erucic (C _22: i).

Rapeseed oil is obtained from rapeseed by pressing and then extracting the moldings with extraction gasoline. The crude rapeseed oil thus obtained is subjected to conventional refining processes for food purposes.

For oleochemistry, the possibility of decomposing oils and fats by either hydrolysis or alcoholysis is important. Hydrolysis yields fatty acids, alcoholysis by fatty acid esters, and a common breakdown product is glycerol. The fatty acids released by hydrolysis are of great importance due to the presence of their reactive double bonds and carboxyl groups. It is known that chemical reactions, where one of the reactants is a fatty acid molecule, take place either on the carboxyl group or on a double bond. Controlled chemical reactions at the double bond and at the carboxyl group lead to a variety of oleochemical products. Reaction of the carboxylic group of fatty acids with hydroxides creates salts of fatty acids -

soaps, fatty acid esters of alcohols, by a double bond reaction e.g. with hydrogen - hydrogenation, saturated fatty acids are formed and the process is oil hardening.

Fats can be hydrolyzed hydrolytically (by binding of a water molecule) to glycerol and carboxylic acids (1) by lipase enzymes or strong mineral acids (1):

CH ₂ —O — CO — R 1 CH ₂ —OH 1 1 CH - O - CO - R + I 3H ₂ O (H ⁺ ) CH - OH | + 3R — COOH (2) 1 CH ₂ —O — CO — R 1 CH ₂ —OH Triacylglycerol (fat) glycerol carboxylic acid (R - hydrocarbon chain) (1,2,3, - propanetriol) lina

Hydrolysis can also be carried out with alkali hydroxides. Treatment of triacylglycerols with sodium hydroxide (NaOH) or potassium (KOH) results in soaps (2). Therefore, alkaline hydrolysis is called saponification. Soaps are sodium or potassium salts of higher fatty carboxylic acids. Sodium soaps are solid and are used as cleaning or laundry detergents. Potassium soaps are cuddly and are used to prepare disinfectants.

CH ₂ —O — CO — R

I

CH — O — CO — R

I

CH ₂ —O — CO — R + 3 NaOH

CH ₂ —OH

I

- * CH - OH

I

CH ₂ —OH + 3 R - COONa (2) triacylglycerol (fat) (R - hydrocarbon chain) glycerol (1,2,3, - propanetriol) sodium carboxyl. acids (sodium soap)

The reaction of triacylglycerols, respectively. the carboxylic acids released in an excess of CH ₃ OH in the presence of a small amount of NaOH or KOH can be used to express the production of the methyl ester from vegetable oils, respectively. animal fats - biodiesel, in which the by-product is glycerol and a small amount of sodium or potassium salts of carboxylic acids (3). Esterification can also take place in an acidic environment.

R-COOH + R'-OH - * R-COO-R '+ H ₂ O (3) carboxylic acid alcohol carboxylic ester (R -, R'- hydrocarbon chains)

A disadvantage of pure vegetable oils for their use as motor fuels is that they have a high viscosity (up to 40 times higher than diesel) and their quality is reduced during storage. Therefore, the vegetable oils are esterified to the methyl ester according to reaction (3). The yield of the vegetable oil methyl ester is from 95% to 99%, according to the chemical parameters of the incoming oil. Esterification reduces the viscosity of the vegetable oil and brings many advantages. Engine operation, fuel production, transport and storage are not a problem after esterification. Such an ester can then be blended into diesel without any problems, which will not have a negative effect on the engine operation, but it also has a positive effect on the reduction of combustion emissions.

In order to circumvent the problems of modifying diesel engines, which are necessary when using pure methyl ester, blended fuel is mainly used. Such a blended fuel is biodiesel which contains 30% methyl ester and the remainder is diesel. For this blended fuel, all problematic properties of pure methyl ester (degradation of rubber seals, engine oil, engine power drop) are eliminated, respectively. significantly reduced. In addition, the presence of 10% methyl ester in diesel brings up to 30% reduction in engine wear. Higher proportions of methyl ester in diesel than 30% lead to problems with oxidation stability, formation of resins and deposits in the engine, and therefore such a mixture is not used. Under current conditions, production capacity could cover about 5% of diesel consumption in developed countries. In the US fuel with a 20% share is promoted, in France, where biodiesel is the most widespread of the EU, a mixture of 5% methyl ester and diesel is sold. In Germany, in addition to biodiesel farmers, taxi services are also commonly used. Its use can also be found in some ships and boats, which is related to the fact that biodiesel does not pollute water. In addition to the methyl esters used in Europe, the ethyl ester is produced (mainly in the USA) from vegetable oils.

The advantage of the methyl ester is its high safety in handling it, unlike conventional diesel, the methyl ester is as safe as food oil. The methyl ester has approximately the same cetane number as diesel, which means that it can be used directly in a diesel engine without additives. In addition, vegetable oil contains almost no sulfur and does not cause sulfur dioxide emissions. Biodiesel has a comparable energy content to diesel and therefore a tank as large as a conventional vehicle is sufficient. Engine power with this fuel is the same as diesel. Although the production price of methyl ester is higher than the production price of diesel, according to data from Germany, the costs of esterification are covered by the profit from the sale of glycerin, which is produced as a by-product in production. Glycerol represents approximately 11% yield when digested by oils. It is a very important trihydric alcohol, which after refining is a raw material for another important sector of organic technology. Other byproducts are squeezes obtained by pressing plant seeds, from which fat extraction yields extracted meal, contains large amounts of protein and other nutrients, and is a valuable compound feed in livestock nutrition.

Glycerol, as a technical product is called glycerin, is the simplest trihydric alcohol chemically 1,2,3-propanetriol HOCH ₂ -CHOH-CH ₂ OH, it is a viscous liquid of syrup-like consistency, colorless, odorless, sweetish taste, non-toxic, hygroscopic - scooping moisture from the air, thereby spontaneously diluting, is well soluble in water and alcohols, but practically insoluble in organic solvents such as acetone, industrial gasoline, ether, chloroform and in fats, oils and fatty carboxylic acids, chemically closely related to propylene glycol. It also occurs in organisms as a product of digestion.

Glycerol is used in more than 1,000 processes and is used to produce more than 2000 products. Worldwide, glycerine consumption was about 800,000 tons ten years ago in 1997, when biodiesel production began. Glycerol is used in the food, pharmaceutical, pharmaceutical, chemical, cosmetics, laundry, detergent, paper, textile, explosive and many other applications. It is used to make skin and hair lotions and care products, soaps, creams, where after application moisturizes, softens, softens and smooths, toothpastes and mouthwashes, perfumes, shampoos, showers, surfactants and detergents, it is used as a solvent for flavorings and colorings in the food industry, as a sweetener, as a preservative in meat and fruit processing, as a refining ingredient, as a filler for reduced-fat biscuits and cakes, in the manufacture of beverages, syrups, wines, liqueurs, confectionery, chocolates production of pet food, pigs and poultry, tobacco treatment (humidification), antifreeze for cars, cooling liquids, printing inks and inks in printing, such as plasticizer and plasticizer for cellophane and paper, wrapping foils, in the manufacture of textiles (thickeners) and printing inks), plastics and rubber (plasticizer) to make a spring and rigid foams (polyurethane foam), alkyd resins, electronic components, used for the production of lubricants, solvents, cement intensifiers, nitroglycerin, a principal component of dynamite, but nitroglycerin is also used as a component in medicaments for chronic heart disease, the drug is also used in medicinal syrups (e.g. cough), etc.

Each single application of glycerin in given directions requires different purity and concentration of glycerol from so-called. 80 to 90%, over 96% (technical) to above 99.5% purity. The purest glycerol is required in pharmacy (over 99.7%) and in the food industry, and the chemical industry requires different concentrations of glycerin in different applications.

In Central Europe, cold pressed rapeseed oil transesterification technology with methanol and an alkaline accelerator is commonly used for the production of methyl ester in a two-phase cycle. Transesterification is the conversion of one type of ester (triacylglycerol) into a new type of ester (vegetable oil methyl ester).

Glycerol, as a by-product of transesterification, is difficult to process in its original state. The crude glycerol is solid after cooling, which complicates its transport and storage. A modern refinery for the production of biodiesel therefore includes a refining block of the glycerol. The refined product obtained is in the form of an aqueous solution and is easy to handle. This block may also contain a vacuum evaporator which allows refining of crude glycerol to pure 99.5% glycerol. Export of crude glycerine with a concentration of about 80-90% represents the strong economic aspect of biodiesel production.

There are two technologies for the production of methyl ester from vegetable oils, namely anhydrous and aqueous, using washing water to purify the methyl ester. The composition of the glycerol phase then depends on the production technology.

The washing-water-methyl ester production technology consists of an oil and catalyst heating step in a blend homogenizer, ie in a reactor, settling steps to separate the methyl ester and glycerol layers, which are separated from each other based on different density to two phases and refining steps for methanol separation. did not participate in the reaction and purification of the methyl ester; the glycerol phase. The NaOH catalyst, respectively. KOH is dissolved in methanol and methanol is metered into the refined rapeseed oil in excess. The crude methyl ester is treated with warm water to remove unreacted methanol. The methyl ester washing and drying section consists of two stages, where the methyl ester is mixed with the washing water in a homogenizer. The mixture is brought to settling where the water after settling is drained off the line. Disconnection of soaps - salts of fatty acids is carried out by injection of phosphoric acid H ₃ PO ₄ or hydrochloric acid HCl, resulting in fatty acids and inorganic salts. The methanol washed into the water is evaporated from the water in a vacuum ring column and fed to a rectification column, where it is free of residual water and intended for reuse in production. The drying is carried out in a vacuum drying column, where the methyl ester is dehydrated to the qualitative properties required by the standard STN EN 14 214. Then the modified methyl ester goes to a homogenizer, where additives are dosed therein and is suitable for oil.

The separated glycerol phase is suctioned from production to the first stage, where it is recycled to the reaction as a source of active catalyst and methanol. It is then extracted from the first stage for further processing. Purification of the glycerin phase includes: separation of unreacted methanol, neutralization, washing with a flow of washing liquid originating from the washing of the methyl ester, cleavage of the soaps and concentration. The glycerol phase from the first stage of transesterification is fed to a ring vacuum column where it is free of methanol, then passed to a stirrer with HCl or H ₃ PO ₄ feed and adjusted to a pH corresponding to the dissociation constant of the soaps in the glycerol phase solution. Upon reaching this acidity, it is released into a separator where fatty acids are separated from glycerol. The composition of the glycerol phase can vary, depending on the production technology, at a level of about 30-40% by weight. glycerol, 2-4% NaCl (or KCl, K ₃ PO ₄ , Na ₃ PO ₄ ), methanol max. 0.1%, fatty acids max. 0.5%, one hundredth% of soaps and has a pH of about 6. This is processed to a final concentration of 80% glycerin. The partially purified glycerin can be further concentrated by distillation above 90%.

A significant difference in the technology of producing the methyl ester without the use of washing water is that no waste water is produced in the production process, so that it is not expensive to purify and the glycerol phase is more concentrated. Prior to transesterification, the feed oil is treated, de-acidified, dewatered and enriched with triglycerides, methyl ester and methanol, which are irreversibly lost in the aqueous manufacturing process, leaving with the glycerol phase. In the line, the inlet oil is heated to an operating temperature of 60 to 70 ° C. The water wash is replaced with a distillation column to distill off the methanol, followed by cooling and centrifuging the precipitated products. The distilled methanol can be reused in the manufacturing process without modification, which significantly reduces the operating costs of purchasing new methanol or costly rectifying it.

Transesterification takes place in two stages in transesterification reactors. A precisely determined amount of a catalytic solution, which is sodium hydroxide or potassium KOH dissolved in methanol, is metered into the treated feed oil, the mixture is sufficiently mixed, soothed and the separated glycerol phase is drained. After the second stage, the methyl ester is pumped into separation tanks where it is at rest for 10 to 12 hours, where the entire transesterification process is completed. Methanol is dosed in greater amounts for a smooth reaction than is necessary for the chemical reaction. Excess methanol dissolves virtually all

Undesirable impurities such as soaps, glycerol and other organic substances present in triglycerols. Methanol is distilled off in a special apparatus - long-distance molecular evaporator. Distillation is carried out under vacuum. Said undesirable impurities begin to drop off gradually after the methanol has been distilled off, which is greatly accelerated when the methyl ester is cooled in an ice water-cooled interinter vessel. From there the methyl ester is transported to the centrifuge. After centrifugation, the final treatment of the methyl ester produced, such as a reduction in the alkali content and a reduction in the water content, has to be carried out in special vacuum apparatuses. The methyl ester produced complies with the relevant marketing standards as a separate fuel for compression-ignition engines or as an admixture for diesel. For use in oil chemistry, however, a much more pure product is required, which can be obtained by distilling the methyl ester.

By-product - the glycerol phase, which is discharged in the transesterification process, is treated. The initial glycerol phase contains, in addition to glycerol, 2-3% water, 3% soap, 10-12% methanol and 10% methyl ester. Centrifuged products from the centrifuge are also added to the initial glycerol phase. In the centrifuge, glycerol, soaps, fatty acid methyl ester residues are centrifuged from the methyl ester into the initial glycerol phase to form a secondary glycerol phase. The glycerol phase is a dark brown-green mass, in the case of a K-catalyst at room temperature a viscous liquid, in the case of a Na-catalyst of semi-solid consistency. The proportion of glycerol phase is 16-18% by weight. by weight of the input oil. The composition of the glycerol phase is not stable and depends on several factors, in particular the acid number of the feed oil. The glycerol phase contains about 56-60% glycerol, 14-16% alkali in the form of alkaline soaps and hydroxides, 18-20% methyl esters, 10-12% methanol, 2-3% water and other ingredients. The basic step in the processing of the glycerol phase is its decomposition by a strong mineral acid in a special reactor. The action of the mineral acid breaks down alkaline soaps, which convert to free higher fatty acids, not mixed with polar glycerol and water, and form a separate phase. By breaking down the soaps, the emulsifier disappears in the system and thus the methyl esters entrained in the transesterification from the ester phase to the glycerol phase are deemulsified and form together with higher fatty acids a separate so-called. lower density organic layer. The free methanol present is then partitioned between the organic layer and the higher density glycerol layer according to complex partitioning equilibria. On average, about 2/3 vol. Of the glycerol phase is decomposed after its decomposition. glycerol layer and about 1/3 vol. organic layer. The amount of entrained methyl esters into the glycerol phase and consequently into the organic layer is reflected in the acid number of the organic layer, which ranges from 70 to 100, the usual values being 80-85 mg KOH / g. The organic layer is essentially a mixture of free fatty acids and methyl ester, containing about 60% methyl esters, 35% higher fatty acids, 5% methanol, and is a dark liquid. The free fatty acids may be subjected to a special, difficult acidic esterification, which improves the overall economic balance of biodiesel production.

In the decomposition of the glycerol phase by mineral acids (HCl, H ₃ PO ₄ , H ₂ SO ₄ ), HCl clearly dominates by the speed and sharpness of layer separation and their ratio. H ₃ PO ₄ is more environmentally preferable, but there is a problem with the glycerol layer where glycerol salt occlusion is observed. The same is true for H ₂ SO ₄ , but at present the problem is already largely solved and the sharpness of the division is sufficient. A great advantage of H ₃ PO ₄ is that the processes do not create a high corrosive environment, as is the case with HCl.

The aqueous glycerol layer solution is refined, free methanol and water are separated by distillation under reduced pressure to give 80% acid glycerol with pH = ca. The composition of the aqueous glycerol solution is about 78-85% by weight. glycerol, 6 - 8% Na ₃ PO ₄ , 10 - 12% water, 1 - 2% organic substances, especially methanol. This glycerol can be neutralized with an aqueous KOH solution to a pH of 8-9. Neither the mineral acids and the higher fatty acid residues are neutralized to form alkaline soaps. After the water has been distilled off, the solubility of the salts is reduced and, upon cooling, they precipitate. Salts can be removed by centrifugation and reverse osmosis using osmosis membranes. The material after removal of precipitated salts can be called crude glycerol and its composition is: 91 - 94% glycerol, 0,5% salts, 1-2% water, the rest are colored components and resins. The return methanol from the glycerol layer treatment can be further refined. Distillation of methanol improves the performance and commercial parameters of crude glycerol. Refined approximately 90% glycerol with low salt content can be further refined in the evaporator to pure glycerol with a glycerol content above 99%. Commercially, glycerol from methyl ester production can be produced as acidic 80% glycerol, neutral 90% glycerol and distilled glycerol 99.8%.

Products must be neutral with a pH between 7-8. Below pH 7 metals dissolve, acid vapors are also aggressive (carboxylic acids do not dissolve the steel at 20 ° C, but when heated above 60 ° C the steel is already dissolved).

Glycerol is also produced as a waste product in the production of soap and free carboxylic acids.

Soaps (sodium or potassium salts of higher fatty acids) are produced by alkaline hydrolysis of the triglycerides of reaction (2). The basic raw materials are in addition to triacylglycerols, alkali metal hydroxide and NaCl. The saponification is carried out at elevated temperature and pressure (temperature about 100 ° C), after the alkaline hydrolysis, the soap is added with sodium chloride, then the mixture is divided into two layers by cooling, the upper layer being soap and the lower liquid layer, strongly alkaline, contains excess hydroxide, NaCl, glycerol and fat-based impurities. Bottoms of soap production are aqueous solutions containing 4-15% glycerol, 8-20% NaCl, up to 0.3% free alkali and many other substances such as Na ₂ SO ₄ , soap residues, oxidized fatty acid soaps and bituminous acid soaps, mucilages, proteins, dyes, hydrocarbons, fat and glycerol breakdown products, etc.

The glycerol waters of the hydrolytic fat breakdown in the fatty acid production of reaction (1) contain 8 to 20% glycerol, some soluble lower fatty acids and organic substances in an amount of 0.2 to 0.4% including fat and glycerol breakdown products. Glycerine waters from fat breakdown are freed from impurities and admixtures by refining prior to evaporation. After refining, the glycerol water is concentrated by evaporation to a concentration of 88% glycerol. The resulting crude glycerin is already suitable for distillation. The soaps are also refined before evaporation. Refining consists of acidification with HCl to liberate fatty acids, removal of colloids by clarification of Al ₂ (SO ₄ ) _3, and removal of excess clarifier by alkalization. The resulting Al (OH) ₃ is removed by filtration or by settling. The refined bottom liquors are evaporated in a single-stage evaporator equipped with a salt collector for separating the crystallized salt which precipitates during evaporation.

However, an increase in the amounts of glycerol produced in the production of soap and free carboxylic acids is not expected, in contrast to the potential increase in the amount of glycerol from biodiesel production.

Glycerol falling off the production is contaminated, and its composition depends on the place of its collection from various interoperative nodes of production lines, it contains water, alcohols, hydroxides, resp. inorganic acids, methyl esters, free carboxylic acids, residual oils, organic, inorganic salts and other substances. However, in the vast majority of practical applications of glycerin, high purity of waste glycerol phases with a glycerol content of over 90% is required, which also requires demanding refining and concentration of glycerol.

The disadvantage is that the boiling point of anhydrous glycerin is at normal atmospheric pressure of 290 ° C, in addition glycerol is a heat-sensitive compound and decomposes and polymerizes at temperatures above 200 ° C, cannot be concentrated in conventional evaporators where degradation would occur, nor can its evaporation and distillation be carried out at normal pressure. Therefore, heavy distillation under vacuum or steam, or a combination thereof, is used.

The disadvantage is that the crude glycerol of the technology, which usually contains several percent of salts and organic substances, has a higher viscosity and boiling point than pure glycerol and its purification - distillation is more difficult. For distillation, a continuous film rotor evaporator is used, in which a thin film of the glycerin layer is formed, from which the glycerin is evaporated by vacuum. However, the crude glycerin must be freed of residual water and volatiles in the thickener prior to distillation. From there, the concentrated glycerin is evaporated in a continuous evaporator by means of vacuum and the glycerin vapor condenses in a system of condensers in which fractional condensation takes place. A multi-stage vacuum rectification in several rectification columns is also used to increase its concentration. The distillation residue, glycerine pitch, is collected in the tanks under the distillation apparatus. Concentrated glycerol can also be made from glycerin waters by ion exchange without distillation. However, all these processes are very expensive and therefore expensive. There is also a problem with the recovery of wastes that arise from the refining and distillation of glycerol phases. The return methanol from the glycerol phase treatment cannot be directly used in the production of the methyl ester. It can be sold or rectified for reuse, but again a rectification column and energy-intensive rectification are required. However, without these demanding modifications, the glycerol phase is not for sale.

By increasing the proportion of biodiesel production, glycerol phase production will also increase. Currently, biodiesel producers benefit from the sale of purified glycerol to its processors. However, increased amounts of glycerol, despite the existence of thousands of possibilities for its utilization in practical applications, will bring problems from its overproduction. Since the possibility of collecting and processing glycerol in the chemical, food, cosmetic, pharmaceutical and industry and explosives industries is limited and the production of biodiesel will increase, the problem of glycerol utilization will have to be addressed.

Therefore, new, yet technologically unmanaged applications are being considered. For example, in the field of biotechnology, glycerol may serve as a carbon source in fermentation processes, but this application requires relatively pure glycerol phases, since fermentation microorganisms are sensitive e.g. even at pH and also in the case of large overproduction of glycerol phases, there will be a spatial and capacity problem for fermentation.

Glycerol is recommended to be used as part of the biogas feedstock - a mixture of methane and CO ₂ in digested anaerobic sludge tanks, where glycerol effectively raises biogas production and then uses this biogas to run the biodiesel production line. Biogas production by anaerobic digestion of glycerol, however, is a lengthy process compared to the methyl ester production rate, requiring large digestion tanks without access to air and then biogas collecting tanks, which is very space and investment-intensive and insufficient for large-scale liquidation.

The use of the glycerol phase in the pyrolysis process of its decomposition and disposal also has several disadvantages. The glycerol phase would be subjected to heat-intensive pyrolysis requiring special equipment, heat consumption, in some cases also increased decomposition pressures, cleavage of long hydrocarbon chains into shorter, more easily combustible gaseous and liquid hydrocarbons. However, glycerol, as the simplest trihydric alcohol containing only three -CH _n - groups and up to three -OH groups, is not suitable for pyrolysis. Pyrolysis of glycerol is more unprofitable than other organic substances with longer hydrocarbon chains (plastics, rubber, etc.). The problem is also the thermal instability of glycerol and the formation of pitch after its polymerization. This process of pre-treatment and disposal of glycerol phases does not solve the problem of the resulting waste residue after pyrolysis, which contains carbon black and difficult to process pitch. The combustion of soot and pitch thus requires high temperatures and an oxidizing atmosphere with excess air.

The solution of the problem by deposition of glycerol phases in landfills is not possible under current EU legislation, on the basis of Directive 1999/31 / EC incinerable, biodegradable wastes can no longer be deposited but have to be heat treated in incinerators. The deposited biomass at waste dumps is subject to uncontrolled decomposition with the development of CH ₄ greenhouse gas.

The disposal of excess glycerin in municipal and industrial waste incineration plants is uneconomical, unecological, and cannot be linked to the current trend of sustainable development. The incineration in waste incineration plants does not use the energy content in the glycerol phases, but in addition there is a risk of incomplete waste incineration, toxic gas leakage, odor spread and unnecessary emission of CO ₂ into the atmosphere.

One possibility is to rework the glycerol phase into an ecological fuel useful e.g. for steam production, el. energy or other energy purposes. Glycerol as a fuel, however, has several disadvantages, and in particular a relatively low calorific value, which results from a low specific combustion enthalpy of 17,974.4 KJ.kg ^-1 , which is lower than conventional fossil fuels, lower than that of brown coal, which in addition to energy thermal aggregates in conventional industrial thermal aggregates practically does not use.

Although glycerin burns well, it does not release toxic acrolein containing flue gas if it is not properly combusted at high temperatures, particularly at 200-300 ° C. In this respect, the combustion of excess glycerin to preheat vegetable oils, to produce methyl ester of vegetable oils, to adjust glycerol phases, to rectify methanol, to heat production halls in simple burners is problematic. The energy use of glycerol for its own production line of methyl esters is also under-dimensioned.

Temperatures above 1000 ° C and residence time at these high temperatures of about 5 seconds are required for glycerin to burn well, in addition, preheating of the glycerin itself and its atomization prior to high temperature combustion are also required.

The glycerol phase contains caustic (NaOH or KOH), it is a caustic substance and is therefore problematic for combustion under normal conditions e.g. in households. Considerable danger also arises from the presence of deadly dangerous, toxic residual methanol in the glycerine phases. Special, chemically resistant boilers would be required. Remodeling boilers in households to heat and heat water from the combustion of solid fuel (coal, wood) and natural gas to burn liquid glycerol would be very expensive, and the heating period is intensive only during the winter.

Use of glycerine as a fuel component, resp. as a component of the combustion enhancing agent has been patented. In US Patent No. 681SO27, protected fuel is based on organically pure biomass. The fuel consists of a mixture of cellulose powder products, sawdust and pulverized charcoal mixed with vegetable oils and vegetable alcohols such as ethanol, methanol, glycerin and other vegetable alcohols from the esterification of vegetable oils. The fuel is in the form of briquettes, ingots or viscous liquid, respectively. is of mushy or creamy consistency. The fuel serves as a substitute or admixture to conventional liquid fossil fuels.

U.S. Pat. No. 5,718,735 discloses the preparation of high calorific fuel based on dried waste water sludge, hydrocarbon-containing materials having an energy content greater than 7,000 BTU (7,385.5 kJ) mixed with alcohols of the triethylene glycol, diethylene glycol, glycerin and propylene glycol addition of a pozzolanic agent such as lime ash, kiln dust, or other lime-containing materials, the resulting mixture being easy to handle in the form of pellets and also suitable as fuel in cement kilns. Glycerol is used in given fuel mixtures, practically only as a binder component for solid components ·

Korean patent 1020040022797 protects the use of glycerin as a component in a special reagent to improve the combustion process (compression ignition, diesel engines) using a catalyst and to remove dust, soot, clinker, sludge and lump materials from internal combustion engines and furnaces. The reagent is prepared by mixing glycerin, an amine stabilizer (triethylamine), hydrogen peroxide, sodium hydroxide, and borax, the mixture is soluble in diesel fuel to increase combustion efficiency, save fuel, and reduce the amount of contaminants.

In U.S. Pat. No. 4204877, polyglycerols have been used in industry and in a different direction, such as cement grinding intensifiers and cement-setting retardants.

Glycerol is also used as a plasticizer in concrete mixes to flow fresh concrete.

These solutions, however, focus only on glycerin as a supplement to the solids, respectively. viscous fuels or as a component to intensify diesel combustion in diesel engines. Such processes where glycerin is only a minor component of fuels, the proportion of glycerin in solutions well below 50% by weight, cannot significantly assist in the use of glycerol phases from the production of vegetable oil methyl esters.

Production of biodiesel. Even glycerol is the most economical than the continuous process, as is the continuous consumption of diesel in transport. Therefore, the most appropriate way to utilize excess glycerol is to use it as an alternative fuel in large combustion units such as cement kilns, kilns for glass, glass and glass products, enamels, glazes, siderite decarbonisation furnaces, magnesite for magnesite clinker , limestone or dolomite to lime, for the manufacture of gypsum and anhydrite binders, for dehydration, dehydroxilization and aluminum hydroxide firing, calcination of Al ₂ O ₃ , for the firing of magnesite products, magnesium -ospinel, magnesium-chromium and other products based on MgO and its compounds, chamotte, chamotte , mullite, corundum and dinas products, refractory materials and fittings, products of fused basalt, pottery, earthenware, porcelain, earthenware, ceramics, for firing of ceramic coverings, wall and floor tiles, bricks and fittings and other silicate products and chemical industry, to the heating plants of thermal power plants and heating plants or drying ovens in the given sectors, which would be able to continuously collect glycerol phases in large quantities.

It is an object of the present invention to provide a fuel mixture based on glycerol with various contents of organic matter, inorganic substances and water which together form solutions, suspensions, emulsions, soles, semi-liquid gels capable of mixing or raising the temperature to a liquid state or a combination thereof, without the need for complex and energy-intensive pre-treatments for energy recovery of this fuel mixture as an alternative fuel, or fuel components replacing noble fossil fuels in thermal industrial and energy aggregates so that the fuel mixture does not adversely affect the combustion process, technology and production quality; emissions to air.

SUMMARY OF THE INVENTION

This object is achieved by a fuel mixture which comprises 9 to 99.97 wt. % glycerol, 0.01 to 90 wt. % of organic substances having a calorific value in the range of 5 to 45 MJ.kg ^{-1 of} 0.01 to 40 wt. % of inorganic substances whose cation or anion in the compound is not bound to the hydrocarbon chain or hydrocarbon cycle and 0.01 to 40 wt. water H ₂ O, wherein the fuel mixture is liquid and has a total calorific value in the range of 5 to 42 MJ ^/ kg.

The components of the fuel mixture may together form solutions, suspensions, emulsions, soles, semi-liquid gels capable of being mixed or combined with each other after mixing or raising the temperature.

Inorganic substances are of the type HCl, H ₃ PO ₄ , H ₂ SO ₄ , NaCl, KCl, Na ₃ PO ₄ , K ₃ PO ₄ , Na ₂ SO ₄ , K ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ , NaOH, KOH, Al (OH) ₃ , and i, wherein the cation or anion in the compound is not bonded to a hydrocarbon chain, or a hydrocarbon cycle.

Organic substances are of the type of alcohols such as methanol, ethanol, propanol, higher alcohols, aromatic and heterocyclyl alcohols, polyhydric alcohols (polyols - glycols and i), glycerol and polyglycerol esters, aldehydes, ketones, organic acids (malic, citric, acetic, tartaric, formic) , lactic, salicylic, oxalic, gluconic ai), higher fatty acids (ricinoleic, lauric, erucic, oleic, stearic, palmitic, petroselinic, linolenic, linoleic, mono-, di- and polycarbonic ai), lower fatty acids, fatty condensates acids, phospholipids, glycolipids, vegetable oil esters (vegetable oil methyl esters, vegetable oil ethyl esters), fatty acid soaps (Na, K and i), oxidized fatty acid soaps, bitumen soaps, fatty acid derivatives, mono-, di- and fatty acids triacylglycerols, animal and vegetable fats, vegetable oils (rapeseed, sunflower, soybean, palm, flax, castor, ai), mineral oils (paraffin, diesel ai), degradation products - oxidative or microbial digestion of glycerides, unsaturated acids, waxes, lanolin, varnishes, gels, tars, essential oils, resins, derivatives of sulphonates (lignosulphonates, melamine- and naphthalene-naphthalines) melamine- and naphthalene-formaldehyde sulfonates, ai), lignosulfonates, sulfite organic compounds, lignosulfonic and hydroxycarboxylic acids, polycarboxylates, naphthalene, formaldehydes, their salts, derivatives and resins (phenol-formaldehydes, melamine-formaldehydes, naphthalene-formaldehydes), naphthalene formaldehydes) , gluconates, stearates, salicylates, oxalates, acetates, acrylates and their resins, melamines and their resins, natural and synthetic resins, stearin, oil, epoxides, latexes, saccharides (glucose, galactose, fructose), oligosaccharides (sucrose), polysaccharides, sugar derivatives, cellulose derivatives (hydroxycellulose, hydroxymethylcellulose) za, hydroxyethylcellulose, ai), protein hydroxylates, polypeptides, oligopeptides, their mutual compounds, gasoline, benzene, acetone, ether, ethyl ether, toulene, trichlorethylene, kerosene, detergents, surfactants, detergents, oil and fat refining wastes, from ester production fats and oils, technical and shortening fats, margarines, from fats and oils, from purification of vegetable oil esters, wastes from distillation of vegetable oil esters, from purification of glycerol, from distillation of glycerol (including co -merized glycerol previously exposed to temperatures above 200 ° C and glycerol pitches from distillation and rectification residues), from falls from soap cleaning, higher fatty acids, mucilaginous substances, mucilages, proteins, lecithins, sterols, chlorophile and carotenoid dyes, natural dyes, urea, wastes from the production of chemical compounds, cleaning, disinfecting and disinfecting detergents, detergents, detergents v, cosmetics, pharmaceuticals, pharmaceuticals, oilseed, leguminous, cereal, nut, waste from agriculture, fat, leather, meat and milk processing industry, organic and waste water treatment, waste from cellulose, lignin, pulp, starch, carbohydrates, protein processing, skins, lipids, fats, waxes, oils, varnish, glue, resin, collagen, gelatine, rubber, rubber, rubber, viscose, tar, bitumen, gasoline, oil, lubricant, petroleum, coal waste , coke, anthracite, lignite, bitumen, combustible slate, peat, oil recovery, paint residues, dyes, varnishes, adhesives, organic solvents, worn table and industrial oils and other liquid organic compounds and waste products.

The water content of H ₂ O in the fuel mixture depends mainly on the technology of obtaining the principal component of glycerol.

Preferably, the fuel mixture has a pH close to 7.

The components of the fuel mixture are liquid solutions, solutions with alcohols, water, solutions containing dissolved salts, sugars, etc., emulsions of insoluble or water-soluble substances. only sparingly soluble liquid substances, suspensions with inorganic or organic salts; sugars, soles, semi-liquid gels capable of mixing or raising the temperature after mixing or raising the temperature, or a combination thereof, without the need for complex and energy-intensive pretreatments such that the fuel mixture is well pumpable by conventional means of transport such as e.g. pumps, well transportable eg. in pipelines, well transportable eg. in tanks, well storable eg. in the trays.

The glycerol phases and layers have different compositions depending on the production technology, the point of collection from the individual production stages, the degree of their purification and the degree of concentration of the glycerol phases and layers to a given final concentration of the glycerol solution.

It is very advantageous if the components of the fuel mixture originate directly from the production of biodiesel without their intensive treatment or addition of components other than those produced in the production of biodiesel.

The solution also makes it possible to form a fuel mixture by the simple addition of contaminated, undistilled, higher fatty acid methyl esters, distillation residues after distillation of higher fatty acid methyl esters and glycerols, return methanol, organic layers, centrifuge components into glycerol phases and biodiesel production layers.

The advantage of the solution is that the glycerol phases and biodiesel layers need not be free of impurities (organic, inorganic salts) and impurities (methanol, hydroxides, water, acids, oils, esters), they need not be acid-cleaved, centrifuged, distilled, rectified or concentrated by ion exchangers. Also, the organic layers from biodiesel production need not be subjected to intensive acid esterification and methanol need not be distilled off from the individual intermediate stages.

However, the solution also makes it possible to form a fuel mixture from high purity rectified glycerols approaching a concentration of 99.97% by weight, respectively. from refined glycerol phases and layers, to different concentrations of glycerol, of which separate portions such as e.g. methanol, free higher fatty acids, were reused in production. Furthermore, also from glycerol phases and layers enriched with other organic or inorganic substances not coming from the production of biodiesel, preferably if these substances are wastes.

Glycerol, respectively. the glycerol phases and layers need not be combined with the solids in the fuel composition of the present invention, as was the case in the prior art.

It is also preferred that the components of the mixture are wastes from the biotechnology, chemical, pharmaceutical, cosmetic, food, fat, leather, meat and milk processing industries, construction, agriculture, woodworking, stationery.

The solution maximizes the use of wastes, especially bio-waste as an alternative fuel in large combustion units such as cement kilns, glass furnaces, glass and glass products, enamels, glazes, siderite decarbonisation furnaces, magnesite for magnesite clinker, limestone or dolomite for lime, for the manufacture of gypsum and anhydrite binders, for dehydration, dehydroxilization and aluminum hydroxide firing, Al ₂ O ₃ calcination, for magnesite products, magnesium -ospinel, magnesium-chromium and other products based on MgO and its compounds, chamotte, mullite , corundum and dinas products, refractory materials and fittings, products of fused basalt, pottery, stoneware, porcelain, earthenware, ceramics, for firing of ceramic coverings, wall and floor tiles, bricks and fittings and other products of the silicate and chemical industry, to k renísk thermal power plants and heating plants, or dryers in those sectors.

The fuel composition of the present invention enables by its composition the energy recovery of the components of the mixture, and in some cases also the material recovery of inorganic components such as cement clinker or lime building, when the inorganic components react into the burnt materials.

In energy recovery, the fuel component replaces expensive and non-renewable fossil refined fuels and indirectly reduces CO ₂ emissions from the incineration of waste in municipal and industrial incinerators. With the increasing proportion of biomass in the fuel mixture, CO ₂ emissions are reduced correspondingly, since biomass is CO ₂ neutral.

In material recovery, the non-combustible inorganic fraction of the ash components of the mixture increases the amount of heat-treated materials as it becomes part of them.

The composition of the fuel mixture is adapted to the type and method of its recovery. In plants where the purity of the resulting product is very important, e.g. production of ceramics, glass, lime, magnesite clinker, drying of raw materials and semi-finished products, the content of combustible components, ie. j. flammable materials and inorganic constituents, i.e. j. The ash in the mixed mixture is reduced as close as possible to the 0.01% by weight. Conversely, in plants where the inorganic portion of wastes ends up in fired materials, slags, ash, slag, ash and dusts suitable for further processing, the ash content in the fuel mixture is increased to near 40% by weight. even welcome, e.g. production of energy, but also firing cement clinker, building lime.

Increased H ₂ O content in the fuel mixture to 40 wt. is even beneficial in some cases, e.g. to reduce emissions of _NOx, where high levels of H ₂ O in the fuel causes a decrease in flame temperature and the formation of the hydroxyl radical OH, which help to reduce thermal _NOx.

The solution ensures perfect, waste-free, ecological and economical disposal of waste forming components of the fuel mixture and prevents the increase of the share of unused waste ending in landfills or waste incineration plants.

The fuel mixture may be a stabilizing fuel, e.g. for firing cement clinker, enabling the combustion of solid alternative fuels prepared mainly from municipal and industrial wastes with lower calorific values than conventional commercial fuels, with lower homogeneity and greater granulometry. By burning these solid alternative fuels, the main burner flame is prolonged, its emissivity decreases, which can lead to clinker firing problems. Therefore, the amount of combusted solid alternative fuels is limited, and thus the saving of fossil fuels. The fuel composition of the present invention, as a liquid fuel, increases flame emissivity, despite the relatively low calorific value of glycerol alone.

Feeding the fuel mixture into conventional heat units equipped with multi-channel burners is problem-free, for heat units equipped with single-fuel burners for gaseous or solid fuels, either modification of the burner or introduction of an auxiliary burner for liquid fuels is necessary. Combustion of fuel mixture in heating plants and thermal power plants equipped with furnaces for combustion of solid fuels in a fluidized bed or on grates is more demanding, requiring the addition of combustion chambers and furnaces with special liquid fuel burners and optimization of heat generation. The same applies to combustion chambers of natural gas-fired heating plants.

The combustion of the fuel mixture in these aggregates is not only not increase the CO ₂ in the atmosphere and helps to reduce _NOx emissions, but the combustion of mixed fuel is obtained and energy with low production emissions of _SOx in comparison with brown coal at virtually zero air contamination by heavy metals.

Combustion of the fuel mixture reduces fuel costs, increasing the competitiveness of production and energy units.

The solution enables the increase of agricultural production by the consumption of increased amounts of plant glycerol associated with the growth of biodiesel production. It helps to economically and ecologically utilize land set aside for food crops, in particular of lower quality and contaminated soils, for the cultivation of technical oilseeds such as oilseed crops. oilseed rape, sunflower. It allows addressing farmers' problems related to overproduction of food and subsidies currently paid to EU farmers for non-tillage. Agriculture and food can be not only food producers but also raw materials for further processing, especially secondary energy sources. This is in line with the strategic aim of EU agrarian policy, namely the active participation of agriculture in the preservation and development of the rural environment and the maintenance of rural settlements, in particular by supporting diversification of agricultural activity towards non-agricultural activity and developing non-food crops that opportunities and incomes for the rural population and thus slow down the migration to cities and also fully in accordance with the national strategy of sustainable development of the SR, where agriculture can significantly contribute to solving energy problems using non-traditional and renewable sources of energy from biomass. According to world forecasts, the role of agriculture in this respect will increase, which is of great strategic importance in a country such as Slovakia, which is dependent on imports of energy raw materials. Domestic non-renewable resources in Slovakia cover only 10% of consumption and the rest must be imported. By 2010, the economy is expected to reduce its energy intensity by 25 to 30%. In 2010, the real usable potential of renewables should account for 7.5% of total fuel-energy consumption, to which the fuel mix under this solution is also actively contributing.

DETAILED DESCRIPTION OF THE INVENTION

The following Examples illustrate the composition of the fuel composition of the present invention, which can serve as a substitute or supplement to noble fuels in industrial and energy combustion units. These examples have no limiting effect on the scope of the claims.

Example 1

The fuel composition of the present invention comprises 90 wt. % glycerol, 7 wt. % organic compounds, in particular methanol and free fatty acids, with a calorific value of 30 MJ.kg ^-1 , 1 wt. % Na 3 PO 4 and 2 wt. H2O, the mixture having a total calorific value of 17.4 MJ.kg ^-1 , pH 6, and comes from the production of biodiesel. The mixture was liquid and incinerated in a cement rotary kiln, replacing 15% of the heat for firing cement clinker. During the firing, there were no technological problems Na3PO ₄ prereagovalo into clinker, which has shown a slight increase in phosphorus in the clinker.

Example 2

The fuel composition of the present invention comprises 50 wt. % glycerol, 48 wt. % of organic substances, in particular rapeseed oil methyl ester with a calorific value of 37 MJ.kg ⁴ and with parameters which did not comply with STN EN 14 214, 1 wt. % KCl and 1 wt. water H ₂ O, the mixture having a total calorific value of 26.3 MJ.kg ^-1 , pH 7, the individual components of the mixture coming from biodiesel production. The mixture was liquid and was burned in a lime kiln rotary kiln to replace the 25% heat burning rate. There were no technological problems during firing, KC1 reacted to lime, which was shown by a slight increase in chlorine in the lime.

Example 3

The fuel composition of the present invention comprises 40 wt. % glycerol, 56.5 wt. % of organic substances, especially waste contaminated motor oils with a calorific value of 38 MJ.kg ¹ , 0.5 wt. % K3PO4 and 3 wt. H2O water, the mixture has a total calorific value of 28.3 MJ.kg ^-1 , pH 6, part of the mixture comes from biodiesel production, contaminated engine oils come from car repair shops. The mixture was liquid and combusted in a magnesite clinker rotary kiln, replacing the 20% fraction of heat at firing. There were no technological problems during firing, K3PO ₄ reacted to the clinker, which was shown only by a slight increase in phosphorus in the clinker.

Example 4

The fuel composition of the present invention comprises 9 wt. % glycerol, 78 wt. % organic matter, in particular waste animal fat, with a calorific value of 36 MJ.kg ^-1 , 3 wt. % NaCl and 10 wt. water H ₂ O, the mixture having a total calorific value of 29.6 MJ.kg ^-1 , pH 8, part of the mixture comes from the production of biodiesel, waste animal fat was produced in the rendering plant. The mixture was heated to 60 ° C to be liquid and incinerated in a ceramic furnace firing furnace, replacing the 10% firing rate. There were no technological problems during firing, the NaCl present did not cause qualitative changes on the surface of the products.

Industrial usability

The fuel composition of the present invention is suitable as a fuel in large combustion units such as cement kilns, glass furnaces, glass and glass products, glass and glass-based products, enamels, glazes, siderite decarbonisation furnace, magnesite for magnesite clinker, limestone or dolomite for lime, for the production of gypsum and anhydrite binders, for dehydration, dehydroxilization and aluminum hydroxide firing, calcination of A1 ₂ O ₃ , for firing magnesite products, magnesium -ospinel, magnesium-chromium and other products based on MgO and its compounds, chamotte, sillimitite corundum and dinas products, refractory materials and fittings, products of fused basalt, pottery products, earthenware products, porcelain, earthenware, ceramics, for firing of ceramic coverings, wall and floor tiles, bricks and fittings and other products of the silicate and chemical industry, for heating electro RNI and heating plants, where dryers.

Claims (1)

Fuel mixture, characterized in that it contains 9 to 99.97 wt. % glycerol 0.01 to 90 wt. % of organic substances having a calorific value in the range of 5 to 45 MJ.kg ^-1 , 0.01 to 40 wt. inorganic substances whose cation or anion in the compound is not bonded to a hydrocarbon chain; or