BR102017004823A2 - synthetic fuel and mixtures for automotive use, diesel formulation s 500 and s 10 derived from municipal solid waste and or biomass by catalytic depolymerization process. - Google Patents

Abstract

for the improvement of the environment by eliminating dumps and landfills in brazil and helping the country achieve its renewable fuel production goals, it refers to the catalytic depolymerization process (kdv, cfc, cpd) for rsu and / or biomass treatment with the addition of plastics, petroleum hydrocarbon derivatives and / or waste oils to improve cetane and decrease sulfur for the production of synthetic or second generation diesel the quality of synthetic diesel produced and also the mixtures of petroleum derived diesel and biodiesel and its additives for the production of s500 and s10 quality synthetic diesel with a material energy efficiency (kcal) of the order of 80% from rsu.

Description

(54) Title: SYNTHETIC FUEL AND ITS MIXTURES FOR AUTOMOTIVE USE, FORMULATION OF DIESEL S 500 AND S 10 DERIVED FROM URBAN SOLID WASTE AND OR BIOMASS BY THE CATALYTIC DEPOLIMERIZATION PROCESS.

(51) Int. Cl .: C10B 53/00; C10B 53/07; C10B 53/02; 1/10 C10G; C10G 3/00 (73) Owner (s): ENRIQUE EDUARDO ORMEZZANO ENRIQUE ORMEZZANO, CONPROL CONSTRUÇÕES E PROJETOS LTDA.

(72) Inventor (s): ENRIQUE EDUARDO ORMEZZANO (85) Start date of the National Phase:

10/03/2017 (57) Abstract: To improve the environment by eliminating dumps and sanitary landfills in Brazil and helping the country to achieve renewable fuel production goals, it refers to the catalytic depolymerization process (KDV, CFC , CPD) for treatment of MSW and or residual biomass with the addition of plastics, petroleum hydrocarbon derivatives and or residual oils to improve cetane and decrease sulfur for the production of synthetic or second generation diesel the quality of the synthetic diesel produced and also mixtures of petroleum-derived diesel and biodiesel and their additives for the production of synthetic diesel with quality of S500 and S10 with an energy yield (kcal) of the material of the order of 80% from the MSW.

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SYNTHETIC FUEL AND ITS MIXTURES FOR AUTOMOTIVE USE, «FORMULATION OF DIESEL S 500 AND S 10 DERIVED FROM SOLID WASTE%, URBAN AND OR BIOMASS BY THE CATALYTIC DEPOLIMERIZATION PROCESS.

01. Renewable fuel industrial sector.

02. The present invention refers to the use of synthetic fuel and its mixture for automotive use, diesel derived from the residue for the production of diesel S500 and S10.

03. The adequacy of the synthetic fuel produced by the catalytic depolymerization process for diesel S500, S10, SB500 and SB10 and other fractions. Diesel S-10, which contains a very low sulfur content of 10 milligrams for every 1,000,000 milligrams of the product (10 parts per million), replaced the Diesel S-50.

04. Petroleum Diesel Oil is a fuel derived from petroleum and consists basically of hydrocarbons (organic compounds that contain carbon and hydrogen atoms). Some compounds present in diesel, in addition to having carbon and hydrogen, also have sulfur and nitrogen. Diesel is normally a "heavier" fuel than gasoline and has a carbon chain of 6 to 30 atoms.

05. The composition of diesel oil includes paraffinic, olefinic and aromatic hydrocarbons. Produced from petroleum refining, diesel oil is formulated by mixing various currents such as gas oils, heavy naphtha, light diesel and heavy diesel, from the various stages of processing crude oil. The proportions of these components in diesel oil are those that make it possible to fit the final product within the previously defined specifications and that are necessary to allow a good performance of the product, minimizing the wear of engines and components and maintaining the emission of pollutants, generated in the burning of this acceptable levels.

06. Types of diesel oil: Currently, four basic types of diesel oil are defined and specified by the National Fuel Department-DNC: A, B, C, and D. Below, some information about these types of diesel: Type A - It is diesel oil used in diesel cycle engines (buses, trucks, trailers, utility vehicles, etc.) and in small heating installations. This oil is available in all regions of Brazil and is characterized by having a sulfur content of, at most, 1.0%.

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Type B - It is the diesel oil known as “metropolitan”. It has the same application as diesel type A ^10, differing from it in that it has a maximum of 0.5% sulfur and because it is currently only commercialized for use in the metropolitan regions of the following capitals: Porto Alegre, Curitiba, Rio de Janeiro, Belo Horizonte, Recife and Fortaleza.

Type C - This type of diesel oil is mainly characterized by having, at most,

0.3% sulfur. Another item that differentiates this type of diesel from the others is the temperature required for the distillation of 85% of its volume: 360 ° C against 370 ° C for the other types. This oil has been available since October 1, 1996, when it was made available by PETROBRAS for use in the metropolitan areas of Salvador, São Paulo, Aracaju, Santos and Cubatão. From October 1997, this type of diesel will be available for use in the metropolitan areas of Fortaleza, Recife, Rio de Janeiro, Curitiba, Porto Alegre, Belo Horizonte, Belém, Campinas and são José dos Campos.

Type D - It is marine diesel oil. It is specially produced for use in marine vessel engines. It differs from Type A diesel in that it has specified its flash point at a maximum of 60 ° C.

07. Additive Diesel Oil:

In addition to the basic types of diesel oil previously presented, diesel fuel with additives is available at some service stations. These are types A, B or C diesel oil, which, after leaving the refinery, receives an additive from distributors that aims to give the product better performance characteristics. At least these additives have demulsifying, antifoam, detergent, dispersant and corrosion inhibitor properties.

08. With these characteristics provided by the additives, diesel is prevented from forming an emulsion with water, which, when it occurs, hinders its separation from the product and prevents its drainage. It is also intended to allow fast and complete filling of vehicle tanks (which was previously hindered by the generation of foam), to keep the fuel system and combustion chamber clean, increasing engine life and minimizing emissions of pollutants. In addition to these benefits, one of the additives (the corrosion inhibitor) minimizes the corrosion of the vehicles' storage tanks and fuel tanks.

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09. Cetane improver (used in diesel)%

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The cetane number of a fuel oil corresponds to the volumetric percentage of cetane and alpha-methylnaphthalene contained in that oil. This index is a key measure of the combustion quality of diesel fuels and is related to the ignition speed (the period between the start of fuel injection and the start of combustion). Good quality combustion occurs with rapid ignition followed by smooth and complete combustion of the fuel. Fuels with a low cetane number have a slow ignition and then a very fast combustion, which leads to an increase in pressure levels. The cetane-improving additive is a compound that self-ignites at a temperature lower than that of diesel, acting as a combustion catalyst and making it smoother and more complete, improves combustion, reduces noise, reduces vibration, reduces smoke, reduces pollutant emissions and improves cold start.

10. Defoamer (used in diesel)

They are agents that prevent and reduce the formation of foam during the time of filling, allowing this operation to be done in a more appropriate and quick way. The reduction of the foam formed by the entry of air into the diesel is achieved through a compound that reduces the surface tension of the diesel. Benefits: Prevents spillage of diesel into the soil, ensures full tank filling.

11. Multifunctional additive for diesel mixes with dispersing properties: the main component is 0 to 40% octyl nitrate.

12. Some quality characteristics of diesel oil - aspect: It is a test that allows you to have a quick visual indication of the quality and even identify a contamination of the product. The diesel must be clear and free from suspended materials such as dust, rust, water, etc. These contaminants, when present, can reduce the useful life of the filters in vehicles and equipment and impair the operation of the engines. The test is performed by observing, against natural light, a 0.91 sample of the product contained in a transparent glass container with a total capacity of 1 liter. The presence of free water or solid materials is not observed and, since the product is clear, the product is considered to have passed this test.

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13. Sulfur content

It is indicative of the concentration of this element in the oil. Sulfur is an undesirable element in any fuel due to the corrosive action of its compounds and the formation of toxic gases such as SO2 (Sulfur Dioxide) and SO3 (Sulfur Trioxide), which occurs during the combustion of the product. In the presence of water, sulfur trioxide leads to the formation of sulfuric acid (H2SO4), which is highly corrosive to the metal parts of the equipment, in addition to being polluting. The test is carried out by burning a small amount of sample in specific equipment for this purpose. This burning transforms the sulfur present in oxides that, after being quantified, provide the concentration of total sulfur in the oil. Equipment is also available that perform the analysis by focusing X-rays on a sample of the product, placed confined to a specific ballot. In this case, the sulfur atoms absorb energy of a specific wavelength in an amount proportional to the concentration of sulfur present in the diesel.

14. Percentage of water and sediment

It is a measure of the water content and other contaminants that are suspended in the product and that settle during the test. The presence of these contaminants at levels higher than those preset, are highly harmful to diesel, as they impair its combustion in addition to accelerating the saturation of the filters and causing damage to the fuel system. In the storage system these contaminants tend to be deposited on the bottom of the tanks and, if water is present, favor the deterioration of diesel by the development of bacterial colonies. The test is performed by centrifuging, in a test tube, 50 ml of the sample mixed with an equal amount of a solvent (toluene). At the end, read the layer of water and sediment present at the bottom of the tube and then calculate the percentage of water and sediment in relation to the sample taken.

15. Care to preserve the quality of diesel oil during storage:

After receiving diesel oil in its storage tanks, some care must be taken to preserve its characteristics, avoiding expenses greater than necessary with the maintenance of both the storage tanks, as well as vehicles and equipment.

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16. Avoid the presence of water in the diesel: The water that appears in the dicsel may come from the condensation of moisture in the storage tanks, from the entry of rainwater, from sabotage, improper handling, accidental contamination or from the contamination itself production process. Water, if present in the diesel oil storage tank, leads to the development and multiplication of colonies of microorganisms (bacteria, fungi and yeasts) that feed on diesel generating a material with a brown or dark mud aspect, which it calls it is made of sludge and consists of colonies of bacteria and corrosion product in the tanks. In addition to sludge, organic acids, alcohols and ethers are generated.

Chemical products formed by microorganisms (acids, alcohols, esters, etc.), in addition to causing corrosion in storage tanks, stabilize the emulsion between water and diesel. Diesel, with these substances is deteriorated and has a strong and sour smell. The emulsified water in this condition is difficult to separate in the coal-filtering filters (primary filters). In this way, contaminated diesel reaches the fuel system, damaging it by corrosion.

17. Avoid diesel aging: Diesel oil oxidizes and degrades. The use of fuel in this condition can cause clogging of vehicle filters, wear of the injection pump and clogging of the burner nozzles, when the product is used for firing.

18. To prevent the aging of diesel, take the following precautions: do not store diesel for a long time, long-term storage favors contamination and aging of the product due to its natural oxidation. This oxidation leads to the formation of sediments of chemical origin and they change the color of the diesel, they dirty the filters of the vehicles and they clog the nozzles of the furnace and boiler burners.

19. Do not use containers, connections, valves, screens, filters or copper, bronze or brass tubing: The contact of diesel with copper or its alloys accelerates its degradation, which is due to the complex chemical reactions that occur between the constituents of the product. This accelerates the change in the color of the product and leads to the formation of sediments that clog the filters of the vehicles and increase the formation of deposits in the engine.

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20. Do not leave diesel exposed to high temperatures: Diesel, if exposed to high temperatures (above room temperature) when stored or even stopped /. in pipes, it “ages” more quickly, generating sediments that, as we have seen, create problems during use.

21. Diesel oil, in its various denominations, is the main fuel sold in the Brazilian market, used in the transportation of cargo and passengers, in vessels, in industry, in power generation, in construction machinery, in agricultural machinery and locomotives, meeting the needs of consumers and the most advanced technologies in engines and combustion.

22. Production and sale of diesel oil in the fuel distribution market for applications defined in accordance with the specifications of the National Agency of Petroleum and Bio-fuels (ANP).

23. Additives and their benefits: Detergent / dispersant: the detergent function reduces the formation of deposits in the injection system, prevents the increase in consumption and emissions during use; The dispersant function, on the other hand, avoids the agglomeration and precipitation of insoluble particles. Benefits: better combustion; greater engine durability (low formation / less waste accumulation); more spaced maintenance (reduction of maintenance costs); improving air quality, reducing the emission of polluting gases; increase in the life of the filtration system.

24. Anti-Corrosive: prevents corrosion of the metallic parts of the fuel system, transfer lines and tanks due to the possible presence of water. Benefit: protection of the engine against corrosion.

25. Anticspumantc: reduces the formation of foam during the time of filling, allowing this operation to be done in a more appropriate and faster way, avoiding the loss of tank volume with the foam that would be formed.

26. Demulsifier: avoids water emulsion, which improves the process of draining and cleaning the storage tank system.

27. Diesel Characteristics: Colorless to yellowish, if S-10 diesel (10 ppm sulfur), and reddish, if S500 diesel (500 ppm sulfur). Differentiated coloring is a measure to prevent diesel with a higher sulfur content from being ^ ^ô3de

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marketed as S-10 diesel; The product has a cetane number of at least 42 ie /

O 'S-500 diesel, and at least 48 if S-10 diesel; The use of S-10 diesel (with or without additives) is mandatory for vehicles produced since January 2012; Vehicles produced until December 2011 will be able to use diesel with 500 ppm of sulfur (additive or not) or S-10 diesel (additive or not).

28. Diesel S-10 contains the equivalent of a maximum sulfur content of 10 milligrams for every 1,000,000 milligrams of the product (10 parts per million), it is suitable for the new emission control technologies of the new diesel engines manufactured as of 2012. It makes it possible to reduce emissions of particulate matter by up to 80% and nitrogen oxides by up to 98%. It also has a cetane number 48 (diesel combustion quality measure), offering any vehicle, even those manufactured before 2012, better engine conservation and reduced maintenance costs.

29. Diesel S-500: The automotive diesel oil S-500 is so called because it contains 500 mg / kg or ppm (parts per million) of maximum sulfur content, being known in service stations as common diesel and are suitable for many fleet of diesel vehicles manufactured before January 1, 2012.

30. Biodiesel is a biodegradable fuel derived from renewable sources, which can be obtained by several processes. It can be produced from animal fats or vegetable oils, with dozens of plant species in Brazil that can be used, such as castor, palm oil, sunflower, babassu, peanuts, jatropha and soy, among others. Its use totally or partially replaces diesel oil in engines for trucks, tractors, automobiles, electricity and heat generators, among others. It can be used pure or mixed with diesel in different proportions. The current blend of biodiesel in the Brazilian market is 7% to petroleum diesel, ο B7. Pure biodiesel is called BI00.

This product meets the specifications of the National Agency of Petroleum, Natural Gases and Fuels (ANP), suitable for the Brazilian market, with different equivalences for other countries.

31. Diesel oil with additives and a product aimed at the diesel consumer market, mainly in large metropolises, provides the following benefits: Reduction of

8/11 consumption up to 3.0%, due to the better quality combustion provided by the additives present in the product; Reduction of foam formation during the supply process, resulting in greater productivity; Protection of the injector system against corrosion, thanks to the anti-rust additive; Lower black smoke emission and lower maintenance cost with your fleet; Important auxiliary product for those wishing to pass CONTROLAR inspections, provided it is used regularly.

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This product means higher yield, less consumption, longer life of the injector system and less environmental impact. It serves all Diesel Oil consumers for vehicle or stationary engines. It represents a cutting edge product, suitable for companies that are certified or intend to be certified by the ISO 14.000 standard.

Synthetic fuel and its characteristics

Analysis of Fuel derived from biomass, wood residues and miscanthus.

Distillation - ° C 178.2 ± 3.9 10% recovered 207.8 ± 3.0 50% recovered 275.7 ± 4.0 85% recovered 296.4 ± 4.4 90% recovered Total sulfur - mg / kg 214 to 522 cctane index 40.3 to 42 Specific gravity at 20 ° C - kg / m ' 826.0 ± 0.5

Source: IPT, PETROLAB gmbh.

32. As a measure to improve the quality and characteristics to produce a diesel for automotive use, it was changed in the process of catalytic depolymerization with the addition of plastic to improve cetane and the reduction of sulfur was added 20% of materials based on plastic, nylon, rubbers and other petroleum products.

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Analysis of diesel derived from biomass and plastic.

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Distillation - ° C 250 ° C 46.7 330 ° C 85.0 350 ° C 95.0 Total sulfur - mg / kg 0.012 cetane number 47.5 to 52 Specific mass at 20 ° C - kg / m ³ 841.0

Source: PETROL d.d., Ljubljana LABORATORIJ PETROL

33. The CDR of solid urban waste (MSW) and the ideal material for the production of synthetic diesel by the content of various plastics, rubbers and other derivatives of petroleum hydrocarbons between 30% and 50% benefiting the increase of cetane by 10% or more and decreasing the sulfur, also the addition of pyrolysis oil, fried oil, used engine oil and other lees increase the cetane content in diesel improving its ignition and diesel quality.

34. The addition of sodium carbonate, sodium hydroxide, hydrated lime and or calcium carbonate to replace other process agents significantly reduces the amount of sulfur in the diesel, thus making it a fuel with low sulfur levels, improving the hydrodesulfurization and thus reducing the costs of operating the process.

35. Of the mixtures, the diesel produced by the catalytic depolymerization process (KDV, CFC, CDP) can be used in various dosages with biodiesel and or petroleum diesel as well as the use of various additives to keep the fuel within the parameters required by the legislation of the In this sector, substances called cetane improvers are being used, which are those capable of acting on the deficiency of fuel cetanage and making them suitable for use in diesel cycle engines.

36. Among synthetic antioxidants, phenolic antioxidants, derived from phenol, have been the subject of extensive studies and application as additives in biodiesel, being already widely used as additives in petrodiesel and lubricants. These substances are characterized by being non-corrosive, containing no acids and being highly soluble in biodiesel.

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These antioxidants contain only oxygen, hydrogen and carbon. Many of the antioxidants have multiple mechanisms of action such as propylgalate (PG). Other examples of antioxidants derived from phenol are butylhydroxyanisole (BHA), butylhydroxytoluene (BHT), 2,5-di-tert-butylhydroquinone (DTBHQ), tert-butylhydroquinone (TBHQ) and pyrogallol (PY).

37. Commercial Antioxidants: The commercial antioxidants Baynox and Baynox Plus, marketed by Lanxcss, have butylhydroxytoluene (BIIT) as their active substance. This is present in Baynox in a percentage of 99.8%, according to the technical data provided by this company. Baynox Plus is referred to as an improved formula from the previous one, referred to as “Bis-BHT”, and specially developed for biodiesel that has a high content of methyl linoleate (Cl8: 2), such as, for example, biodiesel obtained from from soy oil. Kerobit TP 46 from Basf also has butylhydroxytoluene (BHT) as its active substance.

38. Nitrates and organic peroxides are the most effective cetane enhancers. Of these, the most used are 2-ethylhexyl nitrate, which dominates the market for cetane improvers, and di-t-butyl peroxide, octyl nitrates. Biomass-based additives:

2-nitrate-1,3-di (isobutoxy) propane (NIBP), 2-nitrate-1,3-di (isopentoxy) propane (NIPP), 2-nitrate-1,3-di (octanoxy) propane (NOP) , isoamyl nitrate (NIA), isosorbide dinitrate (DNIS), tetrahydrofurfuryl nitrate (NTHF), obtained from different starting materials, derived from the use of biomass. The prepared nitrates were obtained with excellent yields. The test carried out in IQT-LM showed that the nitrates synthesized are efficient cetane improvers, more efficient than EHN (additive most commercialized worldwide), with the ability to vary the number of cetane in the base diesel by up to 10 units.

39. Other commercial additives: Xp3, Actioil A550, Teccom and Reformul, etc.

REFERENCES

Patent: PI 0400912-6 BI Process for the production of diesel oil from residual substances and device for the execution of the process.

Patent: DE 10049377 C2 Catalytic production of diesel oil and gasoline from hydrocarboncontaining waste oils and oils.

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Patent: DE 102005056735 B3 - Preparation of diesel oil from hydrocarbon containing

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- The # 'residual substances in an oil circulation with solid separation and product distillation, comprises providing heat through main energy carriers by one or more high speed mixing chambers.

Patent: DE 102012022710 B4 Method and apparatus for remote mobile processing of Petroleum, coal, grecn waste and recyclcd waste to middle distillates and low-sulfur, anhydrous annealing coal with mixturc turbines.

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Claims (2)

01. Synthetic fuel and mixtures characterized by using the catalytic depolymerization process (KDV, CFC, CPD) to treat MSW and or residual biomass with the addition of plastics, derivatives of petroleum hydrocarbons and residual oils to improve the quality of synthetic diesel produced and also mixtures of diesel derived from petroleum and biodiesel and their additives for the production of synthetic diesel with S500eS10 quality. 02. Synthetic fuel and its mixtures characterized by adding substitutes for additives from the catalytic depolymerization process such as Ca and Magnesium, with sodium carbonate, hydrated lime and or calcium carbonate and or sodium hydroxide in proportions from 0.00% to 100% and thus decreases sulfur and chlorine by producing a crystalline NaCl and Na2SO4 salt fixed in the process residues (ash) and thus improving the quality of synthetic diesel. 03. Synthetic fuel and its mixtures characterized by the catalyst Alumino Silicate Sodium added in proportions from 0.00% to 100% the raw material RSU or biomass accelerating the process of breaking the molecules of the material, catalyst Alumino Silicate Sodium in proportions Alumina 0.00% to 100%, silicates 0.00% to 100% and sodium 0.00% to 100%. 04. Synthetic fuel and mixtures characterized by using the MSW after its treatment and dehydration with a content of 0.00% to 20% humidity, with a composition of plastic material and hydrocarbon derivatives from 0.00% to 100% in catalytic depolymerization processes (KDK, CFC, CDP), thus improving the quality of synthetic diesel with the ability to vary the number of cetane in the base diesel by up to 10 units. 05. Synthetic fuel and mixtures characterized by the addition of residual oils in the catalytic depolymerization process to improve the quality of synthetic diesel as used engine oil from 0.00% to 100%, frying oil from 0.00% to 100 %, fuel sludge from 0.00% to 100%, pyrolysis oil 0.00% to 100%, residual glycerin from the biodiesel production process and electric transformer oil 0.00% to 100%. 2/2 ^ ade, Φ ^{F f} .: » 06. Synthetic fuel and its mixtures characterized by synthetic diesel%% - U. ·> with petroleum diesel 0.00% to 100% and biodiesel 0.00% to 100%. Φ? _ 07. Synthetic fuel and its mixtures characterized by mixtures with the different additives Commercial Antioxidants: The commercial antioxidants Baynox and Baynox Plus, marketed by the company Lanxess, have butylhydroxytoluene (BHT) as their active substance, this is present in the Baynox in a percentage of 99.8%, according to the technical data provided by this company, Baynox Plus is referred to as an improved formula from the previous one, referred to as “Bis-BIIT”, and specially developed for biodiesel that has a high content of methyl linoleate (C18: 2), such as, for example, biodiesel obtained from soybean oil, Kerobit TP 46 from Basf also has butylhydroxytoluene (BHT) in the proportion of 0.00% to 100 % for each separate additive mentioned here. 08. Synthetic fuel and its mixtures characterized by, mixtures with different additives to improve cetane in synthetic diesel, nitrates and organic peroxides are the most effective cetane improvers, of these, the most used are 2-ethylhexyl nitrate, which dominates the market for cetane improvers, and di-t-butyl peroxide, octyl nitrates, biomass additives: 2-nitrate-1,3-di (isobutoxy) propane (NIBP), 2-nitrate-1 , 3-di (isopentoxy) propane (NIPP), 2-nitrate-I, 3-di (octanoxy) propane (NOP), isoamyl nitrate (NIA), isosorbide dinitrate (DNIS), tetrahydrofurfuryl nitrate (NTHF), obtained from different starting materials, derived from the use of biomass, the prepared nitrates were obtained with excellent yields, the test carried out in 1QT-LM allowed to verify that the synthesized nitrates are efficient cetane improvers, more efficient than EHN (additive most commercialized worldwide), other commercial additives Xp3 , Actioil A550, Tcccom and Reformul, with the ability to vary by up to 10 units the cetane number of the base dicscl in the proportion of 0.00% to 100% for each separate additive mentioned here. 1/1