HUP0900611A2 - Solid fuel with reduced ash contain and producing the same - Google Patents

Description

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Solid fuel with reduced ash content and method for its production

Renewable energy sources can be considered an integral part of the energy system that sustains, operates and regulates the world. The goals of the production and utilization of renewable energies, as well as the social, economic, natural and human environmental conditions and constraints, require that we utilize all possible components of the produced biomass. Despite the fact that fuels produced from vegetable oils generally enjoy priority - primarily because of the prices - it is advisable to utilize the by-products of synthesis in such a way that they serve both energetic and economic criteria within an ecological framework, especially considering the fact that any biomass can only be produced within limits.

From an ecological point of view, it is desirable that we can also utilize the secondary component in its primary application area.

Based on a comprehensive analysis of our research and development results and practical experience, we propose this, based on the simple but in practice surprising realization that we bring fossil and renewable energy products into a unified application system, into a composition that is also functional in practice.

Sunflower-based biodiesel production produces two important by-products: glycerin and sunflower hulls. Well-known applications include burning the hulls in a biomass boiler and processing the glycerin into cosmetic and pharmaceutical grade products.

In these cases, a solid by-product adhered to activated carbon is also produced. This, as well as the non-standard fuel components, the settled, extracted material streams, were treated as falling within the scope of the present invention and fuel components were produced that are not referenced in the literature.

Glycerin itself can be burned, but the catalyst residue does not allow these material streams to be utilized in industrial steam generators by suitable additives, i.e. by mixing in special and often prohibitively expensive components to prevent corrosion, softening, and long-term perforation of the pipes. That is why we have developed the present proposal to utilize the heat content of the by-product of 14-17 MJ/kg, i.e. brown coal equivalent, in agricultural and domestic boilers.

Our global plan is to add additional solid fuel that improves combustion heat, in addition to wood chips, straw chips, and dried grasses (the heating value of which only reaches 10 MJ/kg in exceptional cases), with the aim of saving forests planted for non-firewood production from being stockpiled.

With the selected auxiliary components - especially glycerin and its combinations of occurrence - we must guarantee that the final fuel component has a stable, reliable composition. The composition is particularly advantageous from an environmental point of view, because due to the good calorific value, combustion is perfect, and there is no need to use ignition streams for the combustion of materials with a high water content. Another advantageous feature is the low sulfur content and the associated low sulfur oxide emissions. We cannot measure it, but based on the literature, we can verifiably state that the production of nitrogen oxides can also be reduced by using the composition.

We only report ash content and combustion properties for the present composition; the application of the know-how will also require recording the results of emission measurements.

The handling of the proposed fuel is simple because the microcrystalline paraffin product, which forms the continuous phase, solidifies at 60-70 °C, enclosing the glycerin, which is already mixed as a discrete phase, and the sunflower shell powder used as a stabilizer for the Pickering emulsion.

Our surprising discovery is based on the fact that the surface of the emulsion-stabilizing solid preferentially binds to the alkane molecules and disperses them in a dispersed state in the external, continuous glycerin phase. We use a colloid chemical technique to invert the dispersed system and form the wax continuous phase. It is particularly advantageous that we do not add expensive surfactants to the composition, but use components that are enriched in the glycerin stream. The water content of the glycerin phase is favorable because it freezes the chemistry of nitric oxide formation.

Schrader (U.S. Pat. No. 4,333,738) and Tutupalli et al. (U.S. Pat. No. 6,136,054) use wax to increase the heat of combustion of firewood. USPTO Patent Application 20060021276 considers the incomplete combustion of wax to be a disadvantage of the admixture, which results in the formation of volatile hydrocarbons. However, in our measurement program, we were surprised to observe that the limited incomplete combustion was not a disadvantage, but rather an advantage, because the partially gasified hydrocarbons maintained the combustion of the glycerin phase, and the amount of residual ash was reduced.

Other patent literature references relate to the use of waste materials as fuel components, the production of firewood compositions:

1. Sawdust, coffee grounds (U.S. Pat. No. 6,113,662). The disadvantage of wax mixing is that it is not considered a good choice for either aesthetics or combustion properties due to the formation and deposition of soot. Despite all this, their patent was formulated to protect the mixing of 40-50% wax.

2. Waxed cardboard reinforced wood chips in a fuel composition - U.S. Patent 6136054 The role of the wax in the composition is to strengthen the paper fibers to provide sufficient strength. The wax content is 40-65%.

3. The above patent refers to the use of rice husk, waste paper (U.S. Pat. No. 3,297,419), as a paper mill by-product in order to increase the role of the latter in the utilization of the former.

4. Peanut shell (U.S. Pat. No. 4,040,796), like coffee husk, rice husk, and peanut shell, is analogous to our sunflower shell blending philosophy, however, these patents do not feature a unified system approach, nor the practical use of hydrocarbon industry products, nor is wax used to stabilize a disperse system, but only as a binder, analogous to road construction bitumen.

Our proposed fuel solution, our composition is a room temperature solidifying water (glycerol stream) in oil (microcrystalline paraffin mixture) emulsion, which is stabilized by sunflower husk (Pickering emulsion), with the help of surfactants dissolved in the discrete phase. It is obvious that the mineral oil-derived wax component can be replaced by other animal and vegetable waxes, wax waste, characterized by the fact that the solidification point of the wax is at least 70 °C.

The process can be preferably carried out by pouring into a mold following a known emulsification technique and cooling. The composition can be further developed by pouring the emulsion into polyethylene waste molds, and then, after the composition has solidified, the plastic shell is crimped. The composition can be prepared as needed by gelling used grease, used renewable energy-based oils (e.g. hoof oil), using the gel structure as the continuous phase, in which case, however, the fuel composition (waste) must be poured into polyethylene (polyalkane/alkane) bags.

The most important operations and technological parameters of the practical application:

1. The sunflower husk is crushed into particles smaller than 0.1 mm using a suitable grinding device, or it can be ground in a hammer mill.

2. We make sure that the glycerin phase does not contain more than 0.5% methanol (headspace GC analysis). If it does, it cannot be used in the fuel according to this proposal!

3. Heat the glycerin phase to t = 80°C, add 8-32%, preferably 14-23% sunflower husks crushed to particles smaller than 0.1 mm, while stirring continuously.

4. With intensive mixing, add 65% wax by volume to the glycerin phase at t = 80°C. Note the temperature of the emulsion inversion. If this is warmer than the melting point of the wax, increase the proportion of wax until the temperature of the emulsion inversion is at least 5°C warmer than the melting point of the wax. Increase the mixing temperature as necessary, taking care not to exceed the boiling point of the water, as this may cause the system to foam unnecessarily and splash.

5. Pour the inverted, i.e. water-in-oil type emulsion into either molds or a piping bag and let it cool.

6. The fuel prepared in this way is burned in manual and/or automatic feeding boilers.

7. The fuel is also suitable for open-air fires with due care. Due care means adding one or two pellets to the fuel, which is typically wood, to keep mosquitoes and other bugs and insects away.

Solution options for producing sunflower shell glycerin fuel:

I.

During the preparation of 250 g of sunflower pressing, the sunflower husk obtained during the dehulling process was ground in a grinding device, and the resulting material was filtered through a 0.1 mm sieve (without residue).

300 g of methanol-free crude glycerin (pH=12.8, methanol content=0.3%, fat content (including soap content): 18%, glycerin content: 68%, the remainder KOH dissolved in water) was weighed into a 2 1 3-necked flask under reflux. The material was heated to 80°C, then 100 g of sieved sunflower shell powder was added. The mixture was stirred for 10 minutes.

75 g of microcrystalline wax was added to the hot mixture with constant stirring. The addition time was 3 minutes.

Stirring was continued for another 15 minutes. We observed that the dark glycerin phase had transformed into a dispersed phase, with the wax acting as the outer continuous phase.

The 80°C mixture was poured into a 30 mm diameter paper cone and allowed to cool.

After an hour, we heated the paper cone with a heat gun so that the wax cylinder could slide out of it.

We cut 2 cm pieces from the slipped wax cylinder and lit them in a porcelain cup to determine the ash content. The solid fuel burned evenly without splashing, at a flame temperature of 750-782 'C (measured with an infrared thermometer). The amount of ash remaining was 5.2 %.

II.

200 g of microcrystalline paraffin production petrolatum oil were mixed under reflux in a 2-1 3-necked flask with 300 g of methanol-free crude glycerin according to Example I and 15 g of CaCO ₃ at 105 °C. With slight carbon dioxide release, the viscosity of the mixture increased noticeably based on the slowing down of the mixer and the need for higher speed mixing.

To the partially hardened mixture, 120 g of sifted sunflower shell powder and 50 g of wax were added. The mixture was stirred for 10 minutes. The 80°C mixture was poured into a 30 mm diameter paper cone and allowed to cool. After 2 hours, the paper cone was heated with a heat gun so that the wax cylinder could slide out of it.

We cut 2 cm pieces from the slipped wax cylinder and lit them in a porcelain cup to determine the ash content. The solid fuel burned evenly without splashing, at a flame temperature of nearly 800 °C (measured with an infrared thermometer). The amount of ash remaining was 8.6%.

III.

The solid material of Example 11 was chopped and 250 g of it was stirred in a 1000 ml beaker with a magnetic stirrer at 90°C, then 30 g of filler powder with a particle size smaller than 0.1 mm was added to the mixture.

The hot mixture was poured into a 25 mm diameter polyethylene bag. 150 mm long fuel shapes were formed by twisting the ends of the bags. The twisted loops were cooled under water, then the surface of the cold loops was roughened and cut into 2 cm circles.

The flame temperature in the porcelain cup was nearly 750 °C, and the residual ash content (annealed to constant mass at 775 °C) was 9.3%.

ARC.

The solid material of Example 11 was chopped and 20 g of it was stirred in a 600 ml beaker with a magnetic stirrer at 85 °C, then 25 g of carbon powder was added to the mixture.

The hot mixture was poured into a 25 mm diameter polyethylene bag. 150 mm long fuel shapes were formed by twisting the ends of the bags. The twisted loops were cooled under water, then the surface of the cold loops was roughened and cut into 2 cm circles.

The highest flame temperature measured in the porcelain cup was 837 °C, and the residual ash content (annealed to constant mass at 775 °C) was 9.7%.

Claims (8)

Patent claims: 1. A solid fuel with reduced ash content, characterized in that 1-3 parts (typically 1-1.5 parts) of sunflower oil extraction hulling material stream are mixed with 0.5-1 part (typically 0.5-0.75 parts) of biodiesel by-product glycerin phase, 0.005-0.01 parts of CaCOa, and 0.5-2.5 parts (typically 0.5-1 part) of microcrystalline wax at 80 °C, and then the almost solidified mixture is filled into a polyethylene bag at 60-80 °C. 2. The method and solid fuel according to point 1, characterized in that instead of microcrystalline wax, a hydrocarbon gelled with CaCCh or other inorganic gelling agent, typically vacuum light fraction, non-standard biodiesel or macrocrystalline wax, or gacs/petrolatum oil is used, characterized in that typically, but not exclusively, the soap components of the biodiesel glycerin phase are also utilized in the fat cooking. 3. The method and solid fuel according to point 1, characterized in that the diameter of the bag is 1-100, typically 5-8 mm. 4. The method and solid fuel according to point 1, characterized in that the bag material is pierced with a needle after cooling, in order that after being placed on fire, the microcrystalline wax melts and flows out of the bag and ignites the solid fuel component. 5. To the composition stated in point 1, 1-3 parts of briquette production, coal transportation, and petroleum coke waste powder components are optionally mixed before filling the bag. 6. To the composition stated in point 1, optionally mix 1-3 parts of sawdust or finely chopped carpentry waste before filling the bag. 7. To the composition stated in point 1, a mosquito repellent component known for open-air application is mixed in the amount according to the manufacturer's instructions. 8. To the composition stated in point 1, we mix in any quantity of pressed oil cake with an oil content of 7-20, typically 7-15%, or a refining by-product mixed with sawdust in a maximum of 0.2-0.3 parts.